tag:blogger.com,1999:blog-19719367385936062532024-03-13T14:04:20.498-04:00Tree Town ChemistryScience news, perspectives, and opinions with a focus on student views. Twitter: @treetownchemJimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.comBlogger45125tag:blogger.com,1999:blog-1971936738593606253.post-977458847975461222016-03-14T15:18:00.000-04:002016-03-14T19:49:06.078-04:00Editorial: What's the Point of Organic Chemistry Education?On Monday, the American Chemical Society National Meeting hosted a presidential symposium entitled "Is There a Crisis in Organic Chemistry Education?" This is a provocative question that has been floating around the community of chemistry educators for some time.<br />
<br />
The panel of presenters consists mostly of representatives for academic publishers like Elsevier and McGraw-Hill, and their 15-minute talks focused on what their respective companies are doing to innovate and enable learning in new ways for students. From the publishing perspective, changes in curriculum seem motivated by changes in the assessment of that curriculum - namely, standardized tests like the GRE and MCAT which are used as metrics for admission into more advanced degree programs.<br />
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The audience, however, seemed to consist mostly of academics and educators largely responsible for teaching the content. The symposium concluded with a panel-style discussion between the presenters and the audience in which audience members picked brains, voiced concerns, and shared experiences regarding organic chemistry instruction. But the symposium's central question never really got answered.<br />
<br />
Instead, the discussion between the panelists and attendees revealed a bit of a gray area on what the purpose of the organic chemistry course is or, perhaps, should be. Is it to prepare pre-meds for medical school and increase their MCAT scores? Is it to prepare chemistry students for graduate education? Is it to challenge them with a new way of thinking? Do we actually anticipate that students will remember the intimate details of reactivity presented in organic chemistry classes two or three years later? Should we have one or two semesters - or more?<br />
<br />
The comments exchanged between panelists and audience members suggested that all of these purposes are at play. One audience member with over thirty years of experience in teaching actually surveyed medical schools and asked why they even require organic chemistry. According to him, the most insightful reply he received was that organic chemistry tends to be the first time that students are forced outside of their comfort zone. Contrasted with general chemistry, which is very algebraic, organic chemistry introduces the language of molecular architecture.<br />
<br />
Another audience member corroborated, adding that organic chemistry forces students to develop spatial reasoning and study habits that they did not need to get by in previous courses. She actually claimed that these skills were the most important take-aways from an organic chemistry course.<br />
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To me, the discussion suggested that individual academics and publishers may approach organic chemistry with different goals or different sets of goals in mind. Maybe, in the quest to optimize organic chemistry courses to best serve students, organic chemistry educators need to come to a consensus on what particular way students are best served. For example, if the goal is truly to introduce foreign concepts of molecular architecture, should courses cover a more narrow scope of reactions and functional groups to make more time to hammer that concept home?<br />
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The question isn't only important to academics. Publishers are essentially communicators of scientific education materials, and the first step in any effective communication is sitting down and deciding what the goal of that communication ought to be.<br />
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Is there a crisis in organic chemistry education? I don't know. But what I did see during the presidential symposium was an opportunity for publishers and educators to work more closely on refining organic chemistry education's identity and the goals it seeks to accomplish.Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com3tag:blogger.com,1999:blog-1971936738593606253.post-63919538285830098772016-02-04T17:27:00.000-05:002016-02-05T16:18:57.325-05:00Oxygen's Alchemical Origins: The Phlogiston StoryToday, everybody knows about oxygen. We know that it fuels fires and keeps us breathing. It seems to us one of the most basic elements of life, ubiquitously available, irrefutably present. Oxygen is obvious.<br />
But it wasn't always.<br />
<br />
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<tr><td style="text-align: center;"><a href="https://1.bp.blogspot.com/-cEbbJf7S5Do/VrPG3IJvnnI/AAAAAAAAAi8/z-S7nfQaQoQ/s1600/2360656061_6a8b5a9be1_o.jpg" imageanchor="1" style="clear: left; margin-bottom: 1em; margin-left: auto; margin-right: auto;"><img border="0" height="232" src="https://1.bp.blogspot.com/-cEbbJf7S5Do/VrPG3IJvnnI/AAAAAAAAAi8/z-S7nfQaQoQ/s320/2360656061_6a8b5a9be1_o.jpg" width="320" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">Maybe you would have liked chemistry a little more<br />
if your book looked like this. <a href="https://www.flickr.com/photos/bibliodyssey/2360656061">Photo credit</a>: Paul K./flickr.com</td></tr>
</tbody></table>
Let's rewind the clock to the late 1660's, when chemistry texts still looked like spellbooks. At that time, the practice of chemistry was still very much rooted in alchemy - a rich mixture of science, occultism, and superstition. In his 1667 publication of <a href="http://gallica.bnf.fr/ark:/12148/bpt6k84226t/f1.item"><i>Physica Subterranea</i></a>, German alchemist Johann Joachim Becher outlined the theory of a fundamentally flammable element called <i>terra pinguis</i>. Substances that burned easily in air, like oils, waxes, and metals, were rich in <i>terra pinguis</i>. Becher's theory was taken up again and refined in the early 1700s by Georg Ernst Stahl, who renamed <i>terra pinguis</i> to phlogiston (from Greek, "burning up").<br />
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<i><b>Phlogiston Basics</b></i><br />
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What Becher and Stahl observed was that many objects burned readily in air. The substances left behind by that burning were not flammable themselves. Ash leftover from a campfire, for example, can't be reignited. When metals burn, a solid and sometimes brightly colored substance is left behind with completely different properties than the original metal. At the time, the leftover substance was called a calx. Interestingly, Becher and Stahl observed that when flammable objects were burned in a closed container, they burned incompletely and the flames eventually guttered out. If the air from that container was reserved and a new flammable object was inserted, a new fire couldn't be started.<br />
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These observations form the basis of phlogiston theory. Flammable materials and metals are said to be rich in phlogiston, a fundamental element that conferred the properties of fire onto a substance. When a phlogisticated substance is burned in ordinary air, the phlogiston gets released and absorbed by the surrounding air, leaving behind ash or calx that has spent all of its phlogiston and can not therefore be reignited. The theory explains the closed contained observation by postulating that the air can only absorb so much phlogiston, at which point it is fully phlogisticated and can support no more combustion.<br />
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<tr><td style="text-align: center;"><a href="https://3.bp.blogspot.com/-vTROf4mvAYE/VrOd5UyMHNI/AAAAAAAAAio/buOyErf0SoU/s1600/phlogiston.PNG" imageanchor="1" style="margin-left: auto; margin-right: auto;"><img border="0" height="248" src="https://3.bp.blogspot.com/-vTROf4mvAYE/VrOd5UyMHNI/AAAAAAAAAio/buOyErf0SoU/s400/phlogiston.PNG" width="400" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">A cartoon of metals before and after burning, according to phlogiston theory.</td></tr>
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<i><b>That Pesky Mass Problem</b></i><br />
<br />
Stahl popularized phlogiston theory and it became the dominant paradigm for explaining combustion in alchemical circles. Phlogiston was associated with the matter of heat and light - a physical stubstance that was transferred whenever and wherever heat or light were transferred. However, there was a small problem: nobody could agree on whether phlogiston had mass. Some measurements showed phlogiston to have mass, and others showed it to have no mass or even negative mass. How could a substance have negative mass? <br />
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It is here that a somewhat underappreciated <a href="http://blogs.scientificamerican.com/the-curious-wavefunction/chemistry-galisonian-rather-than-kuhnian/">tool-driven revolution</a> comes in. When phlogiston theory was first proposed, the vessels used to house closed container combustion reactions were not very sophisticated. They allowed gases to escape, and if those gases were lighter than air their mass would not be detected by a balance. The gas exchange would have made determining the mass of phlogiston impossible even if it had been the correct explanation for observed phenomena. In the 100 years or so between the time that phlogiston theory hit the scene and Antoine Lavoisier came around, the apparatus used to make (al)chemical measurements improved in accuracy and precision. Specifically, specially-sealed gas-tight vessels were invented.<br />
<br />
<i><b>Enter Lavoisier</b></i><br />
<br />
Antoine Lavoisier, a French chemist active in the late 1700s, is hailed as a founding father of modern chemistry. Using hermetically sealed vessels and improved balances, he was able to observe two things that really threw a wrench into phlogiston theory. First of all, when metals are burned, the mass of the metal plus the calx is actually more than the metal itself. Secondly, when metals are burned in a sealed vessel, the mass of the vessel plus all of its contents remains unchanged. These two observations require that phlogiston has negative mass, so the mass of the metal calx increases when the phlogiston leaves.<br />
<i><b> </b></i><br />
Additionally, there was the problem of charcoal. It was well known that a metal calx, when exposed to charcoal at high temperatures, would "revivify" and reform the surface of the original metal. According to phlogiston theory, phlogiston had been transferred from the charcoal back to the metal. So far so good - since the metal weighs less than the metal plus its calx, it makes sense that it absorbed the negative-mass phlogiston. However, Lavoisier performed an experiment in which he burned charcoal in a closed container all by itself. The charcoal burns completely and the mass of the container is left unchanged, just as in the case of the metal. But, when Lavoisier measured the density of the air inside the container, he found that it had <i>increased</i> after the charcoal was burned. Some material with a positive mass had united with the air to increase its density. How was that possible if phlogiston, which was known to be present in great quantity in charcoal, had a negative mass?<br />
<br />
Lavoisier showed numerous other inconsistencies in phlogiston theory that centered around the question of mass. Essentially, no formulation of phlogiston theory could justify a phlogiston that was sometimes massless, sometimes had positive mass, and sometimes had negative mass. Instead, Lavoisier posited the existence of oxygen - a positive-mass substance that exists in air, is depleted by combustion reactions, can combine with metals to form calces (metal oxides), and reacts with charcoal to make "fixed air," or carbon dioxide. Oxygen works in many ways as phlogiston's opposite.<br />
<br />
Lavoisier presented his findings to the Royal Academy of Sciences in the 1770s and 1780s, systematically breaking down the entrenched phlogiston theory in favor of his new, more rigorous, less magical ideas. The language of his essays is often impassioned. For example, in <a href="http://link.springer.com/article/10.1007/s10698-015-9220-5"><i>Reflections on phlogiston</i></a>, he says of phlogiston theory, "In this essay, I beg of my readers to shed themselves of all prejudices as far as possible, to see in the facts only what they show, to banish all that reasoning has assumed, to transport themselves to a time before Stahl and to forget for a moment that his theory ever existed, if that is possible."* Additionally, Lavoisier talks about the differences in taste of metals compared to their calces, which will make any practicing scientist cringe - this work is from a time when literally lighting a block of lead on fire and eating the result was a commonplace experiment.<br />
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<i><b>Phlogiston's Legacy</b></i><br />
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Lavoisier went on to become one of the most celebrated names in the history of chemistry, and, of course, we kept the principle of oxygen and still use it to describe the world today. Becher, Stahl, and the others who were instrumental in advancing phlogiston theory were buried in history books along with the theory itself (although <a href="http://www.acs.org/content/acs/en/education/whatischemistry/landmarks/josephpriestleyoxygen.html">Joseph Priestley</a> is still connected with the discovery of oxygen, and others, like <a href="https://en.wikipedia.org/wiki/Antoine_Baum%C3%A9">Antoine Baumé</a>, became famous for other discoveries).<br />
<i><b> </b></i><br />
It's tempting to laugh at phlogiston theory as a relic of a less informed time, but to do so is disingenuous. Scientists and the science they produce are products of their time, and discoveries should always be understood in that context. Although phlogiston theory turned out to be incorrect, it did represent some of the first exploration of what air is actually made of. In trying to learn more about phlogiston, early scientists discovered dephlogisticated or "vital air," which was supercharged air capable of absorbing lots of phlogiston (which we now know to be oxygen-enriched air).<br />
<br />
Vital air was so named because of its ability to promote respiration in animals. In that way, phlogiston theory led scientists to link the processes of combustion (burning carbonaceous materials), calcination (burning metals), and respiration - if all were promoted by vital air, then they must at least be related. Today, we know that respiration and combustion, both of metals and organic matter, are oxidations that release energy by consuming some fuel and combining it with oxygen.<br />
<br />
Does that mean you should start wearing a wizard hat to lab and adjusting your yields for the phase of the moon? Well, I suppose you'll have to take that up with your supervisor.<br />
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*Translated from French: Best, N. W. <i>Foundations of Chemistry </i><b>2015</b>, <i>17</i>, 137-151.<br />
<i>If you're on the right side of the paywall, I highly, highly recommend reading <a href="http://link.springer.com/article/10.1007/s10698-015-9220-5">this article</a>. It was so fascinating for me to get a taste of what chemistry was like that long ago!</i>Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com4tag:blogger.com,1999:blog-1971936738593606253.post-9663962076686372672016-01-13T11:02:00.000-05:002016-01-13T11:16:05.100-05:00Great Blogs by Women in ScienceWhat's the day-to-day like for women in science or engineering?<br />
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I don't know, ask them. They're out there, doing science, living life, and blogging about it.<br />
<br />
For chemistry aficionados, Michelle Francl-Donnay (<a href="http://twitter.com/MichelleFrancl">@MichelleFrancl</a>) at <a href="http://cultureofchemistry.fieldofscience.com/">The Culture of Chemistry</a> has a real knack for finding topics in language, teaching, and politics that relate to chemistry in an exciting way. Raychelle Burks (<a href="http://twitter.com/drrubidium">@DrRubidium</a>) of <a href="http://thirtyseven.scientopia.org/">Thirty-Seven</a> is an analytical chemist who does <a href="http://geekgirlcon.com/diy-science-15-return-of-the-zone/">fantastic outreach</a> in support of increasing STEM's inclusiveness towards women, people of color, and LGBTQ folks. Kat Day (<a href="http://twitter.com/chronicleflask">@chronicleflask</a>) of <a href="https://thechronicleflask.wordpress.com/">the chronicle flask</a> has already called BS on one overhyped health article this year (and blogs a lot of other great chemistry stuff). Beth Haas (<a href="http://twitter.com/belehaa">@belehaa</a>) at <a href="http://bethhaas.me/">Casual Science</a> and Jenny Martin at <a href="https://cubistcrystal.wordpress.com/">cubistcrystal</a> blog their reflections on their careers as chemists and educators, and Anna (<a href="http://twitter.com/Lady_Beaker">@Lady_Beaker</a>) at <a href="https://chemistryintersection.wordpress.com/">Chemistry Intersection</a> is documenting her quest for a Ph. D. Jyllian Kemsley (<a href="http://twitter.com/jkemsley">@jkemsley</a>) covers chemical safety in industry and academia for Chemical & Engineering News's <a href="http://cenblog.org/the-safety-zone/">The Safety Zone</a>. Stephani Page (<a href="http://twitter.com/ThePurplePage">@ThePurplePage</a>) runs the blog <a href="https://blackandstem.wordpress.com/">#BLACKandSTEM</a>. The husband and wife team of Geoffrey and Ruth Bowers (<a href="http://twitter.com/carchemprof">@CarChemProf</a>) is behind <a href="http://www.thechemistryofcars.com/">Understanding Chemistry through Cars</a>, which has a great perspective combining knowledge of the automotive industry with some of its fundamental chemistry. Last, but not least, Carmen Drahl (<a href="http://twitter.com/carmendrahl">@carmendrahl</a>) covers exciting and timely chemistry news at <a href="http://www.forbes.com/sites/carmendrahl/#2715e4857a0b6c5cabd47da0">Forbes</a>.<br />
<br />
There are great blogs covering topics in other areas of science as well. <a href="http://thusspakezuska.scientopia.org/">Thus Spake Zuska</a> (<a href="http://twitter.com/TSZuska">@TSZuska</a>) writes beautifully, relaying stories and perspectives from STEM, politics, personal life, and the areas between. Ulli Hain (<a href="http://twitter.com/ulli_hain">@ulli_hain</a>) at <a href="http://www.scilogs.com/science-extracted/">Science Extracted</a> covers a range of topics in research with an emphasis on ethics. The women of <a href="http://portraitofthescientist.scientopia.org/">Portrait of the Scientist</a> document their lives as they pursue a number of different science and science-adjacent paths.<br />
<br />
Finally, leveling the playing field for women in STEM is an area for activism and outreach as well as personal reflection. <a href="http://www.stemwomen.net/about/">STEM Women</a> (<a href="http://twitter.com/STEMWomen">@STEMWomen</a>) is a team of three scientists who aim to bring female scientists together and increase their visibility to the public through blogs, videos, and other great content. <a href="http://soapboxscience.org/">Soapbox Science</a> (<a href="http://twitter.com/soapboxscience">@SoapboxScience</a>) is a media initiative doing much the same by bringing scientists from around the UK "to the soapbox" to talk about their lives and careers in public presentations. And, unless you just plain hate joy, you've got to follow <a href="http://www.geekgirlcon.com/">GeekGirlCon</a> (<a href="http://twitter.com/geekgirlcon">@GeekGirlCon</a>).<br />
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I originally wanted to put this blogroll together to raise awareness of sexual harassment and sexual assault in scientific workplaces. But here's the whole story on that: it happens. <a href="http://www.npr.org/sections/health-shots/2014/07/17/331737485/young-scientists-say-theyre-sexually-abused-in-the-field">A lot</a>. It happens in <a href="https://www.insidehighered.com/views/2015/07/28/essay-being-junior-professor-campus-where-sexist-traditions-are-form-harassment">lecture halls</a> and <a href="https://www.washingtonpost.com/posteverything/wp/2015/09/11/ive-faced-outrageous-discrimination-as-a-female-oceanographer-i-want-better-for-the-next-generation/">on research cruises</a> and <a href="http://www.forbes.com/sites/janetstemwedel/2015/06/01/advice-to-put-up-with-ogling-adviser-hurts-scientists-and-science/">in meetings</a> and on <a href="http://www.npr.org/sections/health-shots/2014/07/17/331737485/young-scientists-say-theyre-sexually-abused-in-the-field">archaeological digs</a>. It happens to women and scientists of all demographics. Sometimes <a href="http://www.buzzfeed.com/azeenghorayshi/famous-astronomer-allegedly-sexually-harassed-students">it's not a secret</a>. It has almost assuredly happened to someone you know. It's unacceptable, it's repugnant, it <a href="https://theconversation.com/change-is-possible-when-sexual-harassment-is-exposed-48992">needs to stop</a>.<br />
<blockquote class="twitter-tweet" data-partner="tweetdeck">
<div dir="ltr" lang="en">
So don't sit and think smugly "oh, biology is OK! Chemistry is free of sexual harassment! It's just those astronomers!"</div>
— Matthew R. Francis (@DrMRFrancis) <a href="https://twitter.com/DrMRFrancis/status/686934964219310082">January 12, 2016</a></blockquote>
<script async="" charset="utf-8" src="//platform.twitter.com/widgets.js"></script>
The links above are, for the most part, to stories from larger outlets dealing with statistics and responses to well-publicized cases. I wanted to go out and find survivors who have shared their stories, to point out that yes, this happens to real people and it's an intensely personal issue.<br />
<br />
I abandoned that search without having found very much. And of course not, I thought. The stakes of publishing a post like that are too high, the emotions too real, and the internet atmosphere too hostile. In the event an investigation actually does get started, it <a href="https://tenureshewrote.wordpress.com/2015/09/21/title-ix-a-step-by-step-guide/#comments">can be a nightmare</a> for the complainant, and it's too easy to misstep.<br />
<br />
But how about this stunning revelation? Scientists don't <i>want</i> to write about sexual harassment. These women didn't start science blogs so they could write posts about how hostile their work environments are. They didn't sign up to be scientists so that they could be harassed or worse. We - all of us - became scientists because we're fascinated by some aspect of the material or social world and we want to poke it with a stick. That experience is what scientist-bloggers are publishing about.<br />
<br />
Normalizing marginalized voices in our scientific community is critical to achieving equality. Add some of these excellent writers to your feeds. They all speak for themselves.<br />
<br />
<i>Special thanks to Beth Haas, Jyllian Kemsley, Chemjobber, Renee Webster, and the rest of Chemistry Twitter for helping me find all of these bloggers. If you know of someone else that I've left off, feel free to add in the comments.</i>Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com2tag:blogger.com,1999:blog-1971936738593606253.post-88324182334351101432015-11-12T14:51:00.003-05:002015-11-12T15:00:51.652-05:00SLACkers: University of Michigan Chemists Experience Premier Research Facility<br />
<i>The #SciBlogReaders survey is still underway! If you enjoy this blog or another science blog, <a href="http://treetownchem.blogspot.com/2015/10/scientists-surveying-science-blog.html">click here to learn</a> how you can help bloggers and win some cool prizes for yourself.</i><br />
<i> </i> <br />
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<tr><td style="text-align: center;"><a href="http://1.bp.blogspot.com/-09QBeKro27o/VkJtQHquEQI/AAAAAAAAAgY/Up2ToogUl8w/s1600/012.JPG" imageanchor="1" style="clear: left; margin-bottom: 1em; margin-left: auto; margin-right: auto;"><img border="0" height="240" src="http://1.bp.blogspot.com/-09QBeKro27o/VkJtQHquEQI/AAAAAAAAAgY/Up2ToogUl8w/s320/012.JPG" width="320" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">From left to right: Nick Miller, Ted Wiley, and Laura Kiefer,<br />
the graduate students who carried out experiments at<br />
SLAC-LCLS last month.</td><td class="tr-caption" style="text-align: center;"><br /></td><td class="tr-caption" style="text-align: center;"><br /></td></tr>
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Inside an underground tunnel about thirty miles south of San Francisco, electrons scream by at nearly the speed of light. Suddenly, they find themselves jerked back and forth along their mile-long path by magnets. As they veer around turns, they spit out high-energy X-rays that are the light source for one of the most advanced lasers humans have ever built.<br />
<br />
Just another day at the lab.<br />
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The Stanford Linear Accelerator Center, or SLAC, is a nationally funded laboratory dedicated to helping scientists answer fundamentally difficult questions about the matter our universe is made of. At SLAC, the Linac Coherent Light Source (LCLS) is home to one of the world's most advanced X-ray lasers - a billion-dollar device about a kilometer long. What is it like to use an instrument that pushes the boundaries of human technology? A group of University of Michigan researchers found that out for themselves this past October.<br />
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The proposal that took the group to SLAC was headed up by Roseanne Sension, in collaboration with Jim Penner-Hahn and Kevin Kubarych, all professors at the University of Michigan, and with University of Louisville professor Pawel Kozlowski. Nick Miller and Ted Wiley, graduate students in the Sension group, and Laura Kiefer, a student of Kubarych's, traveled out to California to conduct the experiments with their advisors. Also accompanying the group was Aniruddha Deb, a staff scientist in the Penner-Hahn group. <br />
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<tr><td style="text-align: center;"><a href="http://3.bp.blogspot.com/-afTTzaQdXv4/VkTo-io3yAI/AAAAAAAAAg4/0u2Z3dd6pbQ/s1600/001.JPG" imageanchor="1" style="clear: right; margin-bottom: 1em; margin-left: auto; margin-right: auto;"><img border="0" height="320" src="http://3.bp.blogspot.com/-afTTzaQdXv4/VkTo-io3yAI/AAAAAAAAAg4/0u2Z3dd6pbQ/s320/001.JPG" width="240" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">Nick Miller in one of SLAC-LCLS's long,<br />
long, <i>long</i> hallways. Image credit: Laura Kiefer</td></tr>
</tbody></table>
<br />
While that might seem like a large group for a science experiment, the shared pool of expertise was instrumental for the group's success. "Each member of the team had something to contribute that the other members didn't know that much about, so it strengthened the proposal," said Wiley. These experiments will make up a large part of his and Miller's theses.<br />
<br />
The application process is very competitive. The group found out in June that the proposal, titled "Investigating Structural Changes in Short-lived Excited States of Vitamin B12," had been accepted and that they would be making the trip. During the time between that and their October 14 start date, they planned for lodging, and also went through several online training modules not unlike what would be required of new employees at any lab. "It's a government lab, so it's under a lot of scrutiny," said Wiley. "So, you know, you have to be able to use a stepladder correctly."<br />
<br />
There were a few more training modules on-site at SLAC-LCLS. Then, the marathon began.<br />
<br />
The group performed measurements between 9 PM and 9 AM for four straight days. "You get delirious on the night shift," said Kiefer. But no time could be wasted. Although the expenses for the actual measurements are paid by grants from the United States Department of Energy, the bill is extremely high - to the tune of tens of thousands of dollars per hour. "So we got to this point where we were just goofing off, talking, and it was like, 'It's eleven dollars a second for you to say that!'" Wiley recalled of the late night experiments.<br />
<br />
The technique the group used is called X-ray pump-probe spectroscopy. The measurement involves "pumping" the sample with a green laser, putting it into an electronic excited state. Then, a pulse of X-ray light, the "probe," comes in, allowing the experimenter to measure the X-ray absorption spectrum of an electronically excited molecule. "These experiments weren't possible a few years ago," notes Wiley.<br />
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<tr><td style="text-align: center;"><a href="http://1.bp.blogspot.com/-a2HnfP13jdQ/VkTpBArYyNI/AAAAAAAAAg8/ICotecW8rfI/s1600/002.JPG" imageanchor="1" style="margin-left: auto; margin-right: auto;"><img border="0" height="97" src="http://1.bp.blogspot.com/-a2HnfP13jdQ/VkTpBArYyNI/AAAAAAAAAg8/ICotecW8rfI/s400/002.JPG" width="400" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">This area of the laser performs diagnostics on the incoming X-ray beam<br />
before hitting the sample at the far right. Image credit: Laura Kiefer. [<a href="https://picasaweb.google.com/lh/photo/DNPqh0SQOrH5B6ACB_PWC6cKw9S8TceyG8VVNSVwCJU?feat=directlink">enlarge</a>]</td></tr>
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SLAC-LCLS technicians had built the experiment preceding the group's arrival based on the specifications of their proposal. Once they arrived, all the group had to do to begin measurements was prepare a sample at a nearby laboratory. That's probably for the best, though, notes Wiley. "It's one of the only two free electron lasers on Earth. They're not going to just let some turkey that doesn't know what they're doing do anything for them."<br />
<br />
Even though the experiment was pre-built, the first day still involved a lot of setup in which the group worked closely with technicians. "During the first day, they have to get both the optical beam and the X-ray beam overlapped in space and time," Miller said. The sample, a jet of solution which shoots downwards through the crossed laser beams, has to be positioned very accurately as well; an error of even 10 micrometers, less than the width of a human hair, is enough to ruin the measurement.<br />
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<tr><td class="tr-caption" style="text-align: center;">The green-themed control room for X-ray pump probe. Each<br />
measurement at SLAC-LCLS is color-coded. "The red was<br />
just obnoxious," said Miller. Image credit: Laura Kiefer</td></tr>
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After the first day of setup, the group became much more independent. From 9 to 9 solid, the entire group, professors included, was buzzing in the control room. Miller credits the group's diverse expertise for their success. "[...] It made us a lot stronger while we were there," he said. Some people worked on conducting the measurements, while others, particularly Kubarych and Deb, built computer programs to analyze the data on-the-fly. Without the ability to quickly analyze data, "we would have been lost," said Miller.<br />
<br />
At that point, the technicians let the researchers do their thing. "It's actually amazing how much freedom you have. Once things are going, you can do it," said Kiefer.<br />
<br />
"It was an exhausting experience," said Wiley. "First of all, you're jet-lagged by three hours by flying to California. Then you invert your sleep schedule and try to sleep during the day." Never mind the four consecutive twelve-hour work days.<br />
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Despite the endurance contest, Miller, Kiefer, and Wiley seem to think that their efforts were a success. The proposal contained a strong plan with all sorts of contingencies laid out in case things went wrong or data didn't come out as anticipated. "I think the thing that we didn't think about was, well, what do we do if it goes really well?" said Wiley. "And it did go well," added Miller. "We ended up doing some unexpected experiments on the third and fourth day, and those actually are going to be maybe some of the most significant results that we found." <br />
<br />
As if performing cutting-edge science wasn't enough, the three were exposed to some of the most advanced devices on Earth just by walking through the LCLS facility. "Seeing the technology that they have is un-freaking-believable," said Kiefer. Wiley added, "They had the world's [smoothest] surface for x-ray lasers. The [smoothest] surface on Earth, ever made, being kept in a vacuum that's a thousand times lower pressure than outer space."<br />
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X-ray pump-probe is just one of the types of measurements that can be conducted at SLAC-LCLS. Overall, there are <a href="https://portal.slac.stanford.edu/sites/lcls_public/instruments/Pages/default.aspx">six different types of experiments</a> available, and a seventh to be added in 2016. With evocative names like Macromolecular Femtosecond Crystallography and Matter in Extreme Conditions, these experiments sit on the fringe of what is possible in experimental science.<br />
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<tr><td class="tr-caption" style="text-align: center;">Ted Wiley takes a long draw off of the sample<br />
jet depicted on the video monitor. Image credit:<br />
Laura Kiefer</td><td class="tr-caption" style="text-align: center;"><br /></td><td class="tr-caption" style="text-align: center;"><br /></td></tr>
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When asked about his favorite part of the experience, Wiley got poetic. "Messing around with all the gizmos, man," he said.<br />
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"My favorite part was being at the helm," Miller said, "being in control of the two million-dollar experiment." Kiefer added, "It's pretty amazing that you can be hands-on at this facility."<br />
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The group wasn't ready to talk about the scientific results yet, but you'll probably be hearing about them soon. <a href="https://www6.slac.stanford.edu/news/2014-10-07-five-years-scientific-discoveries-slacs-lcls.aspx">SLAC reported last year</a> that 341 scientific publications have come out of LCLS in the five years between 2009 and 2014. Of those, 31% were published in high-profile journals - not surprising, considering that the measurements available there can only be performed in a few other places on the planet.<br />
<br />
Now that the data has been collected and they've settled back in Ann Arbor, Miller, Wiley, and Kiefer talk about their trip with obvious enthusiasm. (Kiefer's library of photos is testament to that as well.) "It's big science," Wiley said. "In every sense of the word."Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com2tag:blogger.com,1999:blog-1971936738593606253.post-88458116288803533842015-10-23T15:31:00.001-04:002015-10-23T16:19:42.755-04:00Chemistry Literature Feature, Vol XI: University of Michigan Edition<i>The #SciBlogReaders survey is still underway! If you enjoy this blog or another science blog, <a href="http://treetownchem.blogspot.com/2015/10/scientists-surveying-science-blog.html">click here to learn</a> how you can help bloggers and win some cool prizes for yourself.</i><b><i> </i></b><br />
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<br />
In this episode of the Chemistry Literature Feature, we celebrate chemistry at the University of Michigan! Keep scrolling to learn about chemical reactions happening high in the clouds, how to teach a bad catalyst to keep itself together for longer, and new developments in small molecule cancer treatments. But first, check out the Chem Lit Feature's newest addition: CLFPic!<br />
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<a href="http://2.bp.blogspot.com/-gt6fvU2av4A/ViqIiJXdDGI/AAAAAAAAAfs/QXjfGqY7EMA/s1600/aaron_clf.jpg" imageanchor="1" style="margin-left: 1em; margin-right: 1em;"><img border="0" height="250" src="http://2.bp.blogspot.com/-gt6fvU2av4A/ViqIiJXdDGI/AAAAAAAAAfs/QXjfGqY7EMA/s400/aaron_clf.jpg" width="400" /></a></div>
This volume's CLFPic comes to us from Aaron Goodman, who graduated from the University of Michigan with a B.S. in chemistry and went on to graduate school at MIT. His photo, taken through a microscope eyepiece, shows flakes of molybdenum disulfide, MoS<sub>2</sub>. MoS<sub>2</sub> can be separated into sheets that are only a few atomic layers thick, much in the same way that graphite can be made into graphene. The blue flake in the picture is only 3 atomic layers! Such thin MoS<sub>2</sub>, which is a semiconducting material, could find applications in miniaturized electronics or light-emitting diodes.<br />
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<i><b>Analytical </b></i>- <i>Aqueous Processing of Atmospheric Organic Particles in Cloud Water Collected via Aircraft Sampling [<a href="http://pubs.acs.org/doi/abs/10.1021/acs.est.5b01639">link</a>]</i><br />
Chemical reactions happening in water droplets and clouds high in the atmosphere affect conditions down at the surface. Models exist to describe how various chemicals get incorporated into atmospheric water and how they change once they've been dissolved or once they form particles, but the models fall short in some key areas. The authors of <a href="http://pubs.acs.org/doi/abs/10.1021/acs.est.5b01639">this study, published in Environmental Science and Technology</a> (ACS) flew an airplane through different cloud regions to collect samples of both particle aerosols and water droplets containing dissolved chemicals. They examined differences in the compositions of the particles versus the water droplets in an effort to determine whether and how organic compounds react when dissolved in atmospheric water. Their findings suggest that some organic molecules, particularly organosulfates, react in water to form nitrogen-containing compounds. The result shows a relatively unexplored pathway by which volatile organics can change composition once they become part of the atmosphere.<br />
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<i>University of Michigan research from Dr. Kerri Pratt's group, first author Eric Boone.</i> <br />
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<i><b>Chemical Biology</b></i> <i>- Electron Microscopic Visualization of Protein Assemblies on Flattened DNA Origami [<a href="http://pubs.acs.org/doi/abs/10.1021/acsnano.5b01841">link</a>]</i><br />
DNA is a <a href="http://treetownchem.blogspot.com/2015/10/icyms-4-mirkin-and-schatzs-gold.html">very attractive platform for tailored biomaterials</a> due to its well-characterized and predictable structure. Those features allow chemists to purposefully synthesize artificial DNA that assembles itself in a particular way, macromolecularly speaking. In "DNA origami," strands of DNA assemble themselves into two-dimensional sheets. The <a href="http://pubs.acs.org/doi/abs/10.1021/acsnano.5b01841">authors of this paper in ACS Nano</a> demonstrate a new method for preparing flat DNA origami sheets. They then decorate the sheets with three proteins in order to demonstrate the ability to create precisely controlled arrays of proteins on DNA origami. The proteins can be reliably placed within the same nanometer-sized window across a thousand measured sheets. Discoveries like this pave the way for new advances in biocompatible materials for things like sensing.<br />
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<i>University of Michigan research from Dr. Nils Walter's group, first author Leena Mallik.</i> <br />
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<i><b>Inorganic </b>- A Proton-Switchable Bifunctional Ruthenium Complex That Catalyzes Nitrile Hydroboration [<a href="http://pubs.acs.org/doi/full/10.1021/jacs.5b08406">link</a>]</i><br />
Chemists are always looking for easier and energetically cheaper ways of making molecules. Using catalysts instead of stoichiometric reagents, for example, saves material, thereby saving the energy that goes into making it. The authors of <a href="http://pubs.acs.org/doi/full/10.1021/jacs.5b08406">this open-access publication</a> in the Journal of the American Chemical Society have created a pincer catalyst that reduces nitriles and ketones while adding boron functional groups, a process known as hydroboration. The ruthenium-based catalyst uses its <a href="https://en.wikipedia.org/wiki/Coordination_sphere#Second_coordination_sphere">second coordination sphere</a> to promote reactivity. Lewis acidic groups attached to the complex that point towards the metal center promote the reduction reaction by shuffling electrons around and pinning the molecule in place. A wealth of crystallographic and synthetic data supports the conclusion that this catalyst can hydroborate 13 different nitriles, which can then be easily converted to amines.<br />
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<i>University of Michigan research from Dr. Nate Szymczak's group, first author Jacob Geri</i><br />
Fans of chemical biology might also like the Organic paper.<i> </i><br />
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<i><b>Materials</b></i> <i>- Improving the stability and selectivity for the oxygen-evolution reaction on semiconducting WO<sub>3</sub> photoelectrodes with a solid-state FeOOH catalyst [<a href="http://pubs.rsc.org/en/content/articlelanding/2016/ta/c5ta04747a#!divAbstract">link</a>]</i><br />
<a href="http://misciwriters.com/2015/10/13/store-solar-energy-chemical-bonds-one-weird-trick/">Storing solar energy economically in the form of a fuel</a> is one of the most challenging ideas facing today's chemists. There just has not been a single material discovered that does the reaction for long enough or with enough selectivity to be industrially viable. The authors of <a href="http://pubs.rsc.org/en/content/articlelanding/2016/ta/c5ta04747a#!divAbstract">this paper, published in the Journal of Materials Chemistry A</a> (RSC), are one of many who have turned to two-phase materials that mix and match attractive aspects. By taking tungsten oxide, which quickly dissolves when performing water splitting, and adding a solid layer of a cheap iron oxide catalyst, the authors were able to create a new catalyst that performs for much longer than the original material. They also showed that the material oxidizes water almost exclusively, shutting down side reactions that reduce lifetime and efficiency.<br />
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<i>University of Michigan research from Dr. Bart Bartlett's group, first author Charles Lhermitte.</i><br />
<i> </i> <br />
<i><b>Organic </b>- Synthesis and biological evaluation of pharbinilic acid and derivatives as NF-</i><i><!--[if gte mso 9]><xml>
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</xml><![endif]--></i><i><span style="font-family: "Times New Roman",serif; font-size: 12.0pt; line-height: 107%; mso-ansi-language: EN-US; mso-bidi-language: AR-SA; mso-fareast-font-family: Calibri; mso-fareast-language: EN-US; mso-fareast-theme-font: minor-latin;">κ</span>B pathway inhibitors [<a href="http://pubs.rsc.org/en/Content/ArticleLanding/2015/CC/c5cc02918j#!divAbstract">link</a>]</i><br />
The authors of <a href="http://pubs.rsc.org/en/Content/ArticleLanding/2015/CC/c5cc02918j#!divAbstract">this communication in Chemical Communications</a> (RSC) are interested in the ability of a naturally occurring compound, pharbinilic acid, to kill cancer cells. Pharbinilic acid is found in morning glory seeds, but the process used to extract them isn't very efficient. So, the authors took a commercially available starting material, gibberic acid, and developed an efficient method of creating pharbinilic acid and derivatives. They then tested the drugs with an <i>in vitro</i> assay designed to report how well cells can keep the NF-κB pathway going. NF-κB is an important series of processes for all living cells but is particularly important in cancer cells; in some kinds of cancer, when NF-κB shuts down, the cancer cells die. The initial results in this paper show that pharbinilic acid derivatives are promising candidates for further research on cancer cell inhibition.<i> </i><br />
<br />
<i>University of Michigan research from Dr. Corinna Schindler's group, first author James Annand.</i><br />
<br />
<i><b>Physical</b> - Dynamics of Rhenium Photocatalysts Revealed through Ultrafast Multidimensional Spectroscopy [<a href="http://pubs.acs.org/doi/abs/10.1021/ar500402r">link</a>] </i><br />
Ultrafast spectroscopy is an exciting field of measurement because it allows scientists to see processes that are on the timescale of molecular motion and usually much faster than chemical reactions. The authors of <a href="http://pubs.acs.org/doi/abs/10.1021/ar500402r">this paper in Accounts of Chemical Research</a> (ACS) are concerned with using ultrafast two-dimensional infrared spectroscopy (2DIR) to understand how a well-researched rhenium carbonyl complex catalyzes the reduction of carbon dioxide to carbon monoxide. The paper discusses differences in 2DIR measurements across many different versions of the catalyst in three different solvents. Critically, the paper highlights differences between the 2DIR results when the catalyst is illuminated and when it is not. The authors discuss their findings in the context of a broad field of literature and make suggestions about how 2DIR can be used to understand catalytic processes in the future.<br />
<br />
<i>University of Michigan research from Dr. Kevin Kubarych's group, first author Laura Kiefer.</i><br />
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<b style="font-style: italic;">Remember, </b><i>if you come across an article that you think should be featured here, </i><b style="font-style: italic;">send it in! </b><a href="mailto:treetownchem@gmail.com">treetownchem@gmail.com</a><br />
<br />
<span style="color: #999999;"><i>ACS - American Chemical Society</i></span><br />
<span style="color: #999999;"><i>GDCh - Gesellschaft Deutscher Chemiker (German Chemical Society)<br />RSC - Royal Society of Chemistry</i></span>Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com3tag:blogger.com,1999:blog-1971936738593606253.post-25820996370817134662015-10-19T14:15:00.002-04:002015-10-19T14:16:17.637-04:00Scientists Surveying Science Blog Readers - For Science!Do you have a few minutes for some questions?<br />
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Dr. Paige Jarreau and Dr. Lance Porter of Louisiana State University <a href="http://lsu.qualtrics.com/jfe/form/SV_0dIyegEdCzOFNxr">want to know who reads science blogs and why</a> - and for that, they need your help.<br />
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Tree Town Chemistry has been randomly selected to participate in the #SciBlogReaders survey. If you've enjoyed this blog (or if you read it anyway through some sort of self-inflicted punishment), please take a few minutes to go through this survey. You'll be helping the research team and blog writers everywhere to understand who our audience is so that we can create even better content for you.<br />
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<i><b>But wait! There's more!</b></i><br />
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For completing the survey, you'll be entered into a drawing to receive one of two $50.00 Amazon Gift Cards. Two Tree Town Chemistry readers are guaranteed to win, so based on our readership your odds are pretty high (cough). There are other cool prizes that are being given out randomly as well, including some science t-shirts and artwork. Everyone who fills out the survey gets a <a href="http://paigesphotos.photoshelter.com/#!/index">free science art prize</a> from Paige.<br />
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<i>Please take 10-15 minutes to <a href="http://lsu.qualtrics.com/jfe/form/SV_0dIyegEdCzOFNxr">complete the #SciBlogReaders survey</a>! </i>Thank you! Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com1tag:blogger.com,1999:blog-1971936738593606253.post-78951388481830942212015-10-09T12:05:00.001-04:002015-10-09T12:12:26.837-04:00Cosmic Chemistry: Seasonal salt-water flows could sustain human life on Mars via perchlorate decompositionMy dream job is to work for NASA as a research scientist. In fact, I (kind of) lived this dream the summer before my senior year of college, where I was an intern at NASA Glenn Research Center (GRC) in Cleveland, Ohio in the photovoltaics lab. Of all the things I learned while I was there, one that stuck out, albeit trivial, was that they absolutely love making acronyms. In fact, I listened to one presentation where there were more acronyms on the slides than actual words or pictures. Point being, get ready for the most acronym-filled blog post of Tree Town Chemistry’s existence.<br />
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NASA released in a <a href="https://www.youtube.com/watch?t=4&v=bDv4FRHI3J8">press conference</a> on Monday, September 28th, 2015 that flowing liquid salt water has been discovered on the surface of Mars. This discovery explains the observation of large, seasonal flows that appear as lines on the slopes of many Martian craters, called <a href="http://www.sciencemag.org/content/333/6043/740.full.pdf">Recurring Slope Lineae (RSL)</a>, which can be up to hundreds of meters long and up to ~5 meters wide. The discovery of these RSL - and the chemistry behind them - has prompted NASA to further detail some exciting plans of sending astronauts to Mars.<br />
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<table align="center" cellpadding="0" cellspacing="0" class="tr-caption-container" style="margin-left: auto; margin-right: auto; text-align: center;"><tbody>
<tr><td style="text-align: center;"><a href="http://4.bp.blogspot.com/-pukMkO_FmuY/VhfE73Gh2UI/AAAAAAAAAec/B7ILGi9v6NQ/s1600/rsl.png" imageanchor="1" style="margin-left: auto; margin-right: auto;"><img border="0" height="207" src="http://4.bp.blogspot.com/-pukMkO_FmuY/VhfE73Gh2UI/AAAAAAAAAec/B7ILGi9v6NQ/s400/rsl.png" width="400" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">Recurring Slope Lineae (RSL) that have been observed in NASA’s High Resolution Imaging <br />
Science Experiment (HiRISE) on the Mars Reconnaissance Orbiter (MRO). Images were taken <br />
on the slopes of the Gami Crater. Credit: NASA/JPL/University of Arizona</td><td class="tr-caption" style="text-align: center;"></td><td class="tr-caption" style="text-align: center;"></td></tr>
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These brine flows are discussed in two recently published papers in Nature Geoscience, one with <a href="http://www.nature.com/ngeo/journal/v8/n5/full/ngeo2412.html">indirect</a> evidence and the other with <a href="http://www.nature.com/ngeo/journal/vaop/ncurrent/full/ngeo2546.html">direct</a> evidence of hydrated perchlorate salts (ClO<sub>4</sub><sup>-</sup><b> .</b> xH<sub>2</sub>O) within the RSLs. by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) on the Mars Reconnaissance Orbiter (MRO). The process by which the RSLs form is called deliquescence, the same process that clogs your salt shaker with hydrated salt. As the salt sits on the surface of the planet, it absorbs water vapor from the atmosphere, which causes the water (through freezing-point depression) to maintain its liquid phase even in the low pressure, low temperature conditions on the surface of Mars. In fact, at concentrations observed on Mars, perchlorate salts lower the freezing point of water by up to 80ºC (that’s 176ºF!).<br />
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This mechanism isn’t the only proposed explanation for the RSLs. Others speculate that the water could come from <a href="http://www.planetary.org/blogs/guest-blogs/2014/0513-whats-seeping-on-mars.html">surface ice melting</a> in the presence of perchlorate salts or <a href="http://mars.jpl.nasa.gov/technology/subsurface/">underground water</a> seeping through to the surface.<br />
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Over the four seasons the planet goes through, water slowly makes its way down the slopes of the mountains by the surface salts absorbing water during the warm months (above -23ºC on average, or -10ºC), then fade over the colder months. Scientists believe that the activity of water on Mars’ surface is too low to support life, meaning that the water within the hydrated perchlorate salt is not easily accessible for organisms to live in. In the press conference, Lujendra Ojha, lead author of the Nature Geoscience article proposing direct evidence for brine flows on Mars and graduate student at Georgia Tech in Atlanta, GA, stated that “If RSL are perchlorate-saturated brines, then life as we know [it] on Earth could not survive in such low water activity.”<br />
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<table align="center" cellpadding="0" cellspacing="0" class="tr-caption-container" style="margin-left: auto; margin-right: auto; text-align: center;"><tbody>
<tr><td style="text-align: center;"><a href="http://3.bp.blogspot.com/-HDiHXzuhYNs/VhfHN3tKwVI/AAAAAAAAAeo/S1pdq5Xt1GA/s1600/temp.png" imageanchor="1" style="margin-left: auto; margin-right: auto;"><img border="0" height="220" src="http://3.bp.blogspot.com/-HDiHXzuhYNs/VhfHN3tKwVI/AAAAAAAAAeo/S1pdq5Xt1GA/s400/temp.png" width="400" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">Illustration of the various phases of water on the surface of Mars compared to that of Earth’s surface. The surface temperature of Mars, based on the <a href="http://science.nasa.gov/science-news/science-at-nasa/2000/ast29jun_1m/">Viking landing sites</a>, are believed to be between -60 and 27ºC.</td></tr>
</tbody></table>
The discovery of liquid water on Mars is not only exciting for the aspect of finding Martian life. It also is exciting when you think about sending humans to Mars. Clearly, life on Earth needs water to survive. The astronauts we will eventually send to Mars in ~2030s will need a reliable source of water, but also a reliable source of O<sub>2</sub> to breathe. Finding liquid water in the form of brine could allow astronauts not only to purify this water into fresh drinking water, but potentially to use the perchlorate salts as a source of O<sub>2</sub>.<br />
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Why does perchlorate work as a source of breathable oxygen? The perchlorate anion, ClO<sub>4</sub><sup>-</sup>, is completely stable when dissolved in water. However, its solid anhydrous state can be very unstable to shock. Taking ammonium perchlorate NH<sub>4</sub>ClO<sub>4</sub> as an example, a hit with a hammer of a crystal, or even twisting open the bottle with a crystal stuck between the threads, can cause the <a href="http://www.dtic.mil/dtic/tr/fulltext/u2/673542.pdf">following</a> highly exothermic and entropically favorable reactions, depending on the temperature.<br />
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<a href="http://2.bp.blogspot.com/-XcyrQtr5ZL0/Vhfj2ekaVAI/AAAAAAAAAfA/iQYSTKEvUG4/s1600/temp2.png" imageanchor="1" style="margin-left: 1em; margin-right: 1em;"><img border="0" height="71" src="http://2.bp.blogspot.com/-XcyrQtr5ZL0/Vhfj2ekaVAI/AAAAAAAAAfA/iQYSTKEvUG4/s400/temp2.png" width="400" /></a></div>
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Side note, most fireworks are built with various metal perchlorates, where the metal cation dictates that color that you see! In the perchlorate ion, the chlorine has its density of electrons pulled away by four oxygens, creating a +7 oxidation state on the chlorine. For comparison, chlorine is most commonly found as the chloride anion (e.g. NaCl, or table salt), where the oxidation state is -1. Typically, the electron density in a molecule containing chlorine gets pulled toward the chlorine. However, with four oxygens surrounding the chlorine atom in the perchlorate anion, the electron density gets pulled away from the chlorine toward the oxygen. Because chlorine is highly electronegative compared to most atoms on the periodic table, having a lot of its electron density pulled away by four oxygen atoms in ClO<sub>4</sub><sup>-</sup> makes it very unhappy.<br />
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<table align="center" cellpadding="0" cellspacing="0" class="tr-caption-container" style="margin-left: auto; margin-right: auto; text-align: center;"><tbody>
<tr><td style="text-align: center;"><a href="http://3.bp.blogspot.com/-oIEFZfWYMg8/Vhfke6LuXEI/AAAAAAAAAfI/FAC0lKyGC6c/s1600/NaCl%2Bvs%2BClO4%2BSpartan.png" imageanchor="1" style="margin-left: auto; margin-right: auto;"><img border="0" height="230" src="http://3.bp.blogspot.com/-oIEFZfWYMg8/Vhfke6LuXEI/AAAAAAAAAfI/FAC0lKyGC6c/s400/NaCl%2Bvs%2BClO4%2BSpartan.png" width="400" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">Density of electrons around chlorine and other various atoms in molecules of sodium chloride, <br />
NaCl (right) and the perchlorate ion, ClO<sub>4</sub><sup>-</sup> (left). In this image, electron density increases <br />
from blue to red. Images and calculations made in Spartan. </td></tr>
</tbody></table>
Although direct <a href="http://ntrs.nasa.gov/search.jsp?R=20150001920">evidence</a> for ammonium cation being associated with perchlorate anion has not been observed on the surface of Mars, there is strong evidence for Mg(ClO<sub>4</sub>)<sub>2</sub> and NaClO<sub>4</sub>. In addition, experiments on the Sample Analysis at Mars (SAM) instrument onboard the Curiosity Mars Rover (they unfortunately did not name it after me, but a man can dream…) have strong evidence that supports mixtures of Mg(ClO<sub>4</sub>)<sub>2</sub>, Ca(ClO<sub>4</sub>)<sub>2</sub>, and/or NaClO<sub>4</sub> and iron-rich Martian soil produce O<sub>2</sub> in significant quantities between 225 – 461ºC (437 – 862ºF). Additionally, perchlorate salts can be easily extracted with anion-exchange resins, which can allow astronauts to more easily purify any brine to drinkable water. This also allows them to purify the perchlorate salt into a powder, which is required for decomposition into molecular oxygen. <br />
<br />
Although many astrophysicists and astrobiologists (yes, that’s a field – and it’s awesome) have expressed overwhelming excitement for this new discovery on Mars, others might argue that finding water is not all it’s cracked up to be. For example, we have no direct evidence of the precursors to life such as amino acids, DNA, RNA, etc. Although I agree that finding evidence for these compounds would be an enormous jump in our search for life on Mars, a more acute and still very exciting impact of finding direct evidence for liquid water in the form of hydrated perchlorate salts on the surface is that we are now closer to supporting life on Mars, particularly for astronauts that we send there from Earth. We also have more confidence that some of the elements that we know can support life as we know it are also present on Mars, boosting the probability that life does or once did exist on that planet. <br />
<br />
Through NASAs direct measurements from the HiRISE experiment on the MRO, the SAM instrument on Curiosity, and the spectroscopic measurements of RSLs from the MRO by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM), we now have a deeper understanding of ClO<sub>4</sub><sup>-</sup> salts on the surface of Mars, and can start to design our missions to produce our own oxygen and drinking water from the elements that exist on the Martian surface. If you didn’t catch all of those acronyms, don’t feel bad; I had to look up most of them while I was writing that sentence.Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com3tag:blogger.com,1999:blog-1971936738593606253.post-20358581938055518202015-10-02T10:33:00.002-04:002015-10-02T10:58:35.320-04:00ICYMS 4: Mirkin and Schatz's Gold Nanoparticle Lattices Mess with Light in New WaysWhat do stained glass windows, single molecule sensing, and light-emitting diodes have in common?<br />
<br />
Right now, not much. But research from the laboratories of Northwestern University chemists Dr. George Schatz and Dr. Chad Mirkin are trying to change that. Together, they have published several papers on a new breed of nanoparticle superlattices - materials that are turning out to do unique tricks with light. Their research contributes to the field of plasmonics, which encompasses optical phenomena that <a href="http://www.nytimes.com/2005/02/22/science/tiny-is-beautiful-translating-nano-into-practical.html?_r=0">give stained glass windows their color</a> and could <a href="http://iopscience.iop.org/article/10.7567/JJAP.52.010001/meta">find application in futuristic devices</a>.<br />
<a name='more'></a><br />
Both Dr. Mirkin and Dr. Schatz recently came through the University of Michigan Chemistry department to give seminars. The <a href="http://www.nature.com/nnano/journal/v10/n5/full/nnano.2015.68.html#abstract">most recent fruit of their collaboration</a> has been published in Nature Nanotechnology and describes how large lattices of gold nanoparticles spaced out by tightly controlled lengths of DNA interact with beams of light. These materials function on the basis of plasmon resonance.<br />
<br />
<i><b>Plasmon? Sounds Dangerous...</b></i><br />
Before we dive into plasmons, it's helpful to understand two seemingly unrelated things. First, electrically conductive materials like metals don't hold on to their electrons very tightly. As a result, the electrons are free to move around through a metal particle in response to external forces, such as heat or an applied voltage. Secondly, <a href="http://www.livescience.com/38169-electromagnetism.html">light is electromagnetic radiation</a>. Physically, that means that light is composed of an electric field and a perpendicular magnetic field, both of which are swinging back and forth in direction.<br />
<br />
So, what happens when we put a metal nanoparticle into a beam of light? In the dark, the electrons within the nanoparticle are undisturbed. When we turn the light on, the nanoparticle experiences a field of electromagnetic radiation. The electric field - a voltage, essentially - passes through the nanoparticle. Remember that the electrons in the particle are weakly held, so they move along with the electric field towards one end of the particle. As the electric field changes direction, the electrons go with it.<br />
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<tr><td class="tr-caption" style="text-align: center;">You are feeling sleepy... veerrry sleepy... original .gif via <a href="http://gifmaker.me/">gifmaker.me</a>.</td></tr>
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<br />
Now we have a situation where the electrons are oscillating back and forth within the particle, which causes changes in the light beam. The light transfers some energy to the particle as it drags the electrons back and forth, so an absorptive feature - called the plasmon resonance - appears at a particular wavelength.<br />
<br />
It's important to note that plasmonic effects don't only arise in nanoparticles; plasmons play an important role at many length scales. However, chemists take advantage of plasmons in nanoparticles - usually of gold or silver - to achieve optical effects as well as <a href="http://pubs.acs.org/doi/abs/10.1021/cs400993w">promote catalysis</a>.<br />
<br />
<i><b>The Latest: Small Particles in Huge Lattices</b></i><br />
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<tr><td style="text-align: center;"><a href="http://3.bp.blogspot.com/-kHbuBrYX3Uw/Vg2urQGjtUI/AAAAAAAAAdI/u2xx_Q5Kphw/s1600/chadnano.png" imageanchor="1" style="clear: left; margin-bottom: 1em; margin-left: auto; margin-right: auto;"><img border="0" height="400" src="http://3.bp.blogspot.com/-kHbuBrYX3Uw/Vg2urQGjtUI/AAAAAAAAAdI/u2xx_Q5Kphw/s400/chadnano.png" width="196" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">The top half shows the anatomy of a<br />
spherical nucleic acid. In the bottom,<br />
bonds between sticky ends (circled)<br />
keep the spherical nucleic acids<br />
together and a lattice starts to form.</td></tr>
</tbody></table>
<a href="http://mirkin-group.northwestern.edu/research/spherical-nucleic-acids-snas/">Dr. Mirkin's group has become expert</a> at <a href="http://onlinelibrary.wiley.com/doi/10.1002/anie.201209336/abstract">using DNA to create very carefully spaced superlattices of gold nanoparticles</a>. Strands of DNA bind readily to gold nanoparticles to create what's been termed a spherical nucleic acid. But, the DNA isn't complete; "sticky ends" of DNA half-strands are left hanging. These sticky ends can bind to sticky ends on other spherical nucleic acids and hook the spherical nucleic acids together. By changing the length of the DNA strands, Mirkin's group can change the distance between the gold nanoparticles.<br />
<br />
In the latest collaborative paper between Dr. Mirkin and Dr. Schatz (Michael B. Ross, first author), the authors study the effect that spacing out the gold nanoparticles has on the plasmonic properties. They allow that the composite material can interact with light in two ways: plasmonic absorption, as described above, and <a href="http://www.physicsclassroom.com/class/refrn/Lesson-2/Snell-s-Law">scattering</a>. Using a model called effective medium theory, they predict that sparse lattices of gold nanoparticles will not scatter light, and the only optical features observed will be plasmonic absorption. Furthermore, their model shows that for dense superlattices with lots of gold nanoparticles packed close together, the refractive index of the material changes, and scattering becomes dominant. They also suggest that the mesoscale (micrometer-length) shape of the particles controls the refractive properties.<br />
<br />
Experimentally, the superlattices were prepared in both micron-sized powder form and also as ~150 nm thin films. The thin films aren't thick enough to have a mesoscale structure, so the authors compared how samples of both geometries interact with light. They also quantify the way gold nanoparticle superlattices of increasing gold density differ from one another in both geometries. The findings show that features for thin films are unchanged regardless of the gold content, showing only plasmonic absorption. Large superlattice particles, on the other hand, scatter light at longer wavelengths when the gold content is higher.<br />
<br />
These experimental results are exactly in line with what the authors' model predicted, so they turn around and use the model to make some predictions on how mesoscale particles of differing shape, or crystal habit, will scatter light. The simulations uncover a shape dependence and a gold density dependence on optical features for five different systems.<br />
<br />
<i><b>Wait, but Why?</b></i><br />
As light passes through one of the superlattice particles, it can interact with individual gold nanoparticles through plasmonic absorption. But, as the gold nanoparticles get closer and closer together, a different mechanism starts to dominate.<br />
<br />
<i><b> </b></i><br />
When the gold nanoparticles are close together within the superlattice, the effective refractive index of the whole material goes up. That means that light actually moves more slowly through the superlattice than it does through the surrounding medium. When the light slows down, it changes direction, and that's what gives rise to scattering. You've seen this before - it's the same reason that stuff <a href="http://www.schoolphysics.co.uk/age14-16/Light/text/Refraction_and_fishermen/index.html">underwater looks like it's in a different position</a> from above the water than it
does from below. Scattering isn't observed in the thin films because light doesn't travel through them for long enough for the change in direction to become apparent.<br />
<br />
For the future of optical devices, this realization is a big deal. Researchers are trying to dream up ways of customizing materials to achieve various optical effects. Mirkin and Schatz's paper connects the wavelengths scattered by a material to its internal geometry and also to its crystal habit. Looking at this work, one can imagine dialing in specific optical responses that can't be replicated by any material in nature.<br />
<br />
That would make really tiny particles into really big business.<br />
<br />
<i>Author's note: I had a lot of help with this post because physics is hard. Major, major thanks to Dr. Kevin Kubarych for an hour-long impromptu crash course on plasmonics by which I am still amazed, and thanks as always to my friends in physical chem for answering questions.</i>Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com3tag:blogger.com,1999:blog-1971936738593606253.post-52540017029615562762015-08-14T13:56:00.001-04:002015-08-14T13:56:41.276-04:00Hold the Phone: #Chemoji Are HereThe American Chemical Society, Chemical & Engineering News, and Swyft Media have teamed up to bring you the ACS Chemoji. (Emoji? Emojis? Kids these days.)<br />
<div style="text-align: center;">
<blockquote class="twitter-tweet" data-partner="tweetdeck">
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"There stars and a moon in my hood. Damn astronomers have been at it again." <a href="https://twitter.com/hashtag/ACSchemoji?src=hash">#ACSchemoji</a> <a href="http://t.co/uTI04gng1e">pic.twitter.com/uTI04gng1e</a></div>
— Raychelle Burks (@DrRubidium) <a href="https://twitter.com/DrRubidium/status/631926162655088641">August 13, 2015</a></blockquote>
</div>
<script async="" charset="utf-8" src="//platform.twitter.com/widgets.js"></script>
Nothing captures the frustration of a terrible week in lab like a disgruntled, begoggled emote face. Or, maybe your friend texted you some details of their next experiment, and you want to give your OSHA-approved thumbs-up. No matter what your purposes are, iPhone and Android users can <a href="http://swyftmedia.com/apps/app.php?app=chemoji">grab the ACS Chemoji set for free</a> from the App Store or from Google Play.<br />
<blockquote class="twitter-tweet" data-partner="tweetdeck">
<div dir="ltr" lang="en">
Yep. That would sum up my week for the most part. <a href="https://twitter.com/hashtag/acschemoji?src=hash">#acschemoji</a> <a href="http://t.co/jppdMllxCr">pic.twitter.com/jppdMllxCr</a></div>
— Lauren Wolf (@laurenkwolf) <a href="https://twitter.com/laurenkwolf/status/631869138894503936">August 13, 2015</a></blockquote>
<script async="" charset="utf-8" src="//platform.twitter.com/widgets.js"></script>
The ACS Chemoji app will set up a third-party keyboard on your device that can be accessed through most apps. The Chemoji don't work quite like normal emoji, but are rather more akin to Facebook's stickers. Chemoji can be inserted directly into texts and Facebook Messenger messages - tap once to copy, then paste into your text body. Don't worry about whether the recipient has the set installed on their phone - they'll get your sticker anyway.<br />
<br />
For Twitter, it's a little more complicated. Tap twice to copy the Chemoji of your choice into your photo gallery, then insert the sticker into your tweet like you would any other picture.<br />
<br />
Friends, chemists, and chemistry aficionados! Go forth, obtain the Chemoji, and share your fun on #acschemoji. Or, you know, confuse your grandparents.Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com2tag:blogger.com,1999:blog-1971936738593606253.post-66941060813854829722015-08-11T17:23:00.002-04:002015-08-12T12:55:59.626-04:00"Chasing Molecules" Has a Green Message for Chemists and Consumers<blockquote class="tr_bq">
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<span style="font-family: Georgia,"Times New Roman",serif;">I have synthesized over 2,500 compounds! I have never been taught what makes a chemical toxic! I have no idea what makes a chemical an environmental hazard! I have synthesized over 2,500 compounds! <i>I have no idea what makes a chemical toxic!</i></span><br />
<div style="text-align: right;">
<span style="font-family: Georgia,"Times New Roman",serif;">Chasing Molecules<i>, xxiii</i></span></div>
</blockquote>
<br />
Elizabeth Grossman, the author of <a href="http://www.amazon.com/Chasing-Molecules-Poisonous-Products-Chemistry/dp/161091161X"><i>Chasing Molecules: Poisonous Products, Human Health, and the Promise of Green Chemistry</i></a> (Island Press, 2011), quotes the above from Dr. John Warner, who is the co-founder of the <a href="http://www.warnerbabcock.com/">Warner Babcock Institute for Green Chemistry.</a><br />
<a name='more'></a><br />
Hearing that quote for the first time, and throughout the first pages of the book, my reaction was initially hostile. Of <i>course</i> I know what makes a molecule toxic, I thought to myself. I'm an expert chemist. People literally pay me money to do this. So I picked my favorite example of a toxic molecule: benzene. Every chemist knows benzene is toxic. Its toxicity is obvious. It's toxic because... well, um... it's benzene?<br />
<br />
And carbon tetrachloride? Toxic. <i>Duh</i>. That one's got a halogen. Halogens are toxic, right? Ooh, and lead, of course, which is bad for you because it gets in there somewhere and does... something.<br />
<br />
The more I read forward from Warner's quote, the more I realized that he was absolutely right. As a chemist, I have been given the tools to understand how to make a narrow subset of molecules and solids, carry out some physical characterization, and dispose of waste according to environmental standards. I hope that some day, my research might find an industrial application and improve somebody's life, but I have no perspective on any of the myriad ways in which my activities could inadvertently <i>harm</i> lives or on how to engineer them to avoid doing so.<br />
<br />
<br />
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<tr><td class="tr-caption" style="text-align: center;"><i>Chasing Molecules</i>: you'll devour it.</td></tr>
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In <i>Chasing Molecules</i>, Grossman takes this idea as one of her central theses. I have no perspective on the harm done by my chemistry because bestowing that perspective has not ever been a priority in chemistry education. Toxicology and ecology have been the territory of public health and biology students rather than the chemists designing potentially toxic molecules. Part of green chemistry involves educating chemists on those disciplines. The book begins with an introduction to green chemistry and some of its key players in academia. In the opening chapter, she describes precisely what is meant by green chemistry and makes a case that chemists in all disciplines and in all areas of the industry should practice it.<br />
<br />
In 2015, the word "green" conjures images of expensive off-brand cleaners, your smug Prius-driving friend, and the vegan at your party going on about the clean water cost of large-scale meat production. But for researchers like Warner and Paul Anastas, the director of <a href="http://www.greenchemistry.yale.edu/">Yale's Center for Green Chemistry and Green Engineering</a>, green chemistry boils down to one simple concept: understanding the full toxicity profile of a chemical product <i>before</i> it gets put into lucrative, high-volume production is the best way to minimize cost. Here, cost includes the traditional expenses of capital, raw materials, labor, etc., but is expanded to include the costs of environmental contamination and human exposure. "Benign by design," if you will<br />
<br />
From those beginnings, the book picks up quickly. Grossman takes us on a long tour of the scientific evidence for environmental contamination by chemicals from consumer products. We meet researchers on an Arctic ice ship who are finding industrial pollutants in the most remote and pristine environments on our planet. We learn that babies in every part of the world are being born with plasticizers like bisphenol A and flame retardants like polybrominated diphenyl ethers already in their bloodstream. Grossman shows us that some of these compounds can chemically alter DNA and RNA, leading to diseases and disorders that can show up in your children years after you've been exposed. The discussion progresses through polymers that are used in your non-stick cookware all the way to the nanomaterial frontier. The principles of green chemistry, discussed somewhat dryly in the opening chapters, immediately take full form when held up next to data from environmental monitoring and endocrine toxicology studies. Grossman does an excellent job of juxtaposing the two and letting the science speak on behalf of the science policy.<br />
<br />
In all of these cases, the story remains the same. The manufacturing sector, ever-focused on the bottom line, has studied acute toxicity - in short, whether or not you'll get sick if you're exposed to lots of a substance all at one time. If a product's acute toxicity is acceptably low, or maybe even if it isn't, it gets put into production and money gets made. When new information surfaces about how the material behaves in the environment or may affect populations exposed to small amounts over a long period of time, bringing about change means fighting against companies entrenched by the fact that they are making money. It also means fighting against their money.<br />
<br />
<i>Chasing Molecules</i> is at its strongest when it takes the system to task. Are chemical companies releasing these pollutants into the environment because they're bad people? Are they putting products that they know to be potentially hazardous into large-scale production because they're evil? No. They're doing these things because they're good businesspeople. Research is expensive, and it should come as no surprise that the bulk of a chemical company's research dollars go towards maximizing the performance and cost-efficiency of a given product. The companies focus on crafting the best product possible, then selling it to the public at a price that allows for profit from their "cradle-to-gate" expenses. Whether or not that product breaks down into a harmful chemical once it's in the hands of the consumer just does not factor into the company's bottom line. It's the system, which has historically placed human and environmental costs at a stark minimum compared to material capital, which has endorsed a manufacturing ethic that places profits above all other considerations, that has given rise to the problems. The system continues to prosper in part due to lax regulation from government agencies, particularly in the United States.<br />
<br />
Proponents of green chemistry would hold chemists and chemical manufacturers responsible for producing and selling products in a way that does not produce persistent toxic chemicals. The green chemists Grossman interviews are quick to acknowledge that change will only come from the manufacturing sector when those changes become profitable, which involves changing manufacturing philosophy to regard environmental costs as... well, costs.<br />
<br />
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<tr><td class="tr-caption" style="text-align: center;"><i>Chasing Molecules</i> takes the principles of green chemistry from<br />
the billboard to the laboratory and will make you think about<br />
your research in an entirely new light.</td></tr>
</tbody></table>
Grossman makes the case for change with scads of scientific evidence and expert testimony, along with a healthy dose of adventure stories and personal anecdotes. Each chapter features 20-40 footnotes with sources ranging from interviews with scientists to news reports to primary scientific literature. By interviewing researchers and engaging directly with data, Grossman imbues <i>Chasing Molecules</i> with a high degree of credibility, as her previous publication record attests. The narrative style can be dense while the science is being traversed, but Grossman keeps readers grounded by frequently referring back to the thesis of a particular section. Despite the book's 2009 publication date (2011 republication), almost every piece of the scientific story was new to me, or was something that I had read about briefly without really delving into. I learned a great deal reading this book.<br />
<br />
For its strengths, however, <i>Chasing Molecules </i>falls into some familiar traps with tone and wording. Much of the book takes on an air of "natural = good, synthetic = bad", or more specifically "natural = good, petrochemical = bad", particularly in the opening chapters. Grossman is critical of the toxic effects of synthetic polymers and adhesives, but is surprisingly less critical of their green analogues later in the book when they are introduced. For example, a particular polymer with several attractive properties is described as "thymine-based." The discussion is heavy on the potential applications of the polymer, but light on its details or toxicalogical profile. A similar story is presented on a "castor-based" polymer and "soy-based" adhesive. These materials are certainly emerging subjects of research and perhaps these details are not yet available.<br />
<br />
Science writers translate scientific findings between the technical and exacting language of research to language accessible to non-experts. Most of <i>Chasing Molecules</i> does a great job of that, but some sections are abstracted so far as to become misleading. By way of example, in writing about the toxicity of phenols, Grossman draws parallels between phenols and the broad spectrum of petrochemicals. While phenols are petrochemicals, and phenols are also toxic, their petrochemical origins are not the feature that triggers toxicity. Moments like these pass up on opportunities to arm readers with methods of critically analyzing the chemical structure of a phenol so that they can make predictions about the next suspicious molecule to cross into the spotlight.<br />
<br />
<b><i>The Low Point:</i></b> The low point of <i>Chasing Molecules</i>, if it can be called as much,<i> </i>is actually the beginning. The preface, prologue, and first chapter of the book are fairly redundant. Perhaps it was my impatience to get to the scientific data, perhaps it was my left-leaning tendencies and readiness to accept measures of environmental protection, but I found myself tapping my foot and waiting for the sections to be over. Rather than a particularly dicey section of the book, however, I would label the low point as the tone with which Grossman discusses some of the green alternatives to established chemical products and the broad brush with which she paints petrochemicals, as mentioned above.<br />
<br />
<i><b>The High Point:</b></i> The high point of the book was the seventh chapter, in which Grossman opens by highlighting much of the environmental policy measures already in place in the United States and elsewhere for regulating chemical manufacturing and protecting against environmental exposure. The information is fascinating, but not because the regulations are good, to put it softly. Grossman points out weaknesses and loopholes in the Toxic Substances Control Act in particular. For example, "[a]nother feature of our current chemical regulatory system [...] is that the Toxic Substances Control Act allows manufacturers to claim confidentiality and withhold full details of a material's composition." (Grossman, 138). However, Grossman is not fanatical in this indictment, or in her discussion of toxics in any point of the book. She avoids environmental scare tactics in favor of sober discussions of existing data.<br />
<br />
<i>Chasing Molecules</i><b> </b>is an interesting read for chemists at any station within the discipline. For me, Grossman's book transformed green chemistry from a buzzy set of guidelines posted on the wall of my laboratory breakroom to an exciting intersection of basic chemical research, science policy, public health, and manufacturing strategy. Most chemists only think about one of those things - guess which. <i> </i><br />
<i>Chasing Molecules</i> is not just for chemists by any stretch of the imagination, though. The information is organized logically and clearly, and the natural science is presented at a level accessible to any reader. If you're concerned about the rumors you've heard about why your plastic water bottle is killing you or how chemical exposure affects millions of low-income workers worldwide, then this one is a great place to start.<br />
<br />
<hr />
<br />
<i><b>PS. The Audiobook: </b></i>I frequently drive back and forth between Michigan and Pennsylvania, which leaves me lots of golden listening time to maximize with cool books, so I listened to this book rather than reading it (Audible). The ten-hour narration was one of the more excruciating auditory experiences of my life, and I've seen Mudvayne in concert. I occasionally found myself drifting off and having to repeat sections, which has less to do with the content of the book than it does with the sing-song lullaby voice of its narrator. The narrator also mispronounces some key chemical names that are repeated often throughout the text (tributyltin, for example), which becomes grating. Grossman also uses some long and complex sentences where large amounts of information are given in appositive clauses, and the narrator's delivery often makes those moments quite difficult to understand. I would highly recommend reading this one off of the page instead.Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com1tag:blogger.com,1999:blog-1971936738593606253.post-351343854433205302015-07-31T10:32:00.001-04:002015-07-31T10:40:45.502-04:00Cosmic Chemistry on Pluto and Titan: The Formation of Tholins, and Their Possible Link to Life on Earth<table align="center" cellpadding="0" cellspacing="0" class="tr-caption-container" style="float: right; margin-left: 1em; text-align: right;"><tbody>
<tr><td style="text-align: center;"><img alt="" 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Newly
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<span style="mso-spacerun: yes;"> </span>Image from NASA/Johns Hopkins University
Applied</div>
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Physics Laboratory/Southwest Resarch Institute.<span style="font-family: "Times",serif; font-size: 10.0pt; mso-bidi-font-family: "Times New Roman"; mso-fareast-font-family: "Times New Roman";"></span></div>
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<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Body Text First Indent 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Note Heading"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Body Text 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Body Text 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Body Text Indent 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Body Text Indent 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Block Text"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Hyperlink"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="FollowedHyperlink"/>
<w:LsdException Locked="false" Priority="22" QFormat="true" Name="Strong"/>
<w:LsdException Locked="false" Priority="20" QFormat="true" Name="Emphasis"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Document Map"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Plain Text"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="E-mail Signature"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Top of Form"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Bottom of Form"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Normal (Web)"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Acronym"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Address"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Cite"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Code"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Definition"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Keyboard"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Preformatted"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Sample"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Typewriter"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Variable"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Normal Table"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="annotation subject"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="No List"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Outline List 1"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Outline List 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Outline List 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Simple 1"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Simple 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Simple 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Classic 1"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Classic 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Classic 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Classic 4"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Colorful 1"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Colorful 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Colorful 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Columns 1"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Columns 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Columns 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Columns 4"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Columns 5"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Grid 1"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Grid 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Grid 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Grid 4"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Grid 5"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Grid 6"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Grid 7"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Grid 8"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table List 1"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table List 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table List 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table List 4"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table List 5"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table List 6"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table List 7"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table List 8"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table 3D effects 1"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table 3D effects 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table 3D effects 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Contemporary"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Elegant"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Professional"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Subtle 1"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Subtle 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Web 1"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Web 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Web 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Balloon Text"/>
<w:LsdException Locked="false" Priority="39" Name="Table Grid"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Theme"/>
<w:LsdException Locked="false" SemiHidden="true" Name="Placeholder Text"/>
<w:LsdException Locked="false" Priority="1" QFormat="true" Name="No Spacing"/>
<w:LsdException Locked="false" Priority="60" Name="Light Shading"/>
<w:LsdException Locked="false" Priority="61" Name="Light List"/>
<w:LsdException Locked="false" Priority="62" Name="Light Grid"/>
<w:LsdException Locked="false" Priority="63" Name="Medium Shading 1"/>
<w:LsdException Locked="false" Priority="64" Name="Medium Shading 2"/>
<w:LsdException Locked="false" Priority="65" Name="Medium List 1"/>
<w:LsdException Locked="false" Priority="66" Name="Medium List 2"/>
<w:LsdException Locked="false" Priority="67" Name="Medium Grid 1"/>
<w:LsdException Locked="false" Priority="68" Name="Medium Grid 2"/>
<w:LsdException Locked="false" Priority="69" Name="Medium Grid 3"/>
<w:LsdException Locked="false" Priority="70" Name="Dark List"/>
<w:LsdException Locked="false" Priority="71" Name="Colorful Shading"/>
<w:LsdException Locked="false" Priority="72" Name="Colorful List"/>
<w:LsdException Locked="false" Priority="73" Name="Colorful Grid"/>
<w:LsdException Locked="false" Priority="60" Name="Light Shading Accent 1"/>
<w:LsdException Locked="false" Priority="61" Name="Light List Accent 1"/>
<w:LsdException Locked="false" Priority="62" Name="Light Grid Accent 1"/>
<w:LsdException Locked="false" Priority="63" Name="Medium Shading 1 Accent 1"/>
<w:LsdException Locked="false" Priority="64" Name="Medium Shading 2 Accent 1"/>
<w:LsdException Locked="false" Priority="65" Name="Medium List 1 Accent 1"/>
<w:LsdException Locked="false" SemiHidden="true" Name="Revision"/>
<w:LsdException Locked="false" Priority="34" QFormat="true"
Name="List Paragraph"/>
<w:LsdException Locked="false" Priority="29" QFormat="true" Name="Quote"/>
<w:LsdException Locked="false" Priority="30" QFormat="true"
Name="Intense Quote"/>
<w:LsdException Locked="false" Priority="66" Name="Medium List 2 Accent 1"/>
<w:LsdException Locked="false" Priority="67" Name="Medium Grid 1 Accent 1"/>
<w:LsdException Locked="false" Priority="68" Name="Medium Grid 2 Accent 1"/>
<w:LsdException Locked="false" Priority="69" Name="Medium Grid 3 Accent 1"/>
<w:LsdException Locked="false" Priority="70" Name="Dark List Accent 1"/>
<w:LsdException Locked="false" Priority="71" Name="Colorful Shading Accent 1"/>
<w:LsdException Locked="false" Priority="72" Name="Colorful List Accent 1"/>
<w:LsdException Locked="false" Priority="73" Name="Colorful Grid Accent 1"/>
<w:LsdException Locked="false" Priority="60" Name="Light Shading Accent 2"/>
<w:LsdException Locked="false" Priority="61" Name="Light List Accent 2"/>
<w:LsdException Locked="false" Priority="62" Name="Light Grid Accent 2"/>
<w:LsdException Locked="false" Priority="63" Name="Medium Shading 1 Accent 2"/>
<w:LsdException Locked="false" Priority="64" Name="Medium Shading 2 Accent 2"/>
<w:LsdException Locked="false" Priority="65" Name="Medium List 1 Accent 2"/>
<w:LsdException Locked="false" Priority="66" Name="Medium List 2 Accent 2"/>
<w:LsdException Locked="false" Priority="67" Name="Medium Grid 1 Accent 2"/>
<w:LsdException Locked="false" Priority="68" Name="Medium Grid 2 Accent 2"/>
<w:LsdException Locked="false" Priority="69" Name="Medium Grid 3 Accent 2"/>
<w:LsdException Locked="false" Priority="70" Name="Dark List Accent 2"/>
<w:LsdException Locked="false" Priority="71" Name="Colorful Shading Accent 2"/>
<w:LsdException Locked="false" Priority="72" Name="Colorful List Accent 2"/>
<w:LsdException Locked="false" Priority="73" Name="Colorful Grid Accent 2"/>
<w:LsdException Locked="false" Priority="60" Name="Light Shading Accent 3"/>
<w:LsdException Locked="false" Priority="61" Name="Light List Accent 3"/>
<w:LsdException Locked="false" Priority="62" Name="Light Grid Accent 3"/>
<w:LsdException Locked="false" Priority="63" Name="Medium Shading 1 Accent 3"/>
<w:LsdException Locked="false" Priority="64" Name="Medium Shading 2 Accent 3"/>
<w:LsdException Locked="false" Priority="65" Name="Medium List 1 Accent 3"/>
<w:LsdException Locked="false" Priority="66" Name="Medium List 2 Accent 3"/>
<w:LsdException Locked="false" Priority="67" Name="Medium Grid 1 Accent 3"/>
<w:LsdException Locked="false" Priority="68" Name="Medium Grid 2 Accent 3"/>
<w:LsdException Locked="false" Priority="69" Name="Medium Grid 3 Accent 3"/>
<w:LsdException Locked="false" Priority="70" Name="Dark List Accent 3"/>
<w:LsdException Locked="false" Priority="71" Name="Colorful Shading Accent 3"/>
<w:LsdException Locked="false" Priority="72" Name="Colorful List Accent 3"/>
<w:LsdException Locked="false" Priority="73" Name="Colorful Grid Accent 3"/>
<w:LsdException Locked="false" Priority="60" Name="Light Shading Accent 4"/>
<w:LsdException Locked="false" Priority="61" Name="Light List Accent 4"/>
<w:LsdException Locked="false" Priority="62" Name="Light Grid Accent 4"/>
<w:LsdException Locked="false" Priority="63" Name="Medium Shading 1 Accent 4"/>
<w:LsdException Locked="false" Priority="64" Name="Medium Shading 2 Accent 4"/>
<w:LsdException Locked="false" Priority="65" Name="Medium List 1 Accent 4"/>
<w:LsdException Locked="false" Priority="66" Name="Medium List 2 Accent 4"/>
<w:LsdException Locked="false" Priority="67" Name="Medium Grid 1 Accent 4"/>
<w:LsdException Locked="false" Priority="68" Name="Medium Grid 2 Accent 4"/>
<w:LsdException Locked="false" Priority="69" Name="Medium Grid 3 Accent 4"/>
<w:LsdException Locked="false" Priority="70" Name="Dark List Accent 4"/>
<w:LsdException Locked="false" Priority="71" Name="Colorful Shading Accent 4"/>
<w:LsdException Locked="false" Priority="72" Name="Colorful List Accent 4"/>
<w:LsdException Locked="false" Priority="73" Name="Colorful Grid Accent 4"/>
<w:LsdException Locked="false" Priority="60" Name="Light Shading Accent 5"/>
<w:LsdException Locked="false" Priority="61" Name="Light List Accent 5"/>
<w:LsdException Locked="false" Priority="62" Name="Light Grid Accent 5"/>
<w:LsdException Locked="false" Priority="63" Name="Medium Shading 1 Accent 5"/>
<w:LsdException Locked="false" Priority="64" Name="Medium Shading 2 Accent 5"/>
<w:LsdException Locked="false" Priority="65" Name="Medium List 1 Accent 5"/>
<w:LsdException Locked="false" Priority="66" Name="Medium List 2 Accent 5"/>
<w:LsdException Locked="false" Priority="67" Name="Medium Grid 1 Accent 5"/>
<w:LsdException Locked="false" Priority="68" Name="Medium Grid 2 Accent 5"/>
<w:LsdException Locked="false" Priority="69" Name="Medium Grid 3 Accent 5"/>
<w:LsdException Locked="false" Priority="70" Name="Dark List Accent 5"/>
<w:LsdException Locked="false" Priority="71" Name="Colorful Shading Accent 5"/>
<w:LsdException Locked="false" Priority="72" Name="Colorful List Accent 5"/>
<w:LsdException Locked="false" Priority="73" Name="Colorful Grid Accent 5"/>
<w:LsdException Locked="false" Priority="60" Name="Light Shading Accent 6"/>
<w:LsdException Locked="false" Priority="61" Name="Light List Accent 6"/>
<w:LsdException Locked="false" Priority="62" Name="Light Grid Accent 6"/>
<w:LsdException Locked="false" Priority="63" Name="Medium Shading 1 Accent 6"/>
<w:LsdException Locked="false" Priority="64" Name="Medium Shading 2 Accent 6"/>
<w:LsdException Locked="false" Priority="65" Name="Medium List 1 Accent 6"/>
<w:LsdException Locked="false" Priority="66" Name="Medium List 2 Accent 6"/>
<w:LsdException Locked="false" Priority="67" Name="Medium Grid 1 Accent 6"/>
<w:LsdException Locked="false" Priority="68" Name="Medium Grid 2 Accent 6"/>
<w:LsdException Locked="false" Priority="69" Name="Medium Grid 3 Accent 6"/>
<w:LsdException Locked="false" Priority="70" Name="Dark List Accent 6"/>
<w:LsdException Locked="false" Priority="71" Name="Colorful Shading Accent 6"/>
<w:LsdException Locked="false" Priority="72" Name="Colorful List Accent 6"/>
<w:LsdException Locked="false" Priority="73" Name="Colorful Grid Accent 6"/>
<w:LsdException Locked="false" Priority="19" QFormat="true"
Name="Subtle Emphasis"/>
<w:LsdException Locked="false" Priority="21" QFormat="true"
Name="Intense Emphasis"/>
<w:LsdException Locked="false" Priority="31" QFormat="true"
Name="Subtle Reference"/>
<w:LsdException Locked="false" Priority="32" QFormat="true"
Name="Intense Reference"/>
<w:LsdException Locked="false" Priority="33" QFormat="true" Name="Book Title"/>
<w:LsdException Locked="false" Priority="37" SemiHidden="true"
UnhideWhenUsed="true" Name="Bibliography"/>
<w:LsdException Locked="false" Priority="39" SemiHidden="true"
UnhideWhenUsed="true" QFormat="true" Name="TOC Heading"/>
<w:LsdException Locked="false" Priority="41" Name="Plain Table 1"/>
<w:LsdException Locked="false" Priority="42" Name="Plain Table 2"/>
<w:LsdException Locked="false" Priority="43" Name="Plain Table 3"/>
<w:LsdException Locked="false" Priority="44" Name="Plain Table 4"/>
<w:LsdException Locked="false" Priority="45" Name="Plain Table 5"/>
<w:LsdException Locked="false" Priority="40" Name="Grid Table Light"/>
<w:LsdException Locked="false" Priority="46" Name="Grid Table 1 Light"/>
<w:LsdException Locked="false" Priority="47" Name="Grid Table 2"/>
<w:LsdException Locked="false" Priority="48" Name="Grid Table 3"/>
<w:LsdException Locked="false" Priority="49" Name="Grid Table 4"/>
<w:LsdException Locked="false" Priority="50" Name="Grid Table 5 Dark"/>
<w:LsdException Locked="false" Priority="51" Name="Grid Table 6 Colorful"/>
<w:LsdException Locked="false" Priority="52" Name="Grid Table 7 Colorful"/>
<w:LsdException Locked="false" Priority="46"
Name="Grid Table 1 Light Accent 1"/>
<w:LsdException Locked="false" Priority="47" Name="Grid Table 2 Accent 1"/>
<w:LsdException Locked="false" Priority="48" Name="Grid Table 3 Accent 1"/>
<w:LsdException Locked="false" Priority="49" Name="Grid Table 4 Accent 1"/>
<w:LsdException Locked="false" Priority="50" Name="Grid Table 5 Dark Accent 1"/>
<w:LsdException Locked="false" Priority="51"
Name="Grid Table 6 Colorful Accent 1"/>
<w:LsdException Locked="false" Priority="52"
Name="Grid Table 7 Colorful Accent 1"/>
<w:LsdException Locked="false" Priority="46"
Name="Grid Table 1 Light Accent 2"/>
<w:LsdException Locked="false" Priority="47" Name="Grid Table 2 Accent 2"/>
<w:LsdException Locked="false" Priority="48" Name="Grid Table 3 Accent 2"/>
<w:LsdException Locked="false" Priority="49" Name="Grid Table 4 Accent 2"/>
<w:LsdException Locked="false" Priority="50" Name="Grid Table 5 Dark Accent 2"/>
<w:LsdException Locked="false" Priority="51"
Name="Grid Table 6 Colorful Accent 2"/>
<w:LsdException Locked="false" Priority="52"
Name="Grid Table 7 Colorful Accent 2"/>
<w:LsdException Locked="false" Priority="46"
Name="Grid Table 1 Light Accent 3"/>
<w:LsdException Locked="false" Priority="47" Name="Grid Table 2 Accent 3"/>
<w:LsdException Locked="false" Priority="48" Name="Grid Table 3 Accent 3"/>
<w:LsdException Locked="false" Priority="49" Name="Grid Table 4 Accent 3"/>
<w:LsdException Locked="false" Priority="50" Name="Grid Table 5 Dark Accent 3"/>
<w:LsdException Locked="false" Priority="51"
Name="Grid Table 6 Colorful Accent 3"/>
<w:LsdException Locked="false" Priority="52"
Name="Grid Table 7 Colorful Accent 3"/>
<w:LsdException Locked="false" Priority="46"
Name="Grid Table 1 Light Accent 4"/>
<w:LsdException Locked="false" Priority="47" Name="Grid Table 2 Accent 4"/>
<w:LsdException Locked="false" Priority="48" Name="Grid Table 3 Accent 4"/>
<w:LsdException Locked="false" Priority="49" Name="Grid Table 4 Accent 4"/>
<w:LsdException Locked="false" Priority="50" Name="Grid Table 5 Dark Accent 4"/>
<w:LsdException Locked="false" Priority="51"
Name="Grid Table 6 Colorful Accent 4"/>
<w:LsdException Locked="false" Priority="52"
Name="Grid Table 7 Colorful Accent 4"/>
<w:LsdException Locked="false" Priority="46"
Name="Grid Table 1 Light Accent 5"/>
<w:LsdException Locked="false" Priority="47" Name="Grid Table 2 Accent 5"/>
<w:LsdException Locked="false" Priority="48" Name="Grid Table 3 Accent 5"/>
<w:LsdException Locked="false" Priority="49" Name="Grid Table 4 Accent 5"/>
<w:LsdException Locked="false" Priority="50" Name="Grid Table 5 Dark Accent 5"/>
<w:LsdException Locked="false" Priority="51"
Name="Grid Table 6 Colorful Accent 5"/>
<w:LsdException Locked="false" Priority="52"
Name="Grid Table 7 Colorful Accent 5"/>
<w:LsdException Locked="false" Priority="46"
Name="Grid Table 1 Light Accent 6"/>
<w:LsdException Locked="false" Priority="47" Name="Grid Table 2 Accent 6"/>
<w:LsdException Locked="false" Priority="48" Name="Grid Table 3 Accent 6"/>
<w:LsdException Locked="false" Priority="49" Name="Grid Table 4 Accent 6"/>
<w:LsdException Locked="false" Priority="50" Name="Grid Table 5 Dark Accent 6"/>
<w:LsdException Locked="false" Priority="51"
Name="Grid Table 6 Colorful Accent 6"/>
<w:LsdException Locked="false" Priority="52"
Name="Grid Table 7 Colorful Accent 6"/>
<w:LsdException Locked="false" Priority="46" Name="List Table 1 Light"/>
<w:LsdException Locked="false" Priority="47" Name="List Table 2"/>
<w:LsdException Locked="false" Priority="48" Name="List Table 3"/>
<w:LsdException Locked="false" Priority="49" Name="List Table 4"/>
<w:LsdException Locked="false" Priority="50" Name="List Table 5 Dark"/>
<w:LsdException Locked="false" Priority="51" Name="List Table 6 Colorful"/>
<w:LsdException Locked="false" Priority="52" Name="List Table 7 Colorful"/>
<w:LsdException Locked="false" Priority="46"
Name="List Table 1 Light Accent 1"/>
<w:LsdException Locked="false" Priority="47" Name="List Table 2 Accent 1"/>
<w:LsdException Locked="false" Priority="48" Name="List Table 3 Accent 1"/>
<w:LsdException Locked="false" Priority="49" Name="List Table 4 Accent 1"/>
<w:LsdException Locked="false" Priority="50" Name="List Table 5 Dark Accent 1"/>
<w:LsdException Locked="false" Priority="51"
Name="List Table 6 Colorful Accent 1"/>
<w:LsdException Locked="false" Priority="52"
Name="List Table 7 Colorful Accent 1"/>
<w:LsdException Locked="false" Priority="46"
Name="List Table 1 Light Accent 2"/>
<w:LsdException Locked="false" Priority="47" Name="List Table 2 Accent 2"/>
<w:LsdException Locked="false" Priority="48" Name="List Table 3 Accent 2"/>
<w:LsdException Locked="false" Priority="49" Name="List Table 4 Accent 2"/>
<w:LsdException Locked="false" Priority="50" Name="List Table 5 Dark Accent 2"/>
<w:LsdException Locked="false" Priority="51"
Name="List Table 6 Colorful Accent 2"/>
<w:LsdException Locked="false" Priority="52"
Name="List Table 7 Colorful Accent 2"/>
<w:LsdException Locked="false" Priority="46"
Name="List Table 1 Light Accent 3"/>
<w:LsdException Locked="false" Priority="47" Name="List Table 2 Accent 3"/>
<w:LsdException Locked="false" Priority="48" Name="List Table 3 Accent 3"/>
<w:LsdException Locked="false" Priority="49" Name="List Table 4 Accent 3"/>
<w:LsdException Locked="false" Priority="50" Name="List Table 5 Dark Accent 3"/>
<w:LsdException Locked="false" Priority="51"
Name="List Table 6 Colorful Accent 3"/>
<w:LsdException Locked="false" Priority="52"
Name="List Table 7 Colorful Accent 3"/>
<w:LsdException Locked="false" Priority="46"
Name="List Table 1 Light Accent 4"/>
<w:LsdException Locked="false" Priority="47" Name="List Table 2 Accent 4"/>
<w:LsdException Locked="false" Priority="48" Name="List Table 3 Accent 4"/>
<w:LsdException Locked="false" Priority="49" Name="List Table 4 Accent 4"/>
<w:LsdException Locked="false" Priority="50" Name="List Table 5 Dark Accent 4"/>
<w:LsdException Locked="false" Priority="51"
Name="List Table 6 Colorful Accent 4"/>
<w:LsdException Locked="false" Priority="52"
Name="List Table 7 Colorful Accent 4"/>
<w:LsdException Locked="false" Priority="46"
Name="List Table 1 Light Accent 5"/>
<w:LsdException Locked="false" Priority="47" Name="List Table 2 Accent 5"/>
<w:LsdException Locked="false" Priority="48" Name="List Table 3 Accent 5"/>
<w:LsdException Locked="false" Priority="49" Name="List Table 4 Accent 5"/>
<w:LsdException Locked="false" Priority="50" Name="List Table 5 Dark Accent 5"/>
<w:LsdException Locked="false" Priority="51"
Name="List Table 6 Colorful Accent 5"/>
<w:LsdException Locked="false" Priority="52"
Name="List Table 7 Colorful Accent 5"/>
<w:LsdException Locked="false" Priority="46"
Name="List Table 1 Light Accent 6"/>
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<br />
<span style="font-size: small;"><span style="font-family: inherit;">Unless
you (and your Facebook news feed) have been living under a rock, you know about
the <a href="https://www.nasa.gov/mission_pages/newhorizons/overview/index.html">New Horizons mission to explore Pluto</a>, a mission 9 years in the making. The new high-resolution images have shown us both
that Pluto loves us (i.e. the heart-shaped region in the southern hemisphere),
and it is blushing from all the attention (its red-orange surface). While
astronomers have known the color of Pluto’s surface for years, the high-resolution
images clearly outline the terrain on the dwarf planet. But <a href="https://www.nasa.gov/nh/pluto-the-other-red-planet">why is Pluto red</a>?
The reason may not be the same as you think – and by that, I mean it’s not for
the same reason why Mars is red. It’s
actually because of some cool chemical reactions between methane & nitrogen
with the help of some ultraviolet light and other cosmic rays to produce
tholins, long-thought to be crucial to the existence of a “primordial soup”.</span></span><br />
<a name='more'></a><br />
<span style="font-size: small;"><span style="font-family: inherit;">Mars
is red as a result of the oxidation of iron on the surface of the planet to
form iron oxide (rust), primarily in the form of hematite. Hematite is a deep red semiconductor that
absorbs in the visible region of the spectrum, and is one of the most abundant
materials on the Earth. However, rust is not what causes Pluto’s
terrain to be a similar color. This
color comes from the formation of a class of chemicals called tholin (Greek for
“muddy”). These deposits form as a
result of <a href="http://w.astro.berkeley.edu/~jcohn/lya.html">Lyman-alpha</a>
waves, a specific range of the ultraviolet spectrum emitted from the Sun. Methane
(CH<sub>4</sub>) and nitrogen gas (N<sub>2</sub>) in Pluto’s thin atmosphere
absorb energy from Lyman-alpha waves and other cosmic rays. They spend that
energy in reactions that form a plethora of nitrogen-containing compounds such
as nitriles, dinitriles, etc., believed to have been created through
photo-generated radicals of methane and nitrogen. These larger molecules
undergo subsequent chain reactions, eventually forming high-molecular weight,
nitrogen-rich molecules that fall to the surface. Recently, researchers have
not only suggested that tholins are capable of hydrolyzing to biomolecules in
the presence of water and ammonia, but that these organic molecules are
precursors needed to produce organic-based life (a “primordial soup” for those
who love buzz words). There is a
fantastic <a href="http://pubs.acs.org/doi/abstract/10.1021/cr200221x"><i>review in Chemical Reviews ($)</i></a> entirely dedicated
to the efforts of reproducing tholin synthesis here on Earth, and understanding
the mechanisms by which it is formed and consumed on Titan, one of Saturn’s
moons.</span></span><br />
<span style="font-size: small;"><span style="font-family: inherit;"><br /></span></span>
<img alt="" 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/><br />
<span style="font-size: small;"><span style="font-family: inherit;"><br /></span></span>
While life probably doesn’t exist
on the surface of Pluto due to the cold temperatures (it’s practically a
billion degrees below zero out there… but seriously it’s ~40 K, or <a href="http://coolcosmos.ipac.caltech.edu/ask/155-How-cold-is-it-on-Pluto-">-233ºC</a>),
it does give scientists some useful insight into these types of reactions that
happen or might have happened previously on other planets in our solar system. It also helps determine rock formation
processes that might be similar to those found here on Earth. Learning about how higher-order organic
molecules are formed through the reaction of N<sub>2</sub> and CH<sub>4</sub>
with cosmic rays can also help us better understand how common this process
actually is, and if it really is something from which life could have arisen. However, what lies beneath Pluto’s surface,
and other celestial bodies in our solar system like Titan or Mars, is somewhat
of a mystery, with evidence to suggest ice or liquid water under their surfaces.<br />
<br />
<span style="font-size: small;"><span style="font-family: inherit;">Understanding tholin
chemistry is one interesting piece of the larger puzzle of our solar system’s
chemistry. Physicists have known for a very long time that the raw materials
for matter – carbon, hydrogen, and nitrogen atoms, for example – are formed in
dying stars and released by supernovae. However, that’s just the first step in
creating organic matter. The processes by which those atoms were pieced
together and rearranged into more complicated molecules such as tholins in the
early solar system largely remain mysterious.
In a study from 2010, researchers at The Ohio State University in
Columbus, Ohio published <a href="http://online.liebertpub.com/doi/abs/10.1089/ast.2009.0402">experiments creating tholins similar to those found on Titan ($)</a> (Saturn’s largest moon) in the lab. The authors hydrolyzed them using
ammonia-water mixtures similar to compositions found on Saturn’s moon. After a year of reaction with water at -20 ºC
and +20ºC, they discovered evidence of 6 biomolecules synthesized from Titan’s
tholin, listed below.</span></span><br />
<div align="center">
<img alt="" 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" /></div>
Other groups in the astrobiology field have seen similar
results, concluding that the tholin precursors to more complicated biomolecules
can be hydrolyzed under other various conditions to form amino acids like
glycine, DL-alanine,
and other compounds listed above (Cleaves 2014), particularly when dissolved in
water (tholins + water + energy = biomolecules). Ready for the punch line? All of these compounds are considered
building blocks for DNA and proteins in the organisms found on Earth! In
addition, there is evidence to suggest that Titan, a moon with a surface
temperature of 94 K, could potentially hold liquid water for up to 10<sup>4</sup>
years before freezing due to impacts of cryovolcanism, which is
why Titan has seen so much attention recently.<br />
<br />
<span style="font-size: small;"><span style="font-family: inherit;">Although there is absolutely no evidence to suggest life
is on Pluto (sad face), we do believe that its
color comes from the existence of tholin precipitated from the dwarf planet’s
thin atmosphere based on observations from Titan. And while liquid water
might not exist on Pluto’s surface to convert tholin to useful biomolecules, it may exist on Titan (along
with rivers of methane – cause you know, it’s space). However, <a href="http://scitechdaily.com/data-from-nasas-new-horizons-hints-at-underground-ocean-on-pluto/">new
data</a> collected from New Horizons suggests the existence of oceans inside
Pluto surrounding its rocky core! It’s
quite fascinating how common tholin is believed to exist just within our solar
system. Carl Sagan <a href="http://www.nature.com/nature/journal/v277/n5692/abs/277102a0.html">discussed this in a paper published in 1979 ($)</a>, back when he and <a href="http://www.seti.org/bishun-khare">Bishun Khare</a> first synthesized
tholin in the lab from methane and other basic hydrocarbons. In the paper, he and Khare state that “we
have discussed this material as a constituent of the Earth’s primitive oceans
and therefore as relevant to the origin of life; as a component of red aerosols
in the atmospheres of the outer planets and Titan; as present in comets,
carbonaceous chondrites, and pre-planetary solar nebulae; and as a major
constituent of the interstellar medium…”. To put it simply – this stuff is everywhere, and it could be an
important component in the processes that may have started life here on Earth.</span></span><br />
<br />
<span style="font-size: small;"><span style="font-family: inherit;"><i><span style="font-family: inherit;">Sam Esarey is a 3rd year PhD candidate from Blairsville, Pennsylvania working in the Bartlett group at the University of Michigan. He received his B.S. in Chemistry with a minor in Physics from Denison University in 2013, and currently works on driving selective chemical reactions on light-absorbing semiconductors using sunlight. Feel free to follow him on Twitter @SamEsarey, where he hasn’t posted a serious tweet since 2014.</span></i> </span></span>Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com6tag:blogger.com,1999:blog-1971936738593606253.post-56436995338659398842015-07-21T12:10:00.002-04:002015-07-21T12:10:31.825-04:00Chemistry Buzzword DictionaryUnderstanding scientific literature can be hard. Let's face it: scientists, despite all our claims to the contrary, love words. We love making words up and flaunting them about - and bonus points if they're pronouncable <a href="http://www.acronymslist.com/cat/chemistry-acronyms.html">acronyms</a>.<br />
<br />
Some chemistry words, however, are <a href="https://en.wikipedia.org/wiki/Alexander_Ovechkin">unnecessarily flashy and find their way into headlines a little too often</a>. Buzzwords can be misleading at worst, and tiresome at best.<br />
<br />
If you're trying to understand the chemical literature but keep getting tripped up in the jargon, have no fear. Because I care about <i>you</i>, my dearest readers, I've assembled a list of some of the most common chemistry buzzwords along with clear, concise definitions or, where quotations are used, what the authors probably could have said instead. Armed with this reference, you'll be an unstoppable scientific critic from this point forward.<br />
<br />
<i><b>asymmetric catalysis/reaction: </b></i>"We spent a lot of money on ligands. A <i>lot</i>."<br />
<br />
<i><b>biomimetic:</b></i> has the same metal as a protein that does the reaction faster and better than the molecule under study<br />
<br />
<i><b>challenge:</b></i> something scientists collectively have not figured out yet; what the authors think about to prevent themselves from getting too happy<br />
<br />
<i><b>divergent synthesis: </b></i>"Turns out you can do more than one reaction on the same molecule!"<br />
<br />
<i><b>(photo)electrochemical: </b></i>(even more) questionably relevant<br />
<br />
<i><b>elusive:</b></i> "difficult to make, but come on, that's not <i>our</i> fault."<br />
<br />
<i><b>"from first principles": </b></i>"We have successfully avoided wet labs since undergrad."<br />
<br />
<i><b>ionic liquid: </b></i>salts that are liquid at or near room temperature; definitely not a fad<br />
<br />
<i><b>limitation:</b></i> what happens when physics gets in the way<br />
<br />
<i><b>"mechanistic insight": </b></i>the next best thing to guessing<br />
<br />
<i><b>nano[noun or adjective]:</b></i> oh god please publish this<br />
<br />
<i><b>novel:</b></i> a meaningless adjective<br />
<br />
<i><b>public engagement:</b></i> Twitter<br />
<br />
<i><b>serendipitous:</b></i> accidental<br />
<br />
<i><b>synthesis: </b></i>what the authors do when they're not on Facebook<br />
<br />
<i><b>transformation: </b></i>seriously just a reaction<br />
<br />
<i><b>ultrafast:</b></i> The last time the authors came to your party, they just repeated, "I work with a big fancy laser" until they were either unanimously acknowledged as the coolest person in the room or were later found repeating "I work with a big fancy laser" shakily to themselves in a corner with their drink and all of your chips.<br />
<br />
I hope that this will serve as a valuable tool for your future forays into the scientific literature. No citations will be necessary; everyone knows that scientists don't <i>really</i> care about their H-indexes.<br />
<br />
<i>This article has been submitted to <a href="https://lostinscientia.wordpress.com/2014/01/12/new-sister-journal-to-nature-chemistry/">Nature BuzzChem</a>, pending review by its prestigious board of editors.</i>Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com1tag:blogger.com,1999:blog-1971936738593606253.post-17635124773161723952015-07-15T15:21:00.002-04:002015-07-15T15:32:23.565-04:00Chemistry Literature Feature, Vol. X<br />
<b><i>Have you seen a good paper lately? Written one? Send it in and have it featured here! </i></b><a href="mailto:treetownchem@gmail.com">treetownchem@gmail.com</a><br />
<br />
It's the tenth blog-o-versary of the Chemistry Literature Feature! In celebration, here are ten (minus four) cool chemistry papers, one from each of the chemical disciplines. This time, we'll learn what gives the "sea sapphire" its color, see single molecules of proteins stick to a platinum surface, and see a new technique for learning about the fate of photoexcited electrons in an important photocatalyst material.<br />
<br />
Don't know what a sea sapphire is? Neither did I!<br />
<br />
<i><b>Analytical </b></i>- <i>Observation of Single-Protein and DNA Macromolecule Collisions on Ultramicroelectrodes</i><br />
Chemistry is typically understood "in the ensemble" - that is, a large number of atoms or molecules are observed simultaneously. Recently, particularly in spectroscopic fields, researchers have gone to great lengths to investigate single-molecule systems where ensemble behavior is impossible. The authors of <a href="http://pubs.acs.org/doi/abs/10.1021/jacs.5b04545">this communication ($)</a> in the Journal of the American Chemical Society designed an experiment where large molecules - proteins, polystyrene beads, and strands of DNA - were placed in solution with an <a href="http://www.cnrs.fr/cnrs-images/chimieaulycee/THEMES/electrolyse/Mozaik/8foto7.jpg">extremely small</a> platinum electrode (linked photo shows a carbon fiber ultramicroelectrode). These "insulating objects" block the flow of electric current from the electrode. The study examines how the size and shape of the objects contribute to the observed changes in the current and paves the way for further investigation into macromolecule behavior in solution via electrochemical methods - without the use of a complicated laser.<br />
<br />
<i><b>Chemical Biology</b> - Structural Basis for the Brilliant Colors of Sapphirinid Copepods</i><br />
I never thought I would learn of an animal's existence from the Journal of the American Chemical Society, but the authors of <a href="http://pubs.acs.org/doi/abs/10.1021/jacs.5b05289">this communication ($)</a> took an interest in figuring out what gives color to the sapphirinid copepod. <a href="http://www.deepseanews.com/2014/02/the-most-beautiful-animal-youve-never-seen/">Sappirinid copepods are millimeter-sized animals</a> similar to plankton that inhabit oceans around the globe. The males have crystalline shells that scatter light, <a href="http://www.liquidguru.com/octopod-copepod/">creating brilliant flashes of color</a> when the sun hits them just right - an evolutionary adaptation known as "death wish."* The communication explains why different copepods flash different colors. The authors used scanning electron microscopy to examine the crystal sizes in the copepod shells and also the thickness of the liquid cytoplasm layer between the crystal layers, finding that copepods of different colors show differences in the cytoplasm layer thickness rather than crystal size. The variance in spacing between the crystals in the copepod shells gives rise to the observed colors via photonic effects similar to <a href="https://en.wikipedia.org/wiki/Opal">what gives opals their colors</a>.<br />
<br />
*: editorial, sort of<br />
<i></i><br />
<i><b>Inorganic</b></i> <i>- A Stable Planar-Chiral </i>N<i>-Heterocyclic Carbene with a 1,1'-Ferrocenediyl Backbone</i><br />
<a href="http://chemwiki.ucdavis.edu/Inorganic_Chemistry/Organometallic_Chemistry/Ligands/N-heterocyclic_Carbenes">N-heterocyclic carbenes</a> (NHCs) are some of the most interesting ligands in organometallic chemistry. Sad graduate students have synthesized hundreds of NHCs by varying the size and electronic properties of substituents near the carbene site, and the fruits of these modifications are often made manifest in the catalytic properties of metal-NHC complexes. Traditional NHC ligands are based on a 5-membered imidazole ring. Lately, however, synthetic chemists have explored NHCs with larger rings, showing that straining the bond angles near the carbene increases its reactivity. The authors of <a href="http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.5b01064">this recent paper ($)</a> in Inorganic Chemistry (ACS) perform a thorough investigation of a new series of 6-membered NHCs made chiral by a <a href="http://www.periodicvideos.com/videos/mv_ferrocene.htm">ferrocene</a> backbone. Their NHC molecule is extremely reactive and is capable reacting with dichloromethane and acetonitrile. The authors go on to characterize the compound electrochemically in preparation for future synthetic work to take advantage of its chirality.<br />
<br />
<b><i>Materials</i></b><i> - Fabrication of Self-Cleaning, Reusable Titania Templates for Nanometer and Micrometer Scale Protein Patterning</i><br />
Biological sensing technologies are becoming smaller and smaller, and nanopatterned arrays created using laser etching methods are emerging to the forefront of miniaturization efforts. Both for research and commercial applications, easily-renewed biosensor arrays are cost-effective and attractive. The authors of <a href="http://pubs.acs.org/doi/abs/10.1021/acsnano.5b01636">this paper ($)</a> in ACS Nano present a method for decorating a titanium dioxide surface with organic groups capable of binding proteins. A separate step makes the rest of the surface inert to proteins, allowing the authors to bind proteins in an array pattern in specific locations on the film. This is supported with fluorescence microscopy, which causes the proteins to light up and determines where they are. The protein-bound film can function as a biosensor. Importantly, though, the authors demonstrate that shining strong ultraviolet light on the film causes the titanium oxide to chew up all the proteins, leaving the film surface free to bind a new set of proteins and create a new biosensor from the recycled surface.<br />
<i> </i><br />
<br />
Materials chemistry readers will get an especial kick out of the Chemical Biology article as well.<br />
<br />
<i><b>Organic </b>- Base-Promoted <span style="font-family: "Times New Roman",serif; font-size: 11.0pt; line-height: 107%; mso-ansi-language: EN-US; mso-bidi-language: AR-SA; mso-fareast-font-family: Calibri; mso-fareast-language: EN-US; mso-fareast-theme-font: minor-latin;">β</span>-C(sp<sup>3</sup>)-H Functionalization of Enaminones: An Approach to Polysubstituted Pyridines</i><br />
If you've ever studied or practiced organic chemistry, you know that the reactions can quickly become an excessive soup of starting materials, acids or bases, catalysts, solvents, and additives. In addition to adding up in terms of complexity, all of these reagents contribute to the cost of a reaction, both energetically, monetarily, and environmentally. The group who published <a href="http://pubs.acs.org/doi/abs/10.1021/acs.joc.5b00635">this recent paper ($)</a> in the Journal of Organic Chemistry (ACS) has discovered a very simple base-promoted route for joining ynones to ethylamines for the production of pyridine rings. With only two equivalents of base, the two molecules snap together like Legos, then eliminate water to yield the pyridine product. Pyridines are useful throughout organic chemistry, both as structural motifs and also as common binding sites for metals, so a convenient and versatile route (34 pyridines reported!) such as this could be quite useful.<br />
<br />
<b><i>Physical</i></b><i> - Chronoabsorptometry To Investigate Conduction-Band-Mediated Electron Transfer in Mesoporoous TiO<sub>2</sub> Thin Films</i><br />
Photochemical processes - like solar cells, for example - depend on the ability of an excited-state electron to move throughout a material to a site where it can do useful work. However, a bunch of things can happen to it along the way, and simple methods to understand these various processes and, critically, how quickly they happen relative to one another, are in short supply.<i> </i>A <a href="http://pubs.acs.org/doi/abs/10.1021/acs.jpcc.5b03477">new paper ($)</a> in the Journal of Physical Chemistry C (ACS) provides a thorough mathematical introduction to a technique called chronoabsorptometry, in which optical spectroscopy is used to keep track of the state of a probe molecule bound to the surface of the TiO2 under study. The electronic properties of the TiO<sub>2</sub> film are controlled separately by an electrical potential. The authors vary the potential while watching the probe to learn more about how photoexcited electrons move through the film. By matching their results with previously published conclusions from other, more widely-used techniques, the authors are able to verify the validity of their method.<br />
<br />
<b style="font-style: italic;">Remember, </b><i>if you come across an article that you think should be featured here, </i><b style="font-style: italic;">send it in! </b><a href="mailto:treetownchem@gmail.com">treetownchem@gmail.com</a><br />
<br />
<span style="color: #999999;"><i>ACS - American Chemical Society</i></span><br />
<span style="color: #999999;"><i>GDCh - Gesellschaft Deutscher Chemiker (German Chemical Society)<br />RSC - Royal Society of Chemistry</i></span><br />
<span style="color: #999999;"><i>$ - subscription required to access full text</i></span>Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com1tag:blogger.com,1999:blog-1971936738593606253.post-31025187996603551102015-07-01T15:03:00.004-04:002015-07-01T15:38:13.413-04:00Winter is Coming: Icy Lab Monitors Toxic Gases in Atmosphere<i>Congratulations to the winner of the first Tree Town Chemistry photo contest! The photo and the original caption are below. Read to the end of the article to see the runners-up and other entries from this year's contest.</i><br />
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<div class="separator" style="clear: both; text-align: center;">
<a href="http://2.bp.blogspot.com/-cU6JYWKLWpQ/VZGWQGReQZI/AAAAAAAAAYQ/h4e1ltOIm7c/s1600/Liquid%2BNitro.jpg" imageanchor="1" style="clear: left; float: left; margin-bottom: 1em; margin-right: 1em;"><img border="0" height="300" src="http://2.bp.blogspot.com/-cU6JYWKLWpQ/VZGWQGReQZI/AAAAAAAAAYQ/h4e1ltOIm7c/s400/Liquid%2BNitro.jpg" width="400" /></a></div>
Every day in lab is a winter wonderland. I operate two gas chromatography-mass spectrometers, analyzing ambient air samples for toxic materials. Each system uses almost an entire tank of liquid nitrogen a day to cool the preconcentrator gas traps. The amount of snow and ice formed on the tanks and transfer lines each day are enough to have a full snowball fight, and once a tank is empty, it can take up to 24 hours to melt enough to swap out for a new tank.<br />
<br />
<br />
<a name='more'></a>What is that you're breathing now? Is it clean air? Car exhaust? If your air is clean now in July, will it still be clean in December?<br />
<br />
Don't worry about it. Chemists are on the case.<br />
<i><br /></i>
Dan Gardner, a recent M.S. Chemistry graduate of the University of Michigan, works in a<a href="http://www.mde.state.md.us/Pages/Home.aspx"> Maryland Department of the Environment (MDE)</a> air toxics laboratory that monitors air quality throughout the state. MDE works with the federal Environmental Protection Agency to keep an eye on the quality of air across the country.<br />
<br />
Part of the work of the Air & Radiation division of the EPA is to record levels of hundreds of air pollutants from locations all over the United States. In particular, the <a href="http://www.epa.gov/airtrends/index.html">EPA watches levels of six especially important pollutants</a> for which "national standards" - maximum allowable levels - have been established. Carbon monoxide, sulfur dioxide, nitrogen dioxide, dust, lead, and ozone are all regulated.<br />
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<a href="http://www.epa.gov/airdata/ad_maps.html">Air monitoring locations for the EPA</a> and for <a href="http://www.mde.state.md.us/programs/Air/AirQualityMonitoring/Pages/Network.aspx">state-run agencies like the MDE</a> exist all over the country. A team of scientists works at each one to collect samples of the air that we, all of our plants, and all of our livestock breathe. Samples can be collected in a few different forms depending on what they will be used for. Then the samples are carted off to the analysis labs.<br />
<br />
<table cellpadding="0" cellspacing="0" class="tr-caption-container" style="float: left; margin-right: 1em; text-align: left;"><tbody>
<tr><td style="text-align: center;"><a href="http://4.bp.blogspot.com/-mLtNE4UMnSk/VZMRePPhPKI/AAAAAAAAAaA/dhih-STfeHo/s1600/dan.jpg" imageanchor="1" style="clear: left; margin-bottom: 1em; margin-left: auto; margin-right: auto;"><img border="0" height="320" src="http://4.bp.blogspot.com/-mLtNE4UMnSk/VZMRePPhPKI/AAAAAAAAAaA/dhih-STfeHo/s320/dan.jpg" width="240" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">Dan Gardner, an air toxics chemist at the<br />
Maryland Department of the Environment.<br />
(He's on your side, not the pollution's.)</td></tr>
</tbody></table>
That's where Dan comes in. Samples from the sites come in at far too high of a concentration for analysis, so part of Dan's job is to carefully dilute the samples to a strength that the instruments can handle. He also prepares standards - samples with a known composition that are run along with the environmental samples - to ensure that the instrument is properly tuned.<br />
<br />
The team Dan works with is specifically quantifying volatile organic
compounds (VOCs) in the atmosphere. These harmful compounds come from a
wide number of sources but are most typically used as refrigerants or
industrial solvents, or are produced as car exhaust. The EPA compiles
the data and <a href="http://www.epa.gov/airtrends/reports.html">offers freely available air quality reports</a> that show how
the concentrations of all sorts of airborne pollutants change over time. <br />
<br />
What does the work? "I operate two separate gas chromatography/mass spectrometers (GC/MS). I run every sample on both of them and compare the results," Dan writes. The GC/MS is actually two instruments coupled together. Inside the gas chromatograph, a vaporized sample is pushed through a column by an inert carrier gas. The column is made of a material that separates the components of the sample based on some chosen property, most typically polarity. After flying through the gas chromatography column, the sample components reach the next step of the process at different times, which allows them to be detected independently of one another.<br />
<br />
In the case of GC/MS, the next step is a mass spectrometer, which ionizes the sample materials and measures their mass. A <a href="http://treetownchem.blogspot.com/2014/12/astrochemistry-in-action-rosetta.html">mass spectrometer was used by the Philae probe</a> last year to answer questions about the origin of water on Earth. Mass spectrometers can also give structural information that is often critical in identifying compounds. GC/MS is a very powerful tandem measurement and is useful across nearly every discipline of chemistry.<br />
<br />
The work is all carried out according to <a href="http://www.epa.gov/ttnamti1/files/ambient/airtox/to-15r.pdf">procedures written by the EPA</a>. "After the runs, I do a very basic look through the data to make sure it all seems reasonable and does not need to be re-run," Dan writes. He then hands off the test results to another member of the team that is responsible for doing a detailed analysis of the data.<br />
<br />
What you see in Dan's winning photo is the preconcentrator set-up for the GC/MS that he works on. "The preconcentrator is the fun part," he writes. "Since the concentrations of the components we are looking for are very small and many of them are volatile, this is used to compile enough in one place to be detected." The samples pass through the traps, which are cooled by liquid nitrogen to temperatures as low as -160 <span style="font-family: "Calibri",sans-serif; font-size: 11.0pt; line-height: 107%; mso-ansi-language: EN-US; mso-ascii-theme-font: minor-latin; mso-bidi-font-family: "Times New Roman"; mso-bidi-language: AR-SA; mso-bidi-theme-font: minor-bidi; mso-fareast-font-family: Calibri; mso-fareast-language: EN-US; mso-fareast-theme-font: minor-latin; mso-hansi-theme-font: minor-latin;">º</span>C. The cold temperatures force the volatile components to condense as solids or liquids and thereby prevent their escape until they're ready to be injected onto the column. <br />
<br />
"We go through a lot of liquid nitrogen. We go through 2/3 to an entire tank each run. Then multiply that by my two instruments and a third one run by a coworker... we go through a <i>lot</i> of liquid nitrogen." All that liquid nitrogen makes for some pretty frosty working conditions as water from the air is frozen onto the pipes. In fact, the ice condensing on the preconcentrator plumbing is one of the largest hang-ups Dan faces in his work. "By the end of a sequence, there's often 5-6 inches of snow and ice. Sometimes it's very powdery and can easily be swept off (or made into snowballs), but some days it's pure, solid ice and we have to take a mallet to it just to close the valve."<br />
<br />
The next time you step outside and breathe deep on a fresh, sunny day, send a thought to Dan and his teammates. You never know when all that ice will get the better of them.<br />
<br />
<hr />
<b><i>First Runner-up:</i></b> <i>Jessica Gagnon</i><br />
Jessica performs molecular dynamics simulations on receptor proteins in Dr. Charlie Brooks's lab at the University of Michigan. Research like hers helps to build accurate models of protein-pharmaceutical interactions and is an important part of modern drug discovery.<br />
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<a href="http://4.bp.blogspot.com/-ogudoYN0RH0/VZL9iZUjHGI/AAAAAAAAAYw/M_oUx4tsgFk/s1600/gagnonj_treeTownChemPhotoContest_2015.png" imageanchor="1" style="clear: left; float: left; margin-bottom: 1em; margin-right: 1em;"><img border="0" height="400" src="http://4.bp.blogspot.com/-ogudoYN0RH0/VZL9iZUjHGI/AAAAAAAAAYw/M_oUx4tsgFk/s400/gagnonj_treeTownChemPhotoContest_2015.png" width="400" /></a></div>
Protein-ligand docking has become a method integral to the drug discovery and lead optimization process. Proteins exist in an inter-converting ensemble of conformational states, but traditional docking methods kept the protein as a rigid entity for efficiency. To effectively and efficiently search the conformational space available to both the receptor and ligand I have implemented a mixed resolution approach of the receptor. As depicted in this figure, part of the receptor is represented as a series of grids while other regions are kept in an all-atom representation. This allows for ligand and receptor sampling to occur simultaneously without much loss of computational efficiency. <br />
<br />
<i><b>Second Runner-up:</b></i> <i>Jordan Boothe</i><br />
Jordan is a 4th-year graduate student working with Dr. John Wolfe in pursuit of biologically active heterocyclic compounds. He studies palladium-catalyzed reactions with the goal of adding two different nucleophiles across a carbon-carbon double bond.<br />
<i> </i><br />
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<a href="http://4.bp.blogspot.com/-yVTNIi7A9f8/VZL9ly-_K_I/AAAAAAAAAY4/MrO0uBY-3rY/s1600/Screen%2Bshot%2B2015-06-12%2Bat%2B4.33.29%2BPM.png" imageanchor="1" style="clear: left; float: left; margin-bottom: 1em; margin-right: 1em;"><img border="0" height="225" src="http://4.bp.blogspot.com/-yVTNIi7A9f8/VZL9ly-_K_I/AAAAAAAAAY4/MrO0uBY-3rY/s400/Screen%2Bshot%2B2015-06-12%2Bat%2B4.33.29%2BPM.png" width="400" /></a></div>
<i> </i>Sometimes even the most mundane days can be opportunities to find wonder. For example, I wanted to get a picture of my stirring reaction for my boss, so that I could show him my experimental setup. I ended up being able to capture the different viscosities of the oil bath in contact with the heating coil. SCIENCE!<br />
<br />
<br />
<hr />
<br />
And finally, by popular demand, here are the remainder of the photo contest entries. Thank you to everyone who entered! Choosing a winner was
difficult, and I'm looking forward to the next contest. Thanks again to
Sung-Hei Yau and Emily Nelson for helping out with the judging.<br />
<table>
<tbody>
<tr><td width="33%"><table align="center" cellpadding="0" cellspacing="0" class="tr-caption-container" style="margin-left: auto; margin-right: auto; text-align: center;"><tbody>
<tr><td style="text-align: center;"><a href="http://2.bp.blogspot.com/-Dp7ceCQ_De8/VZME_3Rp6EI/AAAAAAAAAZs/3zCvjtIjlF8/s1600/Slide2.png" imageanchor="1" style="margin-left: auto; margin-right: auto;"><img border="0" height="150" src="http://2.bp.blogspot.com/-Dp7ceCQ_De8/VZME_3Rp6EI/AAAAAAAAAZs/3zCvjtIjlF8/s200/Slide2.png" width="200" /></a></td></tr>
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am a two-dimensional infrared spectroscopist. This is a visual of the laser
setup my lab uses to study solvent dynamics on a picosecond timescale. All
optics shown are used to take an 800 nm laser beam and, through nonlinear
optical processes of optical parametric amplification and difference frequency
generation, produce four 2000 cm<sup>-1</sup> infrared pulses. These interact
with a sample and produce a signal field, which is converted back to visible
light through another nonlinear optical process called sum-frequency
generation. This is done so we can detect the signal in the visible region.
This technique is #distractinglysexy and I cry every time I think about it.<br />
<i><b>Submitted by:</b></i> Kimberly Daley<br />
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<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="List Number"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="List 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="List 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="List 4"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="List 5"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="List Bullet 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="List Bullet 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="List Bullet 4"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="List Bullet 5"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="List Number 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="List Number 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="List Number 4"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="List Number 5"/>
<w:LsdException Locked="false" Priority="10" QFormat="true" Name="Title"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Closing"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Signature"/>
<w:LsdException Locked="false" Priority="1" SemiHidden="true"
UnhideWhenUsed="true" Name="Default Paragraph Font"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Body Text"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Body Text Indent"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="List Continue"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="List Continue 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="List Continue 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="List Continue 4"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="List Continue 5"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Message Header"/>
<w:LsdException Locked="false" Priority="11" QFormat="true" Name="Subtitle"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Salutation"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Date"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Body Text First Indent"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Body Text First Indent 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Note Heading"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Body Text 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Body Text 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Body Text Indent 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Body Text Indent 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Block Text"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Hyperlink"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="FollowedHyperlink"/>
<w:LsdException Locked="false" Priority="22" QFormat="true" Name="Strong"/>
<w:LsdException Locked="false" Priority="20" QFormat="true" Name="Emphasis"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Document Map"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Plain Text"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="E-mail Signature"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Top of Form"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Bottom of Form"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Normal (Web)"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Acronym"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Address"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Cite"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Code"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Definition"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Keyboard"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Preformatted"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Sample"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Typewriter"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="HTML Variable"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Normal Table"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="annotation subject"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="No List"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Outline List 1"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Outline List 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Outline List 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Simple 1"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Simple 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Simple 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Classic 1"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Classic 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Classic 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Classic 4"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Colorful 1"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Colorful 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Colorful 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Columns 1"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Columns 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Columns 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Columns 4"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Columns 5"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Grid 1"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Grid 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Grid 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Grid 4"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Grid 5"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Grid 6"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Grid 7"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Grid 8"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table List 1"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table List 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table List 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table List 4"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table List 5"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table List 6"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table List 7"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table List 8"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table 3D effects 1"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table 3D effects 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table 3D effects 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Contemporary"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Elegant"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Professional"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Subtle 1"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Subtle 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Web 1"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Web 2"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Web 3"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Balloon Text"/>
<w:LsdException Locked="false" Priority="39" Name="Table Grid"/>
<w:LsdException Locked="false" SemiHidden="true" UnhideWhenUsed="true"
Name="Table Theme"/>
<w:LsdException Locked="false" SemiHidden="true" Name="Placeholder Text"/>
<w:LsdException Locked="false" Priority="1" QFormat="true" Name="No Spacing"/>
<w:LsdException Locked="false" Priority="60" Name="Light Shading"/>
<w:LsdException Locked="false" Priority="61" Name="Light List"/>
<w:LsdException Locked="false" Priority="62" Name="Light Grid"/>
<w:LsdException Locked="false" Priority="63" Name="Medium Shading 1"/>
<w:LsdException Locked="false" Priority="64" Name="Medium Shading 2"/>
<w:LsdException Locked="false" Priority="65" Name="Medium List 1"/>
<w:LsdException Locked="false" Priority="66" Name="Medium List 2"/>
<w:LsdException Locked="false" Priority="67" Name="Medium Grid 1"/>
<w:LsdException Locked="false" Priority="68" Name="Medium Grid 2"/>
<w:LsdException Locked="false" Priority="69" Name="Medium Grid 3"/>
<w:LsdException Locked="false" Priority="70" Name="Dark List"/>
<w:LsdException Locked="false" Priority="71" Name="Colorful Shading"/>
<w:LsdException Locked="false" Priority="72" Name="Colorful List"/>
<w:LsdException Locked="false" Priority="73" Name="Colorful Grid"/>
<w:LsdException Locked="false" Priority="60" Name="Light Shading Accent 1"/>
<w:LsdException Locked="false" Priority="61" Name="Light List Accent 1"/>
<w:LsdException Locked="false" Priority="62" Name="Light Grid Accent 1"/>
<w:LsdException Locked="false" Priority="63" Name="Medium Shading 1 Accent 1"/>
<w:LsdException Locked="false" Priority="64" Name="Medium Shading 2 Accent 1"/>
<w:LsdException Locked="false" Priority="65" Name="Medium List 1 Accent 1"/>
<w:LsdException Locked="false" SemiHidden="true" Name="Revision"/>
<w:LsdException Locked="false" Priority="34" QFormat="true"
Name="List Paragraph"/>
<w:LsdException Locked="false" Priority="29" QFormat="true" Name="Quote"/>
<w:LsdException Locked="false" Priority="30" QFormat="true"
Name="Intense Quote"/>
<w:LsdException Locked="false" Priority="66" Name="Medium List 2 Accent 1"/>
<w:LsdException Locked="false" Priority="67" Name="Medium Grid 1 Accent 1"/>
<w:LsdException Locked="false" Priority="68" Name="Medium Grid 2 Accent 1"/>
<w:LsdException Locked="false" Priority="69" Name="Medium Grid 3 Accent 1"/>
<w:LsdException Locked="false" Priority="70" Name="Dark List Accent 1"/>
<w:LsdException Locked="false" Priority="71" Name="Colorful Shading Accent 1"/>
<w:LsdException Locked="false" Priority="72" Name="Colorful List Accent 1"/>
<w:LsdException Locked="false" Priority="73" Name="Colorful Grid Accent 1"/>
<w:LsdException Locked="false" Priority="60" Name="Light Shading Accent 2"/>
<w:LsdException Locked="false" Priority="61" Name="Light List Accent 2"/>
<w:LsdException Locked="false" Priority="62" Name="Light Grid Accent 2"/>
<w:LsdException Locked="false" Priority="63" Name="Medium Shading 1 Accent 2"/>
<w:LsdException Locked="false" Priority="64" Name="Medium Shading 2 Accent 2"/>
<w:LsdException Locked="false" Priority="65" Name="Medium List 1 Accent 2"/>
<w:LsdException Locked="false" Priority="66" Name="Medium List 2 Accent 2"/>
<w:LsdException Locked="false" Priority="67" Name="Medium Grid 1 Accent 2"/>
<w:LsdException Locked="false" Priority="68" Name="Medium Grid 2 Accent 2"/>
<w:LsdException Locked="false" Priority="69" Name="Medium Grid 3 Accent 2"/>
<w:LsdException Locked="false" Priority="70" Name="Dark List Accent 2"/>
<w:LsdException Locked="false" Priority="71" Name="Colorful Shading Accent 2"/>
<w:LsdException Locked="false" Priority="72" Name="Colorful List Accent 2"/>
<w:LsdException Locked="false" Priority="73" Name="Colorful Grid Accent 2"/>
<w:LsdException Locked="false" Priority="60" Name="Light Shading Accent 3"/>
<w:LsdException Locked="false" Priority="61" Name="Light List Accent 3"/>
<w:LsdException Locked="false" Priority="62" Name="Light Grid Accent 3"/>
<w:LsdException Locked="false" Priority="63" Name="Medium Shading 1 Accent 3"/>
<w:LsdException Locked="false" Priority="64" Name="Medium Shading 2 Accent 3"/>
<w:LsdException Locked="false" Priority="65" Name="Medium List 1 Accent 3"/>
<w:LsdException Locked="false" Priority="66" Name="Medium List 2 Accent 3"/>
<w:LsdException Locked="false" Priority="67" Name="Medium Grid 1 Accent 3"/>
<w:LsdException Locked="false" Priority="68" Name="Medium Grid 2 Accent 3"/>
<w:LsdException Locked="false" Priority="69" Name="Medium Grid 3 Accent 3"/>
<w:LsdException Locked="false" Priority="70" Name="Dark List Accent 3"/>
<w:LsdException Locked="false" Priority="71" Name="Colorful Shading Accent 3"/>
<w:LsdException Locked="false" Priority="72" Name="Colorful List Accent 3"/>
<w:LsdException Locked="false" Priority="73" Name="Colorful Grid Accent 3"/>
<w:LsdException Locked="false" Priority="60" Name="Light Shading Accent 4"/>
<w:LsdException Locked="false" Priority="61" Name="Light List Accent 4"/>
<w:LsdException Locked="false" Priority="62" Name="Light Grid Accent 4"/>
<w:LsdException Locked="false" Priority="63" Name="Medium Shading 1 Accent 4"/>
<w:LsdException Locked="false" Priority="64" Name="Medium Shading 2 Accent 4"/>
<w:LsdException Locked="false" Priority="65" Name="Medium List 1 Accent 4"/>
<w:LsdException Locked="false" Priority="66" Name="Medium List 2 Accent 4"/>
<w:LsdException Locked="false" Priority="67" Name="Medium Grid 1 Accent 4"/>
<w:LsdException Locked="false" Priority="68" Name="Medium Grid 2 Accent 4"/>
<w:LsdException Locked="false" Priority="69" Name="Medium Grid 3 Accent 4"/>
<w:LsdException Locked="false" Priority="70" Name="Dark List Accent 4"/>
<w:LsdException Locked="false" Priority="71" Name="Colorful Shading Accent 4"/>
<w:LsdException Locked="false" Priority="72" Name="Colorful List Accent 4"/>
<w:LsdException Locked="false" Priority="73" Name="Colorful Grid Accent 4"/>
<w:LsdException Locked="false" Priority="60" Name="Light Shading Accent 5"/>
<w:LsdException Locked="false" Priority="61" Name="Light List Accent 5"/>
<w:LsdException Locked="false" Priority="62" Name="Light Grid Accent 5"/>
<w:LsdException Locked="false" Priority="63" Name="Medium Shading 1 Accent 5"/>
<w:LsdException Locked="false" Priority="64" Name="Medium Shading 2 Accent 5"/>
<w:LsdException Locked="false" Priority="65" Name="Medium List 1 Accent 5"/>
<w:LsdException Locked="false" Priority="66" Name="Medium List 2 Accent 5"/>
<w:LsdException Locked="false" Priority="67" Name="Medium Grid 1 Accent 5"/>
<w:LsdException Locked="false" Priority="68" Name="Medium Grid 2 Accent 5"/>
<w:LsdException Locked="false" Priority="69" Name="Medium Grid 3 Accent 5"/>
<w:LsdException Locked="false" Priority="70" Name="Dark List Accent 5"/>
<w:LsdException Locked="false" Priority="71" Name="Colorful Shading Accent 5"/>
<w:LsdException Locked="false" Priority="72" Name="Colorful List Accent 5"/>
<w:LsdException Locked="false" Priority="73" Name="Colorful Grid Accent 5"/>
<w:LsdException Locked="false" Priority="60" Name="Light Shading Accent 6"/>
<w:LsdException Locked="false" Priority="61" Name="Light List Accent 6"/>
<w:LsdException Locked="false" Priority="62" Name="Light Grid Accent 6"/>
<w:LsdException Locked="false" Priority="63" Name="Medium Shading 1 Accent 6"/>
<w:LsdException Locked="false" Priority="64" Name="Medium Shading 2 Accent 6"/>
<w:LsdException Locked="false" Priority="65" Name="Medium List 1 Accent 6"/>
<w:LsdException Locked="false" Priority="66" Name="Medium List 2 Accent 6"/>
<w:LsdException Locked="false" Priority="67" Name="Medium Grid 1 Accent 6"/>
<w:LsdException Locked="false" Priority="68" Name="Medium Grid 2 Accent 6"/>
<w:LsdException Locked="false" Priority="69" Name="Medium Grid 3 Accent 6"/>
<w:LsdException Locked="false" Priority="70" Name="Dark List Accent 6"/>
<w:LsdException Locked="false" Priority="71" Name="Colorful Shading Accent 6"/>
<w:LsdException Locked="false" Priority="72" Name="Colorful List Accent 6"/>
<w:LsdException Locked="false" Priority="73" Name="Colorful Grid Accent 6"/>
<w:LsdException Locked="false" Priority="19" QFormat="true"
Name="Subtle Emphasis"/>
<w:LsdException Locked="false" Priority="21" QFormat="true"
Name="Intense Emphasis"/>
<w:LsdException Locked="false" Priority="31" QFormat="true"
Name="Subtle Reference"/>
<w:LsdException Locked="false" Priority="32" QFormat="true"
Name="Intense Reference"/>
<w:LsdException Locked="false" Priority="33" QFormat="true" Name="Book Title"/>
<w:LsdException Locked="false" Priority="37" SemiHidden="true"
UnhideWhenUsed="true" Name="Bibliography"/>
<w:LsdException Locked="false" Priority="39" SemiHidden="true"
UnhideWhenUsed="true" QFormat="true" Name="TOC Heading"/>
<w:LsdException Locked="false" Priority="41" Name="Plain Table 1"/>
<w:LsdException Locked="false" Priority="42" Name="Plain Table 2"/>
<w:LsdException Locked="false" Priority="43" Name="Plain Table 3"/>
<w:LsdException Locked="false" Priority="44" Name="Plain Table 4"/>
<w:LsdException Locked="false" Priority="45" Name="Plain Table 5"/>
<w:LsdException Locked="false" Priority="40" Name="Grid Table Light"/>
<w:LsdException Locked="false" Priority="46" Name="Grid Table 1 Light"/>
<w:LsdException Locked="false" Priority="47" Name="Grid Table 2"/>
<w:LsdException Locked="false" Priority="48" Name="Grid Table 3"/>
<w:LsdException Locked="false" Priority="49" Name="Grid Table 4"/>
<w:LsdException Locked="false" Priority="50" Name="Grid Table 5 Dark"/>
<w:LsdException Locked="false" Priority="51" Name="Grid Table 6 Colorful"/>
<w:LsdException Locked="false" Priority="52" Name="Grid Table 7 Colorful"/>
<w:LsdException Locked="false" Priority="46"
Name="Grid Table 1 Light Accent 1"/>
<w:LsdException Locked="false" Priority="47" Name="Grid Table 2 Accent 1"/>
<w:LsdException Locked="false" Priority="48" Name="Grid Table 3 Accent 1"/>
<w:LsdException Locked="false" Priority="49" Name="Grid Table 4 Accent 1"/>
<w:LsdException Locked="false" Priority="50" Name="Grid Table 5 Dark Accent 1"/>
<w:LsdException Locked="false" Priority="51"
Name="Grid Table 6 Colorful Accent 1"/>
<w:LsdException Locked="false" Priority="52"
Name="Grid Table 7 Colorful Accent 1"/>
<w:LsdException Locked="false" Priority="46"
Name="Grid Table 1 Light Accent 2"/>
<w:LsdException Locked="false" Priority="47" Name="Grid Table 2 Accent 2"/>
<w:LsdException Locked="false" Priority="48" Name="Grid Table 3 Accent 2"/>
<w:LsdException Locked="false" Priority="49" Name="Grid Table 4 Accent 2"/>
<w:LsdException Locked="false" Priority="50" Name="Grid Table 5 Dark Accent 2"/>
<w:LsdException Locked="false" Priority="51"
Name="Grid Table 6 Colorful Accent 2"/>
<w:LsdException Locked="false" Priority="52"
Name="Grid Table 7 Colorful Accent 2"/>
<w:LsdException Locked="false" Priority="46"
Name="Grid Table 1 Light Accent 3"/>
<w:LsdException Locked="false" Priority="47" Name="Grid Table 2 Accent 3"/>
<w:LsdException Locked="false" Priority="48" Name="Grid Table 3 Accent 3"/>
<w:LsdException Locked="false" Priority="49" Name="Grid Table 4 Accent 3"/>
<w:LsdException Locked="false" Priority="50" Name="Grid Table 5 Dark Accent 3"/>
<w:LsdException Locked="false" Priority="51"
Name="Grid Table 6 Colorful Accent 3"/>
<w:LsdException Locked="false" Priority="52"
Name="Grid Table 7 Colorful Accent 3"/>
<w:LsdException Locked="false" Priority="46"
Name="Grid Table 1 Light Accent 4"/>
<w:LsdException Locked="false" Priority="47" Name="Grid Table 2 Accent 4"/>
<w:LsdException Locked="false" Priority="48" Name="Grid Table 3 Accent 4"/>
<w:LsdException Locked="false" Priority="49" Name="Grid Table 4 Accent 4"/>
<w:LsdException Locked="false" Priority="50" Name="Grid Table 5 Dark Accent 4"/>
<w:LsdException Locked="false" Priority="51"
Name="Grid Table 6 Colorful Accent 4"/>
<w:LsdException Locked="false" Priority="52"
Name="Grid Table 7 Colorful Accent 4"/>
<w:LsdException Locked="false" Priority="46"
Name="Grid Table 1 Light Accent 5"/>
<w:LsdException Locked="false" Priority="47" Name="Grid Table 2 Accent 5"/>
<w:LsdException Locked="false" Priority="48" Name="Grid Table 3 Accent 5"/>
<w:LsdException Locked="false" Priority="49" Name="Grid Table 4 Accent 5"/>
<w:LsdException Locked="false" Priority="50" Name="Grid Table 5 Dark Accent 5"/>
<w:LsdException Locked="false" Priority="51"
Name="Grid Table 6 Colorful Accent 5"/>
<w:LsdException Locked="false" Priority="52"
Name="Grid Table 7 Colorful Accent 5"/>
<w:LsdException Locked="false" Priority="46"
Name="Grid Table 1 Light Accent 6"/>
<w:LsdException Locked="false" Priority="47" Name="Grid Table 2 Accent 6"/>
<w:LsdException Locked="false" Priority="48" Name="Grid Table 3 Accent 6"/>
<w:LsdException Locked="false" Priority="49" Name="Grid Table 4 Accent 6"/>
<w:LsdException Locked="false" Priority="50" Name="Grid Table 5 Dark Accent 6"/>
<w:LsdException Locked="false" Priority="51"
Name="Grid Table 6 Colorful Accent 6"/>
<w:LsdException Locked="false" Priority="52"
Name="Grid Table 7 Colorful Accent 6"/>
<w:LsdException Locked="false" Priority="46" Name="List Table 1 Light"/>
<w:LsdException Locked="false" Priority="47" Name="List Table 2"/>
<w:LsdException Locked="false" Priority="48" Name="List Table 3"/>
<w:LsdException Locked="false" Priority="49" Name="List Table 4"/>
<w:LsdException Locked="false" Priority="50" Name="List Table 5 Dark"/>
<w:LsdException Locked="false" Priority="51" Name="List Table 6 Colorful"/>
<w:LsdException Locked="false" Priority="52" Name="List Table 7 Colorful"/>
<w:LsdException Locked="false" Priority="46"
Name="List Table 1 Light Accent 1"/>
<w:LsdException Locked="false" Priority="47" Name="List Table 2 Accent 1"/>
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<tr><td style="text-align: center;"><a href="http://2.bp.blogspot.com/-NQKh0NKR3_w/VZME_IGS7LI/AAAAAAAAAZo/wGB6apaQjhU/s1600/ADF_7.tif" imageanchor="1" style="margin-left: auto; margin-right: auto;"><img border="0" height="200" src="http://2.bp.blogspot.com/-NQKh0NKR3_w/VZME_IGS7LI/AAAAAAAAAZo/wGB6apaQjhU/s200/ADF_7.tif" width="200" /></a></td></tr>
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is an image of titanium dioxide. On the macroscale, this appears as a
white powder. However, as demonstrated with this image, when using
transmission electron microscopy it can be viewed at the nanoscale.
Depending on the conditions in a synthesis, the morphology of a compound can be
changed. The synthesis used to make this particular sample yields
nanosheets. These are approximately 7 nanometers thick and 60 nanometers
in length and width. The pattern seen on the sides of these nanosheets is
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<tr><td style="text-align: center;"><a href="http://2.bp.blogspot.com/-68Vhu150lGI/VZME-I68TgI/AAAAAAAAAZQ/LEugRjhOsT8/s1600/IMG_20150527_142416.jpg" imageanchor="1" style="margin-left: auto; margin-right: auto;"><img border="0" height="150" src="http://2.bp.blogspot.com/-68Vhu150lGI/VZME-I68TgI/AAAAAAAAAZQ/LEugRjhOsT8/s200/IMG_20150527_142416.jpg" width="200" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">This is the robot that I've helped design. It moves forward, reverse, rotates, and can slide sideways. We've designed the circuit boards that go in it which control the motors, sensors, and on board computing. We created the drive control that allows it to move. It can move autonomously and avoid obstacles. A lot of theory went into the PCB design and electronics’ circuitry, creating and integrating the drive control, generating the path planning for the robot to travel, interpreting and filtering sensor data, and building a pretty impressive control system to tie everything together! <br />
<i><b>Submitted by:</b></i> Mikey Norman</td></tr>
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<br /></td></tr>
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<tr><td style="text-align: center;"><a href="http://2.bp.blogspot.com/-cJJbc8mj6Gk/VZME_HhG2TI/AAAAAAAAAZk/oq99O2deEm8/s1600/IMG_2386.JPG" imageanchor="1" style="margin-left: auto; margin-right: auto;"><img border="0" height="200" src="http://2.bp.blogspot.com/-cJJbc8mj6Gk/VZME_HhG2TI/AAAAAAAAAZk/oq99O2deEm8/s200/IMG_2386.JPG" width="150" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">This photo depicts a two-dimensional infrared experiment being performed on a photo-catalyst in effort to assign infrared peaks of potential photo-products. The 400 nm handheld laser is implemented to generate the photo-products. Detailed information cannot be revealed because this work is not published yet.<br />
<i><b>Submitted by:</b></i> Laura Kiefer</td></tr>
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<tr><td style="text-align: center;"><a href="http://1.bp.blogspot.com/-CvQRhbAyPRc/VZME-9qduQI/AAAAAAAAAZg/FYFpQLclxQE/s1600/IMG_0275.jpg" imageanchor="1" style="margin-left: auto; margin-right: auto;"><img border="0" height="200" src="http://1.bp.blogspot.com/-CvQRhbAyPRc/VZME-9qduQI/AAAAAAAAAZg/FYFpQLclxQE/s200/IMG_0275.jpg" width="150" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">Third backup safety officer in the Kennedy group, Claire Ouimet, is simultaneously preparing to enter the clean room while also impersonating an Oompa Loompa. She is developing state-of-the art micro-fabricated chip electrophoresis devices in order to perform high-throughput screening of modulators of protein-protein interactions. Coincidentally, she is also 5'1" and orange.<br />
<i><b>Submitted by:</b></i> Alec Valenta</td></tr>
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Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com2tag:blogger.com,1999:blog-1971936738593606253.post-19876439854600986972015-06-11T10:50:00.000-04:002015-06-11T11:19:10.243-04:00Crystals in Chemistry: The How and (Some of) the Why<i>Welcome to Crystals in Chemistry, Part II. In this installment, we'll talk about how crystals are made and a few of the things that chemists and physicists use them for. For the previous installment, in which we covered some basics about what crystals are and how they form defects, click <a href="http://treetownchem.blogspot.com/2015/04/crystals-in-chemistry-wait-what.html">here</a>.</i><br />
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<tr><td style="text-align: center;"><a href="http://4.bp.blogspot.com/-4J8x5uNcAi4/VXigqzhWNDI/AAAAAAAAAXo/FI0foJf6YlM/s1600/xtals_crop.jpg" imageanchor="1" style="margin-left: auto; margin-right: auto;"><img border="0" height="232" src="http://4.bp.blogspot.com/-4J8x5uNcAi4/VXigqzhWNDI/AAAAAAAAAXo/FI0foJf6YlM/s400/xtals_crop.jpg" width="400" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">A few of Dr. David Chow's crystallization reactions in the Pecoraro lab. <br />
For puzzling out crystallization conditions, quantity equals quality.</td></tr>
</tbody></table>
<br />
One of the most painstaking parts of being an inorganic chemist is crystallization. When it comes time in your research to crystallize a new compound so you can study its structure, that task becomes the <a href="http://whatshouldwecallgradschool.tumblr.com/post/41796579051/what-i-tell-myself-after-a-failed-experiment">dark beast lurking in your lab</a> that you have to think about facing <a href="http://whatshouldwecallgradschool.tumblr.com/post/118451452513/when-my-friends-assume-i-get-the-summer-off">every day</a>. Crystallizations are difficult because the conditions for growing high-quality crystals are not always obvious.<br />
<br />
<a name='more'></a>Or, in the words of recent Ph. D. graduate David Chow, "You just try frickin' everything until something works." The picture above shows about half of the crystallizations he has running currently in his lab. When I asked how many different molecules he was working on, he said, "Really just one."<br />
<br />
It's not totally a shot in the dark, though. David has three solvents that he uses that typically work well with the materials he's interested in. Crystallization reactions can provide information even when they don't yield great crystals. "If you get powder [polycrystalline material] or crystals that aren't X-ray quality, you can just tweak the conditions a bit and then maybe it'll work."<br />
<br />
"And sometimes you just get lucky."<br />
<br />
Why all the work? In this segment, we'll go over how crystals form, why crystallizations are hard, and what chemists can do with crystals once they've got them.<br />
<br />
<i><b>Crystal Formation</b></i><br />
The magic word in crystal growth is nucleation. Nucleation refers to the event in which solute molecules stop floating around randomly in solution and decide to stick together to form the beginnings of a crystal. Most crystal growth techniques force nucleation by gradually changing the conditions that solute molecules experience. The goal is to create an environment where the more of the solute exists in solution than should be possible; this condition is called supersaturation. A supersaturated solution will respond by producing crystals. If crystallization happens slowly and the environment is not disturbed too much, a high-quality crystal is born.<br />
<br />
Well, <i>sometimes</i>. Nucleation is affected by lots of factors that are hard to control in practice, such as dust particles in the solution, microscopic (nanoscopic, really) irregularities in the glass container, temperature fluctuations, and vibrations from nearby movement. A recipe that gives a high-quality crystal once might not do so a second time, but might again the fifth time.<br />
<br />
Difficulties aside, how is supersaturation achieved? We'll run through three basic techniques in the next few paragraphs, using saline solution as an example.<br />
<br />
<i>Slow Evaporation</i><br />
The simplest way to make salt crystals is to make a saturated salt solution, which has just enough water to dissolve the salt, and then remove some of the water by evaporation. All of a sudden, there's too much salt for the water that's left, and salt crystals will form from the excess salt. In practice, the rate of evaporation can be very important for crystal quality, and it can be controlled by crystallizing in a small vial with a tiny hole punched in the cap. With more holes, or larger ones, the evaporation rate will be faster.<br />
<br />
<i>Heating, then Cooling</i><br />
Salt crystals can also form when salt is dissolved in just enough hot water. For most solutes, the solubility goes up with temperature; most things are more soluble in hot solvents than in cold ones. Therefore, as the water cools down to room temperature, the salt becomes less soluble and might even become supersaturated, at which point crystals will form. Cooling the water even further (using an ice bath, for example) could help even more. Again, the cooling rate can be important to the crystal quality; for this reason, it's usually best to let the solution cool to room temperature before putting it in the freezer.<br />
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For many inorganic solids, crystals are formed using heating and cooling, but the solvent is skipped. Scientists grow crystals of materials like silicon by melting down a bunch of polycrystalline material, then produce crystals from the melt by a number of different methods. You can see a <a href="https://www.youtube.com/watch?v=cYj_vqcyI78">time-lapse video of silicon crystal growth here</a>, where a singly-crystalline ingot is pulled out of a vat of molten silicon over a period of 31 hours.<br />
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<i> </i><br />
<table cellpadding="0" cellspacing="0" class="tr-caption-container" style="float: left; margin-right: 1em; text-align: left;"><tbody>
<tr><td style="text-align: center;"><a href="http://3.bp.blogspot.com/-uUzvfDVlu3Y/VXhm0yvYEAI/AAAAAAAAAXE/vQIbszrm5m8/s1600/layering.JPG" imageanchor="1" style="clear: left; margin-bottom: 1em; margin-left: auto; margin-right: auto;"><img border="0" height="320" src="http://3.bp.blogspot.com/-uUzvfDVlu3Y/VXhm0yvYEAI/AAAAAAAAAXE/vQIbszrm5m8/s320/layering.JPG" width="240" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">A liquid-liquid diffusion, or layering, crystallization<br />
that I set up. The red layer contains the molecule<br />
of interest, and the clear layer is the "bad solvent."</td></tr>
</tbody></table>
<i>Good Solvent, Bad Solvent</i><br />
The last general way for making salt crystals is to reduce the solubility of the salt by changing the solvent. For our example, salt is very soluble in water ("good solvent") but not very soluble in alcohols ("bad solvent"). By allowing alcohol to slowly mix with the water, the salt solubility is gradually brought down, and supersaturation can be achieved. In practice, this is usually done one of two ways. In one method, the bad solvent is added to the good solvent containing the salt we want. The addition is done so slowly that the solvents don't actually mix, as shown at the left; instead, they form two separate phases and diffuse into one another over time. This method is called liquid-liquid diffusion, or "layering." In the second method, the good solvent and salt are placed in a small vial, which is then put inside of a larger chamber containing some bad solvent. The large chamber is then sealed such that the good and bad solvent don't mix, but they share the same atmosphere. Bad solvent will vaporize and then dissolve into the good solvent. The idea is the same as it is in layering, but this second vapor diffusion method is much slower.<br />
<br />
<i><b>If You Build It, They Will Come</b></i><br />
Once a crystal has nucleated, the hard part is over. The rest of the salt ions in solution still float around randomly, but once they hit the surface of the growing crystal they form strong bonds and are much more likely to stick than to dissolve back off.<br />
<br />
This brings us to the first application of crystallization: purification. Crystals are very precise geometric networks, and only molecules of the exact right size and shape can be incorporated. If you're crystallizing Compound A, molecules of Compound B aren't likely to <i><b></b></i>fit into the crystal - like putting a square peg into a round hole. Instead, Compound B stays in solution and can be washed away. (This normally only works when you have lots of Compound A and not a lot of B, or when B is very soluble and A is not.) For a great explanation of this process, check out this <a href="http://orgchem.colorado.edu/Technique/Procedures/Crystallization/Crystallization.html">University of Colorado Boulder website</a>.<br />
<br />
<b><i>Now What?</i></b><br />
Eureka! You've finally got your crystal. That's great! But now what do you do with it?<br />
<br />
Much of the time in chemistry labs, purification is the main goal. However, single crystals are very useful in a range of analytical methods. By performing measurements on single crystals, chemists can learn a lot about a compound's fundamental properties.<b><i> </i></b>The list is long and varied; here, we'll go through two common examples.<br />
<b><i> </i></b> <br />
<i>What Do You Look Like?: Structure Determination</i><br />
One of the more powerful single crystal techniques is to determine a compound's molecular structure by shining a beam of X-rays on it and measuring how they bounce off. For organic molecules, there are simpler ways of deducing the structure. However, for some molecules, particularly inorganic complexes, techniques common to organic molecules can be ambiguous or impossible.<br />
<br />
The method is called X-ray diffraction, and its development led to multiple Nobel Prizes in Physics (<a href="http://www.nobelprize.org/nobel_prizes/physics/laureates/1914/">1914</a> and <a href="http://www.nobelprize.org/nobel_prizes/physics/laureates/1915/">1915</a>). In short, X-rays are fired at a crystal of the compound whose structure is to be determined. The angle at which the X-rays hit is varied, either by rotating the crystal or the X-ray source. The X-rays diffract off of the sample in ways that are characteristic of its structure at the atomic level. By measuring the angles at which X-rays are diffracted and processing the data (which can be very hard!), the structure of the crystal can be determined.<br />
<br />
<i>Electrical Conductivity</i><br />
Plenty of chemists are working on developing new semiconductors or re-engineering old ones for practical applications like solar cells or converting sunlight into fuel. Many applications of semiconductors require them to be able to conduct electricity very effectively, so measurements of conductivity are important. But, as we mentioned <a href="http://treetownchem.blogspot.com/2015/04/crystals-in-chemistry-wait-what.html">last time</a>, defects in the semiconductor like impurities and grain boundaries can dominate the conductivity. When we are evaluating a semiconductor for a particular application, we want to know the conductivity of the material itself, not the conductivity of the grain boundaries or of the impurities. The best way to do that is by performing the measurement on a highly pure single crystal.<br />
<br />
That doesn't mean, however, that impure crystals are useless. For example, silicon-based solar cells have had impurities added intentionally through a process called doping because pure silicon isn't very conductive. Polycrystalline materials are often more useful for technological applications than single crystals. For teasing out fundamental properties, though, you can't beat single crystal measurements.<br />
<br />
Crystallization challenges chemists in unique ways. In no other kind of experiment are a chemist's "hands" - how smoothly and calmly they can pipette solutions and move vials - so important. But, especially in inorganic chemistry and some areas of chemical biology, the data gained by studying single crystals is indispensable. Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com1tag:blogger.com,1999:blog-1971936738593606253.post-6650321665226394822015-05-28T14:01:00.002-04:002015-06-03T12:47:21.881-04:00Announcing the Tree Town Chemistry Photo ContestScience is cool. If you're reading this blog, you don't need any convincing on that point. But, there are some days when science is cooler than usual. The day you fill the laser lab with mist. The day you've got an air-free reaction rig that's bigger than you. The day you get the hugest, prettiest crystals.<br />
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I want to see that day. It's time for a Tree Town Chemistry photo contest.<br />
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<i><b>The Contest</b></i><br />
Submit your photo along with a ~100 word caption to treetownchem@gmail.com by June 12. If you're a computational/theoretical chemist, no worries - we'll accept screenshots and visualizations as well. I'll be judging the entries along with two celebrity* judges: world-famous science photographer Sung-Hei Yau and the Queen of Magnesium Emily Nelson, both recent graduates from our department. Entries will be judged on the quality of the composition and the clarity of the caption. (Don't worry about explaining your project in 100 words. Just let us know what's going on in the picture.)<br />
<br />
<i><b>The Prizes</b></i><br />
The winner locks down a cash prize of $20 and will be the subject of a blog article featuring their research and elaborating on the 100 word photo caption. The winning photo will also become the blog's banner image until next summer's contest (provided this one is successful).<br />
<br />
Two runners-up will also have their photos displayed in the blog.<br />
<br />
<i><b>The Rules</b></i><br />
1) The photo must be your original work, and you agree to have it potentially published on this blog under a Creative Commons license. <br />
2)<b> Photos depicting unsafe lab conditions (inadequate PPE, unsafe reaction setups, or unnecessary use of dangerous chemicals) will be disqualified.</b> <i>Please</i> don't pull out the <a href="https://www.youtube.com/watch?v=EmkBH-ncG1Y">diethyl zinc</a> just to win the photo contest.<br />
3) If there are any people besides yourself depicted in the photo, make sure you have their permission before submitting. Similarly, if you're depicting any unpublished data in your photo, clear it with your PI.<br />
4) Each person can only submit one photo.<br />
<br />
Email submissions to treetownchem@gmail.com by June 12. Winners will be announced shortly thereafter. I'm looking forward to your submissions!Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com0tag:blogger.com,1999:blog-1971936738593606253.post-33140298666607255912015-05-12T12:11:00.003-04:002015-05-13T13:56:53.640-04:00It's Time to Face Your Fear of Scorpionates<div style="text-align: justify;">
Scorpions.</div>
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The little arachnids are one of the most recognizable members of the animal kingdom. Just reading the word conjures images - perhaps of monsters with fangs and spines dripping with venom, perhaps of a household pe(s)t, perhaps of <a href="http://www.imdb.com/title/tt0277296/">Dwayne Johnson</a>. No matter the association, the scorpion is an iconic figure.</div>
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For inorganic chemists, scorpions are associated with a broad class of metal-organic complexes with a unique molecular shape. These molecules are called scorpionates.</div>
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<i><b>Metals in the Teeth of the Beast</b></i></div>
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<a href="http://1.bp.blogspot.com/-oiYqJX8iDXY/VVId2v7odJI/AAAAAAAAAVU/qvelgGZ-DFc/s1600/scorpionates.PNG" imageanchor="1" style="clear: left; float: left; margin-bottom: 1em; margin-right: 1em;"><br /></a></div>
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<a href="http://3.bp.blogspot.com/-oiYqJX8iDXY/VVId2v7odJI/AAAAAAAAAVY/Gczh35xY1Co/s1600/scorpionates.PNG" imageanchor="1" style="margin-left: 1em; margin-right: 1em;"><img border="0" height="176" src="http://3.bp.blogspot.com/-oiYqJX8iDXY/VVId2v7odJI/AAAAAAAAAVY/Gczh35xY1Co/s200/scorpionates.PNG" width="200" /></a></div>
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<a href="http://1.bp.blogspot.com/-SVhJ23vs0DA/VVId-e0Bb9I/AAAAAAAAAVc/TQxlagcDshE/s1600/scorpion.jpg" imageanchor="1" style="clear: left; margin-bottom: 1em; margin-left: auto; margin-right: auto;"><img border="0" height="142" src="http://1.bp.blogspot.com/-SVhJ23vs0DA/VVId-e0Bb9I/AAAAAAAAAVc/TQxlagcDshE/s200/scorpion.jpg" width="200" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;"><i><b>Top:</b></i> cartoon of a scorpionate complex,<br />
with the ligand-bound triangular face<br />
highlighted. [original work] <i><b>Bottom:</b></i> an <br />
actual scorpion. [attribution: by Shantanu <br />
Kuveskar (Own work) [CC BY-SA 4.0 <br />
(http://creativecommons.org/licenses/by-sa/4.0)],<br />
via Wikimedia Commons</td></tr>
</tbody></table>
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Organometallic complexes have two main parts. The first is the central metal atom or ion. Second comes the nonmetallic molecules that bind to the metal, called the ligands. Metals don't usually do much quality work on their own, so tons of research has gone into creating ligands that impart a desired function to a particular metal ion.</div>
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Scorpionate ligands have three different sites that can bind to a metal ion. Traditionally, scorpionates are used in octahedral metal complexes, and all three of the binding sites bind to one triangular face of the octahedron as shown in the cartoon at left.</div>
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Metal-scorpionate complexes are quite strong for two reasons. First, the ligand is tetrahedrally-shaped. Tetrahedra have triangular faces, so sticking the triangular ligand onto the octahedral metal is a bit like snapping Lego blocks into place - the ligand does not have to distort much to make it work. Secondly, scorpionates bind strongly due to their multiple binding sites. The <a href="http://chemwiki.ucdavis.edu/Inorganic_Chemistry/Coordination_Chemistry/Complex_Ion_Equilibria/Chelation">chelate effect</a> shows that one ligand that binds the metal multiple times (a chelate) is always more stable than several singly-bound ligands due to a smaller decrease in entropy for the multiply bound case. Put simply, molecules like to be able to flop around, and chelate molecules lose less floppiness than non-chelate molecules, which makes the metal-ligand bond stronger.</div>
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Scorpionates were discovered by Dr. Swiatoslaw Trofimenko in 1966 during his time at DuPont. At that time, researchers at DuPont actively pursued side projects. As Dr. Trofimenko said in a 2003 <a href="http://pubs.acs.org/cen/coverstory/8117/8117ligands.html">interview with Chemical & Engineering News</a>, the first scorpionates came out of his interest in reacting boron compounds with <a href="http://en.wikipedia.org/wiki/Pyrazole">pyrazole</a> to create trispyrazolylborates (abbreviated Tb). He reacted Tb with metals to study coordination chemistry. The complexes he isolated showed two arms of the Tb ligand grabbing onto the metal ion, with a third reaching over the top, much the way a scorpion grabs its prey before delivering a sting.<br />
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Trofimenko coined the term "scorpionate" and the name has stuck ever since.</div>
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Trofimenko's <a href="http://www.ukrweekly.com/old/archive/2003/210319.shtml">work resulted in over 100 published articles</a>, plus a <a href="http://www.amazon.com/Scorpionates-Polypyrazolylborate-Ligands-Coordination-Chemistry/dp/1860941729">book</a>. An American Chemical Society symposium was held in his honor in 2003, and he <a href="http://www.udel.edu/chem/burmeister/bh34/trof.html">died in 2007</a>.</div>
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<i><b>Scorpionates Today</b></i></div>
<table cellpadding="0" cellspacing="0" class="tr-caption-container" style="float: right; margin-left: 1em; text-align: right;"><tbody>
<tr><td style="text-align: center;"><a href="http://4.bp.blogspot.com/-OdMM_qDVkZ8/VVIiK_sQ5aI/AAAAAAAAAVo/bahc2Tjk9gE/s1600/co_scorpionate.png" imageanchor="1" style="clear: right; margin-bottom: 1em; margin-left: auto; margin-right: auto;"><img border="0" height="217" src="http://4.bp.blogspot.com/-OdMM_qDVkZ8/VVIiK_sQ5aI/AAAAAAAAAVo/bahc2Tjk9gE/s320/co_scorpionate.png" width="320" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">A cobalt scorpionate crystal structure. In this orientation, <br />
the scorpion is lookingoutward from the screen and<br />
a little to the left. Original artwork created in Mercury 2.2 <br />
from crystallographic data in Silva et al.<i> Dalton Trans.</i> <b><br />2012</b>, <i>41</i>, 12888. [<a href="http://pubs.rsc.org/en/Content/ArticleLanding/2012/DT/c2dt11577h#!divAbstract">link</a>]</td></tr>
</tbody></table>
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Trispyrazolylborates provided a new ligand geometry that allowed chemists to investigate a huge number of complexes with facial geometry. The structural aspects of scorpionate complexes, which can be easily modified to target different sizes or electronic properties, are still being explored. Trofimenko preferred to research the synthesis and structure of scorpionates more than anything, <a href="http://pubs.acs.org/cen/coverstory/8117/8117ligands.html">telling C&E News</a>, "I consider myself a gunsmith rather than a hunter."</div>
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However, research on scorpionates has evolved in many different directions to include more applications-focused projects. Given that scorpions themselves are hunters, three recent publications on metal scorpionate complexes are featured below.</div>
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<i>Cobalt complexes bearing scorpionate ligands: synthesis, characterization, cytotoxicity and DNA cleavage</i> - Dalton Transactions (RSC, $) [<a href="http://pubs.rsc.org/en/Content/ArticleLanding/2012/DT/c2dt11577h#!divAbstract">link</a>]</div>
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The authors of this study have found a way to combine esoteric structural inorganic chemistry investigations with practical forays into cancer therapy research. They synthesize a number of cobalt scorpionate complexes and study their crystal structures, one of which is pictured above. The complexes are formed after the breaking of a cobalt-sulfonate bond, which is an uncommon reaction motif. The cobalt scorpionates mediated DNA cleavage <i>in vitro</i> by an undetermined mechanism, and also were found to be active in killing colorectal cancer cells. </div>
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<i>Scorpionate-Type Coordination in MFU-4/Metal-Organic Frameworks: Small-Molecule Binding and Activation upon the Thermally Activated Formation of Open Metal Sites</i> - Angewandte Chemie, International Edition (GDCh, $) [<a href="http://onlinelibrary.wiley.com/doi/10.1002/anie.201310004/abstract">link</a>]</div>
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If you get excited about cool crystal structures, this is a paper for you. The researchers who published this study inspected a known zinc metal organic framework called MFU-4 and found coordination centers reminiscent of scorpionate complexes. They then used a series of reactions to displace some zinc centers with copper(I) ions, and in another step stripped chloride from the MOF, resulting in exposed copper(I) ions with open coordination sites. Such sites are anticipated to be very reactive. They then demonstrate that the modified MOF effectively performs some hydride transfer reactions and shows activity towards small molecules interesting to energy science.</div>
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<i>Enantiopure N,N,O-scorpionate zinc amide and chloride complexes as efficient initiators for the heteroselective [Ring Opening Polymerization] of cyclic esters</i> - Dalton Transactions (RSC, $) [<a href="http://pubs.rsc.org/en/Content/ArticleLanding/2014/DT/C4DT02178A#!divAbstract">link</a>]</div>
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In this paper, the authors expand on some of their previous work by preparing new members of a series of zinc scorpionates contaning only to pyrazole units. The tail of the scorpion is left available for synthetic modification. The researchers prepare an interesting dinuclear zinc scorpionate where one zinc is octahedrally coordinated, and the other is tetrahedral. Several complexes in their series were active towards the polymerization of lactides and lactones, evidently by an attractive living single-site mechanism.</div>
Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com0tag:blogger.com,1999:blog-1971936738593606253.post-51135128480932414762015-04-21T12:17:00.000-04:002015-05-13T13:57:37.770-04:00Chemistry Literature Feature, Vol. IX<b><i>Have you seen a good paper lately? Written one? Send it in and have it featured here! </i></b><a href="mailto:treetownchem@gmail.com">treetownchem@gmail.com</a><br />
<br />
<i><b>Overheard at Michigan: Snapchat Edition</b></i><br />
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<tr><td style="text-align: center;"><a href="http://1.bp.blogspot.com/-FdpUWgLlo2I/VTZ2lvEsJdI/AAAAAAAAAU0/6ax8Zu577_0/s1600/IMG_0651.PNG" imageanchor="1" style="margin-left: auto; margin-right: auto;"><img border="0" height="320" src="http://1.bp.blogspot.com/-FdpUWgLlo2I/VTZ2lvEsJdI/AAAAAAAAAU0/6ax8Zu577_0/s1600/IMG_0651.PNG" width="213" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">These results not sponsored by Dell, but I can't<br />
really understand why.</td></tr>
</tbody></table>
Once again, it's time to look at six cool papers from five cool fields and also organic chemistry! In this ninth episode of the Chemistry Literature Feature, we'll take a look at a paper that pulls the old bait-and-switch on drug-resistant cancers, a one-step experimental verification of some really old kinetics thinking, and a new look at how frustrated Lewis pairs catalyze hydrogen activation. But first, at your left, a simulation gone horribly wrong!<br />
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<i><b>Analytical -</b> Microimaging of Transient Concentration Profiles of Reactant and Product Molecules during Catalytic Conversion in Nanoporous Materials</i><br />
Studying chemical kinetics - the individual steps that compose a chemical reaction and their respective rates - is hard. Kinetic information is even more elusive during reactions on solid surfaces where the diffusion of substrates to small, stationary active sites plays an intimate role. The authors of <a href="http://onlinelibrary.wiley.com/doi/10.1002/anie.201409482/abstract">this study ($)</a> in Angewandte Chemie (GDCh) present a cutting-edge technique that uses infrared spectroscopy to track the progress of benzene molecules through a network of porous glass decorated with nickel catalyst particles during gas-phase benzene hydrogenation. The infrared technique provides information not only on the rates of benzene consumption and cyclohexane production, but also on where within the catalyst material these processes occur. The data is the among the first in-situ verifications of <a href="http://en.wikipedia.org/wiki/Thiele_modulus">kinetics principles</a> that were proposed in the early part of the 20th century.<br />
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<i><b>Chemical Biology - </b>Nucleotides with Altered Hydrogen Bonding Capacities Impede Human DNA Polymerase </i><i><!--[if gte mso 9]><xml>
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</xml><![endif]--></i><i><span style="font-family: inherit;"><span style="font-size: 11pt; line-height: 107%;">η</span></span> by Reducing Synthesis in the Presence of the Major Cisplatin DNA Adduct</i><br />
Cisplatin, a surprisingly simple inorganic complex, is a widely-used drug in cancer therapy. It functions by binding to DNA and fouling up the action of enzymes called polymerases that make new copies of DNA during cell replication. However, some cancers become resistant to platinum treatments by using specialized polymerases capable of working around cisplatin. The authors of <a href="http://pubs.acs.org/doi/abs/10.1021/ja512547g">this paper ($)</a> in the Journal of the American Chemical Society have studied the effects of a synthetic nucleotide - a DNA building block - administered along with cisplatin. The idea is that the synthetic nucleotide inhibits a specific kind of DNA polymerase capable of working around the cisplatin. The authors found that polymerase grabs their synthetic nucleotide, which is too large for it to handle, and incorporates it into the DNA strand, but then the polymerase is prevented from completing DNA replication. While far from an <i>in vivo</i> cell study, this paper furthers an interesting new addition to cancer therapies.<br />
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<i><b>Inorganic - </b>Anionic Metal-Organic Framework for Adsorption and Separation of Light Hydrocarbons</i><br />
If you've been following this blog for a while now, you'll have realized that <a href="http://treetownchem.blogspot.com/2014/09/icyms-1-mofs-and-more-with-dr-joe-zhou.html">I can't resist sharing a good paper about metal-organic frameworks</a> (MOFs). MOFs are solid-state "coordination polymers" with huge internal surface areas that have promise for applications in a number of important chemical processes. In <a href="http://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.5b00316">this recent communication ($)</a>, published in Inorganic Chemistry (ACS), the authors report a new nickel-based MOF with an interesting "interpenetrated" structure. The MOF is capable of adsorbing very high quantities of light hydrocarbons like acetylene and methane due to a crystal structure which is more than half void space. This compound shows initial promise as a separation agent for light hydrocarbons - a process which is accomplished currently by time- and energy-intensive fractional distillation.<br />
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<i><b>Materials - </b></i>Ab initio <i>study of doping effects on LiMnO<sub>2</sub> and Li<sub>2</sub>MnO<sub>3</sub> cathode materials for Li-ion batteries</i><br />
So-called "over-lithiated oxides" have been investigated recently as electrode materials for lithium-ion batteries; the idea here is that with more lithium ions jammed into the structure, the compound stores more charge, which translates to a longer lifetime for your cell phone battery. However, over-lithiated oxides such as Li<sub>2</sub>MnO<sub>3</sub> are rarely used in pure form, and studies to understand the effects of doping these materials - intentionally adding impurities to produce a desired effect - are underway. <a href="http://pubs.rsc.org/en/content/articlelanding/2015/ta/c5ta01445j#!divAbstract">This computational work</a> ($), published in the Journal of Materials Chemistry A (RSC) investigates the effects of 12 total dopants on key performance metrics for lithium-ion cathode materials: electronic conductivity, ionic conductivity, thermodynamic stability, and electrochemical potential. The paper is brimming with information. Highlighting only one conclusion would be a disservice, but this work could serve as a great reference for synthetic chemists in the battery field.<br />
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<i><b>Organic - </b>Biomimetic Total Synthesis of Santalin Y</i><br />
Total synthesis is a phrase used by chemists to refer to the painstaking process of synthesizing large and complex molecules, usually of a biological origin. These molecules usually contain many stereocenters or reactive functional groups, making their artificial synthesis a huge challenge. The authors of <a href="http://onlinelibrary.wiley.com/doi/10.1002/anie.201411350/abstract">this short paper</a> ($) in Angewandte Chemie (GDCh) have developed a total synthesis for santalin Y, a bright yellow pigment found in certain kinds of <a href="http://anpsa.org.au/APOL31/sep03-3.html">sandalwood</a>. The highlight of the paper is the installation of five (!) stereocenters in a single chemical step - usually one is hard enough. This step earned the study the "Very Important Paper" designation by Angewandte's editors. While santalin Y might not be the most exciting molecule ever, these total synthesis investigations force chemists to develop creative ways of building molecular motifs which expands the set of tools available for creating other molecules.<br />
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<i><b>Physical - </b>Are intramolecular frustrated Lewis pairs also intramolecular catalysts? A theoretical study on H<sub>2</sub> activation</i><br />
A frustrated Lewis pair arises when two groups on the same molecule, one Lewis acid and one Lewis base, are prevented from <a href="http://www.chem.ucla.edu/harding/IGOC/L/lewis_acid_base_adduct.html">forming an adduct</a> by some steric factor, such as a carbon skeleton that keeps them apart.<i> </i>Frustrated Lewis pairs (FLPs) are a little like two angry hockey players held
apart by the referee - when they want to go at it, the space between
them is a very dangerous place to be. This high-energy non-interaction has been investigated for its role in catalysis, specifically small-molecule activation. The prevailing hypothesis is that the FLP binds a small molecule and then, in order to stabilize the high energy cost of not forming an adduct, rips the molecule apart. <a href="http://pubs.rsc.org/en/content/articlelanding/2015/cp/c5cp00368g#!divAbstract">A recent paper</a> ($) published in Physical Chemistry and Chemical Physics (RSC) presents the results of some calculations that suggest that some types of FLPs may not catalyze reactions by that mechanism at all, but by a dimeric pathway in which two FLP molecules cooperate to catalyze the reaction two times at once. The authors propose that their pathway is favored due to steric considerations, paving the way for an experimental kinetic investigation.<br />
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<b style="font-style: italic;">Remember, </b><i>if you come across an article that you think should be featured here, </i><b style="font-style: italic;">send it in! </b><a href="mailto:treetownchem@gmail.com">treetownchem@gmail.com</a><br />
<br />
<span style="color: #999999;"><i>ACS - American Chemical Society</i></span><br />
<span style="color: #999999;"><i>GDCh - Gesellschaft Deutscher Chemiker (German Chemical Society)<br />RSC - Royal Society of Chemistry</i></span><br />
<span style="color: #999999;"><i>$ - subscription required to access</i></span>Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com1tag:blogger.com,1999:blog-1971936738593606253.post-51914364192993831062015-04-06T12:03:00.000-04:002015-04-07T12:47:07.892-04:00Crystals in Chemistry: Wait, What?<div style="text-align: justify;">
<i>This is the first in a multi-part post about crystals in chemistry. Stay tuned for more!</i></div>
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I have been spending a lot of time on crystallizations lately. (Read: I have been a very sad chemist lately.) Last week, as I was hanging dejectedly out of the glove box like some shamed medieval peasant, peering into impossibly dark solutions looking for the smallest sign of a crystal, it occurred to me that these little nuggets of perfection might be the kind of thing that people want to read about.</div>
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What are crystals? Why do chemists care about them so much? Why am I trying so hard to make one? How are they made, and what do we do with them after we have them? For all this and more, read on.</div>
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<i><b>Crystals - Not (Exactly) Magic</b></i></div>
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Whether you know it or not, you've seen a crystal in your lifetime. The salt and sugar in your kitchen, gemstones in jewelry, and the <a href="http://ffmedia.ign.com/lotr/journey/multimedia/gandalf_moria_01.jpg">tip of Gandalf's staff</a> are all crystalline materials.<b> </b>But not all crystals are shiny, pretty things. The solar cell in your high school calculator was probably a crystal. Metals, drugs, and all kinds of other things can form crystals.</div>
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Let's start with a definition. A crystal is a collection of atoms, ions, or molecules that comes together</div>
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<tr><td style="text-align: center;"><a href="http://3.bp.blogspot.com/-fPpWepcR7h0/VSKWGRKOfaI/AAAAAAAAAT4/xTJzkhXcq-8/s1600/mp-22862_conventional_standard_withcube.tif" imageanchor="1" style="clear: right; margin-bottom: 1em; margin-left: auto; margin-right: auto;"><img border="0" src="http://3.bp.blogspot.com/-fPpWepcR7h0/VSKWGRKOfaI/AAAAAAAAAT4/xTJzkhXcq-8/s1600/mp-22862_conventional_standard_withcube.tif" height="255" width="320" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">The crystal structure of sodium chloride, called the "rock salt"<br />
structure (rather appropriately).</td></tr>
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to form a regular, repeating pattern in three-dimensional space. Crystals are most frequently made out of small species like atoms or molecules, such as is the case with diamonds (crystalline carbon). However, some fields of science have labored painstakingly to produce crystals of much larger species like proteins and <a href="http://www.mol.biol.ethz.ch/groups/ban_group/Ribosome">an entire ribosome</a>.</div>
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Sodium chloride, table salt, has a fairly simple crystal structure, shown here at the right. The red cube shows the smallest repeating unit of the crystal, called the unit cell. The entire crystal, no matter how big it gets, is just many copies of this tiny unit cell stacked over and over and over again in three dimensions.</div>
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Crystals form because they force their constituent atoms or molecules to pack in as closely and as tightly as possible to one another. The extended network of bonds gives the crystal extraordinary stability. We'll talk more about crystal formation in another installment.</div>
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<tr><td style="text-align: center;"><a href="http://2.bp.blogspot.com/-vLV-xlZGmJg/VSKViPcIrqI/AAAAAAAAATo/7EbKKL1siZo/s1600/iron_phen.jpg" imageanchor="1" style="clear: left; margin-bottom: 1em; margin-left: auto; margin-right: auto;"><img border="0" src="http://2.bp.blogspot.com/-vLV-xlZGmJg/VSKViPcIrqI/AAAAAAAAATo/7EbKKL1siZo/s1600/iron_phen.jpg" height="240" width="320" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">Red crystals of an iron phenanthroline complex prepared<br />
by my labmate Kayla. Crystals containing transition metals<br />
like iron are often brightly colored.</td></tr>
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<i><b>Damn It, Entropy! This Is Why We Can't Have Nice Things!</b></i></div>
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Of course, the packing isn't always 100% perfect. By the second law of thermodynamics, processes that increase entropy are favored. Crystals, with their regular packing and rigid bonds, are not very entropic, so defects form readily and increase the crystal's overall entropy.</div>
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There are <a href="http://www.academia.edu/8778046/Introduction_To_Materials_Science_Chapter_4_Imperfections_in_solids">many different ways a crystal can be imperfect</a> or defective. Atoms or groups of atoms can switch places, get swapped out for other atoms, or be missing entirely. Another defect that can appear in crystals is the grain boundary. A grain boundary is a line usually formed when two crystals fuse together to become part of the same particle, or when a crystal changes orientation during growth.</div>
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This means that a single particle of a given material can be composed of more than one grain, also called a crystalline domain. In the case where each particle of a material is composed of only one crystalline domain, we call the material a single crystal. In the other case, where each particle of a material is composed of several crystalline domains all stuck together, we call the material polycrystalline. If a material has totally random ordering at the molecular level, it is called amorphous </div>
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<tr><td class="tr-caption" style="text-align: center;">Needle-like crystals of tetrabutylammonium<br />
hexafluorophosphate. These crystals have poor clarity and<br />
are probably polycrystalline - lots of grain boundaries.</td></tr>
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<i><b>One Grain or Many?</b></i></div>
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Outside of the analytical world, both single crystalline and polycrystalline materials have important uses. Generally speaking, single crystalline materials are more conductive of heat and electricity because heat and electricity both have a hard time transferring through grain boundaries. That's why solar cells are often made from highly crystalline silicon wafers.</div>
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Polycrystalline materials, on the other hand, tend to respond better to stress and strain than single crystals. The grain boundaries stop the spread of dislocations and other signs of stress that eventually end in material failure. The bones in your body and metal support beams for buildings are both polycrystalline; a single crystalline material would be far too brittle.</div>
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<i><b>Get Ready to Go Deeper...</b></i></div>
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We've only scratched the surface of the properties of crystals and what they can do for scientists. Next time, we'll talk about techniques used by lab workers for crystal growth, both in research and in industry.</div>
Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com1tag:blogger.com,1999:blog-1971936738593606253.post-27944622357500711942015-04-01T09:19:00.002-04:002015-04-01T09:19:28.376-04:0013 Outright LIES Scientists Are Telling the Public<br />
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<span style="font-size: large;"><i><b>APRIL FOOLS! This blog still has integrity! </b></i></span><br />
<a href="http://1.bp.blogspot.com/-4C2lRJ8qbwI/VRvvvp7tLnI/AAAAAAAAATM/WeMzMscubh4/s1600/60858233.jpg" imageanchor="1" style="clear: left; float: left; margin-bottom: 1em; margin-right: 1em;"><img border="0" src="http://1.bp.blogspot.com/-4C2lRJ8qbwI/VRvvvp7tLnI/AAAAAAAAATM/WeMzMscubh4/s1600/60858233.jpg" height="320" width="320" /></a><br />
But, while I'm posting, let me publicly thank those of you who filled out the feedback survey I posted a few weeks ago. I really appreciate hearing back from the readership about how the blog is going and thanks for your time.<br /><br />In other news, I'm focusing on my thesis work hardcore this semester, but I'm not dead! I've (We've?) got a few interesting things moving (slowly) through the pipeline, coming soon to a social media feed near you.<br /><br />So, stay tuned, and as always, thanks for reading and making this a fun adventure.Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com1tag:blogger.com,1999:blog-1971936738593606253.post-56189417261781631212015-03-04T19:59:00.000-05:002015-03-05T09:43:38.814-05:00Chemistry Literature Feature, Vol. VIII<b><i>Have you seen a good paper lately? Written one? Send it in and have it featured here! </i></b><a href="mailto:treetownchem@gmail.com">treetownchem@gmail.com</a><br />
<i><b></b></i><br />
In this episode of the Chemistry Literature Feature, we'll take a look at sticky slides that trap bacteria for disease identification, cheap iron catalysts that make expensive chiral molecules, and an experiment with <i>way</i> too many lasers. But first, how precise is your day-to-day performance?<br />
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<i><b>Overheard at Michigan</b></i><br />
<blockquote class="tr_bq">
<i>"I feel like I don't suck at science today. Yesterday, I definitely did, but today I actually know what I'm doing."</i></blockquote>
<i><b>Analytical - </b>Supramolecular Scaffolds on Glass Slides as Sugar Based Rewritable Sensor</i><i> for Bacteria </i>[sic]<i><br /></i><br />
Methods for detecting diseases are expensive. On top of the materials cost, a trained technician must be paid to perform the analyses, so both the cost of the device and the cost of the labor needed to run it factor in to the price tag of a diagnostic procedure. As part of an effort to address that concern, the authors of <a href="http://pubs.rsc.org/en/content/articlelanding/2015/cc/c5cc01019e#!divAbstract" target="_blank">this paper ($, advance article)</a> in Chemical Communications (RSC) have developed a simple procedure for detecting troublesome microbes. The authors coated glass slides with a specially-designed binding agent and a type of <a href="http://www.sigmaaldrich.com/technical-documents/articles/biofiles/cyclodextrins.html" target="_blank">ring-shaped sugar called cyclodextrin</a>.The researchers took advantage of the fact that bacteria naturally bind to certain sugars to show selective adhesion of certain cells to the slides based on which types of sugar they prefer. This simple device has the potential to quickly detect and identify infectious microorganisms in a very simple fashion.<br />
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<i><b>Chemical Biology - </b>Polymerase synthesis of DNA labelled with benzylidene cyanoacetamide-based fluorescent molecular rotors: fluorescent light-up probes for DNA-binding proteins</i><br />
Scientists often use <a href="http://www.lifetechnologies.com/us/en/home/references/molecular-probes-the-handbook/introduction-to-fluorescence-techniques.html" target="_blank">fluorescence-based methods to detect</a> when important biological molecules are interacting with one another. This molecule goes to this molecule and then <i>boom</i> - they light up. However, for DNA-protein interactions, these methods are only well-developed for proteins that change the DNA. The authors of <a href="http://pubs.rsc.org/en/content/articlelanding/2015/cc/c5cc00530b#!divAbstract" target="_blank">this paper (open access)</a>, published in Chemical Communications (RSC), investigated a<i> </i>new type of fluorescence probe capable of reporting on non-enzymatic DNA-protein interactions. These probes are sensitive to the viscosity of their environment. <a href="http://pubs.acs.org/doi/abs/10.1021/jp300835k" target="_blank">Water near big biomolecules ($)</a> like proteins and DNA tends to be more viscous. The authors showed that their probes lit up much more brightly in viscous environments. Probes of this nature could allow researchers to learn more about hugely important cell processes such as <a href="https://www.youtube.com/watch?v=WsofH466lqk" target="_blank">DNA transcription</a> and coiling/uncoiling.<br />
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<i><b>Inorganic - </b>Silica-Supported Tungsten Carbynes (</i><i><!--[if gte mso 9]><xml>
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</xml><![endif]--></i><b><span style="font-family: "Times New Roman",serif; font-size: 12.0pt; line-height: 107%; mso-ansi-language: EN-US; mso-bidi-language: AR-SA; mso-fareast-font-family: "Times New Roman"; mso-fareast-language: EN-US; mso-font-kerning: 18.0pt;">≡</span></b><i>SiO)<sub>x</sub>W(</i><b><span style="font-family: "Times New Roman",serif; font-size: 12.0pt; line-height: 107%; mso-ansi-language: EN-US; mso-bidi-language: AR-SA; mso-fareast-font-family: "Times New Roman"; mso-fareast-language: EN-US; mso-font-kerning: 18.0pt;">≡</span></b><i>CH)Me<sub>y</sub> (x=1, y=2; x=2, y=1): New Efficient Catalysts for Alkyne Cyclotrimerization</i><br />
Traditionally, catalysts for chemical reactions have been soluble molecules that react with soluble starting materials to produce the desired product. But separating products out of solutions after the reaction is over can be a pain, which translates to higher processing costs at industrial scale. Binding catalysts to solid surfaces to create a <a href="https://www.boundless.com/chemistry/textbooks/boundless-chemistry-textbook/chemical-kinetics-13/catalysis-102/heterogeneous-catalysis-430-4700/" target="_blank">heterogeneous catalyst</a>, which can be simply filtered from the reaction, is a growing trend in many areas of chemistry. In a <a href="http://pubs.acs.org/doi/abs/10.1021/om500684e" target="_blank">recently-published paper ($)</a> in Organometallics (ACS), researchers bound tungsten-based catalysts to a silica surface and demonstrated that their hybrid catalyst had high activity for cyclotrimerization reactions with alkynes. Additionally, by making the safe assumption that tungsten catalysts were far away from one another (molecularly speaking), the authors were able to shed some more light on the mechanism by which the tungsten catalyst achieves cyclotrimerization.<br />
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Inorganic students who love extended solids might also love the Physical paper. <br />
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<i><b>Materials - </b>Controlling the Size of Hot Injection Made Nanocrystals by Manipulating the Diffusion Coefficient of the Solute</i><br />
<a href="http://www.labmate-online.com/news/microscopy-and-microtechniques/4/breaking_news/an_introduction_to_nanocrystals/30231/" target="_blank">Nanocrystalline materials are extremely useful</a>. In addition to showing great promise in a number of different technical applications, their <a href="http://www.explainthatstuff.com/quantum-dots.html" target="_blank">extremely small sizes allow chemists and physicists to investigate fundamental questions</a> related to light-matter interaction. Making nanocrystals uniformly and in specific sizes, then, is very important. The authors of <a href="http://pubs.acs.org/doi/abs/10.1021/ja509941g" target="_blank">this paper ($)</a> in the Journal of the American Chemical Society delve into the very popular hot injection method for the synthesis of cadmium selenide nanocrystals. They conduct a detailed investigation of what makes this reaction work. Their data shows that cadmium and selenium ions bind to carboxylate additives in solution, and that those carboxylates in turn determine how fast the ions can travel throughout the solution. Using a rigorous model based on classic theories of crystal nucleation, the authors show that control of the diffusion coefficient, or how fast the ions float around solution, is what establishes control over nanocrystal size.<br />
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<i><b>Organic - </b>Relay Iron/Chiral Br</i><i><!--[if gte mso 9]><xml>
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Like your right and left hands, <a href="http://chemwiki.ucdavis.edu/Organic_Chemistry/Chirality" target="_blank">chiral molecules</a> are mirror images of one another and cannot be superimposed. Unlike your right and left hands, separating a mixture of chiral molecules into batches of a specific handedness, or chirality, is extremely difficult. In fact, chemists have usually avoided this problem entirely by developing stereoselective synthesis methods that produce exclusively molecules of a given chirality (stereoisomers). Methods that selectively produce one stereoisomer over another are always in high demand. The authors of <a href="http://pubs.acs.org/doi/abs/10.1021/jacs.5b00085" target="_blank">this paper ($)</a>, published in the Journal of the American Chemical Society, have developed a method by which an iron carbonyl catalyst can be used along with a chiral acid to stereoselectively hydrogenate molecules called benzoxazinones. This method improves on other known syntheses by using an extremely cheap iron catalyst as opposed to expensive metals like palladium or ruthenium.<br />
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<i><b>Physical - </b>Channeling Vibrational Energy To Probe the Electronic Density of States in Metal Clusters</i><br />
Electronic structure describes the energy levels available for compounds to move electrons to and from when making and breaking bonds. Seems important for chemists, right? When it comes to electronic structure, molecules behave one way, bulk solids behave another way, and we know a great deal about both of those regimes. However, when it comes to metal clusters - molecules containing only tens of metal atoms - things get very blurry. The authors of <a href="http://pubs.acs.org/doi/abs/10.1021/jz502669s" target="_blank">this recent study ($)</a> in the Journal of Physical Chemistry Letters (ACS) used a highly sophisticated laser apparatus to vaporize cobalt metal into small clusters of about ten cobalt atoms. These clusters were then heated by an infrared laser, then hit with an ultraviolet laser. By studying how the clusters' interactions with the ultraviolet laser changed with temperature, the authors were able to experimentally map out the clusters' electronic structure. Information of this nature typically comes from computer simulations, so an experimental verification of those simulations is extremely important.<br />
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<i>Author's note: If you're keeping track at home, yes, that was three lasers. This paper has quite possibly the coolest methods section I have ever read.</i><br />
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<b style="font-style: italic;">Remember, </b><i>if you come across an article that you think should be featured here, </i><b style="font-style: italic;">send it in! </b><a href="mailto:treetownchem@gmail.com">treetownchem@gmail.com</a><br />
<br />
<span style="color: #999999;"><i>ACS - American Chemical Society<br />RSC - Royal Society of Chemistry</i></span><br />
<span style="color: #999999;"><i>$ - subscription required to access</i></span>Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com1tag:blogger.com,1999:blog-1971936738593606253.post-70716942658363179452015-02-05T13:51:00.001-05:002015-02-06T10:24:56.641-05:00ICYMS 3, Student Edition: Get More Out of Your Salts with Bijay Bhattarai<div style="text-align: justify;">
In the past, <a href="http://treetownchem.blogspot.com/2014/09/introducing-icyms-in-case-you-missed.html" target="_blank">In Case You Missed Seminar</a> has focused on the achievements of a traveling scholar who recently visited Michigan for a talk. This time, though, we'll take a look at some research done by a second-year student gearing up for their departmental seminar. </div>
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Bijay Bhattarai is a second-year organic chemistry student in <a href="http://www.umich.edu/~nagornyp/" target="_blank">Dr. Pavel Nagorny's research group</a>. Dr. Nagorny's group pursues natural product synthesis with particular emphasis on the chemistry of sugars and other carbohydrates. Bijay, along with co-author Jia-Hui Tay, recently <a href="http://pubs.rsc.org/en/content/articlelanding/2014/cc/c4cc08604j#!divAbstract" target="_blank">published the results</a> ($) of his research with Dr. Nagorny in Chemical Communications (RSC).</div>
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<i><b>Ion Activation: Splitting Salts to Increase Reactivity</b></i></div>
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<tr><td class="tr-caption" style="text-align: center;">The structure of diphenyliodonium<br />
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Organic chemists are always looking for newer and better ways of building up small molecules piece by piece. Often, the starting materials for organic reactions take the form of salts, which are composed of positive and negative ions. The positive ion is called the <span style="color: red;">cation</span>, and the negative ion the <span style="color: blue;">anion</span>. The picture at the left shows an example of one salt, diaryliodonium triflate, used in the authors' paper.</div>
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When reactions are carried out in non-polar solvents such as toluene and hexanes, the ions in salts tend to stay close to one another. The attraction of positive and negative charges keeps them together. When another molecule tries to come in and react with either the cation or anion, the strong salt bond must be overcome first, which can prevent the reaction from happening at all.</div>
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Enter "ion activation." The focus of Bhattarai and Tay's paper is the use of a cooperative reaction additive that is known to bind to anions. The specific type of molecule they employed is called a thiophosphoramide. After the thiophosphoramide has partnered up with the anion, the bond between cation and anion is weakened, and the cation can more easily participate in reactions.</div>
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Bijay and Tay used this scheme to attempt to improve upon <a href="http://pubs.acs.org/doi/abs/10.1021/ja801767s" target="_blank">a known reaction</a> ($) in which benzoic acid is transformed to its phenyl ester via a copper(II) catalyst. The results? Adding in the thiophosphoramide not only greatly increases the yield of the products, but also reduces the temperature needed to activate the reaction. They show that the reaction works for a variety of different diaryliodonium and copper reagents. Under their optimized conditions, they were able to esterify several different kinds of carboxylic acids, including some steroid compounds.</div>
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For Bhattarai, it was rewarding to see some of the same principles at work in his reaction flask that are so important to protein function in biology. "Proteins do the exactly the same thing. It's cool to think of it that way," he said. Proteins have highly specific binding pockets that isolate molecules and orient them in a certain way to direct their reactivity. Often, ion pairing is an important part of that process.</div>
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<b><i>All According to Plan</i></b></div>
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<tr><td style="text-align: center;"><a href="http://3.bp.blogspot.com/-QszP_rcysro/VNOznopFQDI/AAAAAAAAARU/x-Q5_5nbg4Y/s1600/bijay_cropped_2.jpg" imageanchor="1" style="clear: right; margin-bottom: 1em; margin-left: auto; margin-right: auto;"><img border="0" src="http://3.bp.blogspot.com/-QszP_rcysro/VNOznopFQDI/AAAAAAAAARU/x-Q5_5nbg4Y/s1600/bijay_cropped_2.jpg" height="257" width="320" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">Bijay Bhattarai, the paper's first author.</td></tr>
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According to Bhattarai, the results were not very surprising. "When I started, we already knew something like that might happen," he said. The project grew out of
<a href="http://onlinelibrary.wiley.com/doi/10.1002/anie.201307133/pdf" target="_blank">results published previously by another lab member</a> ($) and some further
preliminary experiments conducted by Tay.</div>
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In fact, the authors were surprised that their method was not more
widely applicable. It was originally anticipated that the ion activation
scheme would work for a wider variety of nucleophiles, not just
carboxylic acids. When the results did not come right off the bat, Dr.
Nagorny suggested building on the results his students already had with
carboxylic acid esterification. "We just took this reaction and said,
yeah, we're just going to make it bigger and do a lot of substrate
scope, do some catalyst scope," said Bhattarai.</div>
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For this type of paper, the short form of a communication worked out nicely. "We were just looking for an initial picture of the activity of the thiophosphoramides," said Bhattarai. With so much promise on the project, it was appropriate to submit the communication right away. After two months of hard work, the paper was well-outlined.</div>
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<i><b>Onward and Upward</b></i><br />
Bhattarai credits his quick success in publishing to a combination of luck and long hours spent in the lab. "I just got lucky that I had a working project," he said. "But then, of course, we work late into the night, and that is the only factor that really matters. When you work long hours, you get more results, and more data," which, he added, allows you to sort through the uninteresting results more quickly.</div>
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"This is just a starting point," he said of the publication. He seemed excited to pursue further research on the subject in the future, rather than moving to something new after writing the paper. "We have a bigger picture of [this reactivity], and we just started small to see if it would work." As always, there is a whole pile of science left to be done.</div>
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With a smile, Bijay added, "Hopefully the bigger picture is going to work as well."</div>
Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com0tag:blogger.com,1999:blog-1971936738593606253.post-73960373649916300032015-01-23T09:15:00.000-05:002015-10-25T14:54:41.474-04:00Faculty Panel Gives Advice for Grad Students Seeking Academic Postdocs<i>The #SciBlogReaders survey is still underway! If you enjoy this blog or another science blog, <a href="http://treetownchem.blogspot.com/2015/10/scientists-surveying-science-blog.html">click here to learn</a> how you can help bloggers and win some cool prizes for yourself.</i><br /><br />Last week at the University of Michigan, the department's<a href="http://cpdo.chem.lsa.umich.edu/home" target="_blank"> Chemistry Professional Development Organization</a> (CPDO) organized a seminar called "Ascending the Summit: How to Make the Best Postdoc Application and Interview." The goal of the seminar was to prepare current graduate students in chemistry for the process of landing a postdoctoral position after graduation.<br />
<br />
Viewed by many as a stepping stone to a faculty position, a postdoctoral fellowship allows a newly-minted doctorate to stretch their legs and apply themselves in a new research lab, sometimes dedicated to drastically different research. Choosing where to do a postdoc, figuring out which research labs to approach, and getting hired are often critical steps for a chemistry graduate looking to continue along an academic career track.<br />
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The seminar was composed of a faculty panel of four chemistry professors, ranging in experience from the newly-hired <a href="http://www.schindlerresearchgroup.com/" target="_blank">Professor Corinna Schindler</a> ([bio]organic) to <a href="http://www.umich.edu/~caflab/index.htm" target="_blank">Professor Carol Fierke</a> (chemical biology), who has served as chair of the department since 2005. The panel was rounded out by <a href="http://www.umich.edu/~lehnert/NLehnert.html" target="_blank">Professors Nicolai Lehnert</a> ([bio]inorganic) and <a href="http://www.umich.edu/~ruotolo/index.html" target="_blank">Brandon Ruotolo</a> (analytical/chemical biology). CPDO presented a list of questions compiled from suggestions by seminar registrants. Once the room settled down, it was off to the races.<br />
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The following is a summary of the seminar, which was dense with good advice and important information. Use the list below to jump to the question that interests you most, or read the whole post top-to-bottom. And when you finish, feel free to leave a comment! Many of these questions are open-ended, and more voices answering means more perspective for everyone reading.<br />
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<a href="https://www.blogger.com/null" name="top"></a><a href="https://www.blogger.com/blogger.g?blogID=1971936738593606253#Q1">Q1: When hiring a postdoc for your own lab, what do you look for?</a><br />
<a href="https://www.blogger.com/blogger.g?blogID=1971936738593606253#Q2">Q2: Do you have a preference as to whether your potential postdoc wants to end up in academia or industry?</a><br />
<a href="https://www.blogger.com/blogger.g?blogID=1971936738593606253#Q3">Q3: How much involvement do you expect postdocs to have? What role do you typically expect them to play?</a><br />
<a href="https://www.blogger.com/blogger.g?blogID=1971936738593606253#Q4">Q4: In transitioning from graduate studies to postdoctoral research, how much of a change should you make in terms of entering a new field?</a><br />
<a href="https://www.blogger.com/blogger.g?blogID=1971936738593606253#Q5">Q5: How involved do you expect postdocs to be in the teaching process?</a><br />
<a href="https://www.blogger.com/blogger.g?blogID=1971936738593606253#Q6">Q6: How long is too long for a postdoc?</a><br />
<a href="https://www.blogger.com/blogger.g?blogID=1971936738593606253#Q7">Q7: What should a postdoc do as far as procuring their own funding?</a><br />
<a href="https://www.blogger.com/blogger.g?blogID=1971936738593606253#Q8">Q8: As a graduate student, how early is too early to start lining up a postdoctoral position?</a><br />
<a href="https://www.blogger.com/blogger.g?blogID=1971936738593606253#Q9">Q9: How much independence does a postdoc have to pursue new ideas/discoveries (perhaps off the path of the grant)?</a><br />
<a href="https://www.blogger.com/blogger.g?blogID=1971936738593606253#Q10">Q10: Are there disadvantages inherent to doing a postdoc outside of the USA if your Ph. D research was conducted there, or vice versa?</a><br />
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<a href="https://www.blogger.com/null" name="Q1"></a><i><b>Q1: When hiring a postdoc for your own lab, what do you look for?</b></i><br />
The panel's responses to this question dealt mostly with the way in which a postdoc's application was presented. "Make your email exciting to the PI," said Professor Ruotolo. The panel agreed that the onus was on the potential postdoc to make plain what they were going to add to the PI's lab, regardless of the postdoc's field of origin. These ideas would be fleshed out more in the fourth question.<br />
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Other suggestions during this discussion came from Professor Schindler, who suggested sending a paper letter along with an electronic application to the PI of interest. For Schindler, the tangible paper letter makes a postdoc application a little more difficult to forget, increasing the applicant's chances of landing an interview. Professor Fierke also stressed that postdocs would do well to meet their prospective PIs in person at conferences or seminars. Additionally, a letter of reference from the postdoc's previous advisor goes a lot further when both the previous advisor and the prospective advisor are in good contact.<br />
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<a href="https://www.blogger.com/null" name="Q2"></a><i><b>Q2: Do you have a preference as to whether your potential postdoc wants to end up in academia or industry?</b></i><br />
Discussion on this point was very concise, with the panel members agreeing that from the perspective of a PI, the postdoc's future plans were not very relevant. However, Professor Ruotolo stressed the importance of potential postdocs considering how taking on a postdoctoral fellowship will benefit their careers. In some industries, such as pharmaceuticals, having done a postdoc can give you an edge in landing what is sure to be a competitive position. However, in other industries, the experience may carry less weight (or none at all).<br />
<i>[<a href="https://www.blogger.com/blogger.g?blogID=1971936738593606253#top" target="_blank">back to top</a>]</i> <br />
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<a href="https://www.blogger.com/null" name="Q3"></a><i><b>Q3: How much involvement do you expect postdocs to have? What role do you typically expect them to play?</b></i><br />
As could be expected, different professors on the panel had different ideas about how to answer this question. Professor Fierke expects postdocs to bring maturity and scientific perspective to her group, but does not expect postdocs to be responsible for directly mentoring graduate students. Professor Ruotolo agreed, noting that he prefers a "flat architecture" for intellectual hierarchy in his lab.<br />
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Professor Lehnert offered a contrasting opinion. He expects postdocs to take on direct leadership roles, contribute to grants, and develop management skills. His view is that the postdoctoral experience is a critical intermediate step between ending one's career as a graduate student and beginning one's career as an independent principal investigator. Even if a postdoc comes to his lab from a different field and does not know how to do a certain reaction, for example, the postdoc's broader experience as a researcher allows them to learn and troubleshoot the reaction faster than a graduate student.<br />
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<a href="https://www.blogger.com/null" name="Q4"></a><i><b>Q4: In transitioning from graduate studies to postdoctoral research, how
much of a change should you make in terms of entering a new field?</b></i><br />
Professor Lehnert jumped on this question. He advised researchers seeking postdocs to primarily look for something that they're really excited about. He acknowledged that getting a position might be harder the further a postdoc moves from their original field of research, but said, "You just have to get the interview. Once you get the interview, everything changes."<br />
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The panel also reiterated (as in Q2) that it is critical for postdocs to consider how taking a particular position will set them up for the next step of their career. For postdocs considering branching out, the options are many, so careful decision-making is critical.<br />
<blockquote class="twitter-tweet" lang="en">
A4, C. Fierke: There are so many directions, and the more u know what you want, the more you'll be able to make sure u get the right skills.<br />
— Tree Town Chemistry (@treetownchem) <a href="https://twitter.com/treetownchem/status/554723866984333312">January 12, 2015</a></blockquote>
<a href="https://www.blogger.com/null" name="Q5"></a><i><b>Q5: How involved do you expect postdocs to be in the teaching process?</b></i><br />
The panel agreed that they prefer postdocs to be uninvolved in teaching. Postdocs are typically hired as researchers, so PIs want to maximize the benefit of their hire by maximizing the time available for research. However, if a postdoc is interested in getting more teaching experience, perhaps in preparation for applying for a job at a primarily undergraduate institution, then that can be made to happen as well. Again, though, the onus is on the postdoc to shape their own experiences in preparation for the professional future they envision for themselves.<br />
<i>[<a href="https://www.blogger.com/blogger.g?blogID=1971936738593606253#top" target="_blank">back to top</a>]</i> <br />
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<a href="https://www.blogger.com/null" name="Q6"></a><i><b>Q6: How long is too long for a postdoc?</b></i><br />
"This is probably going to be very discipline-specific," said Professor Ruotolo. His own postdoc was 4 years. At the outset, he had expected it to be shorter, but "there are lots of things that can complicate timelines for postdocs." He stressed that the most important thing is for postdocs to leave having accomplished something. If it takes an honest 4 or 5 years for a promising project to pan out, and if the funding holds up, there is nothing wrong with that.<br />
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Professor Schindler noted that postdocs in organic chemistry are significantly shorter. She looks for postdocs with the expectation that they will work for a year with the option to renew their contract after that year, with a two-year average.<br />
<i>[<a href="https://www.blogger.com/blogger.g?blogID=1971936738593606253#top" target="_blank">back to top</a>]</i> <br />
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<a href="https://www.blogger.com/null" name="Q7"></a><i><b>Q7: What should a postdoc do as far as procuring their own funding?</b></i><br />
None of the four panel members expected postdocs to be able to arrive at the job with funding. It requires an unrealistic amount of anticipation to think that a postdoctoral researcher will know where they will end up and what they will be working on early enough in advance to secure an appropriate grant. However, all of the panel members voiced expectations that postdocs will contribute to grant applications to help renew or procure new funding for the laboratory.<br />
<i>[<a href="https://www.blogger.com/blogger.g?blogID=1971936738593606253#top" target="_blank">back to top</a>]</i> <br />
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<a href="https://www.blogger.com/null" name="Q8"></a><i><b>Q8: How early is too early to line up a postdoc as a graduate student?</b></i><br />
Between six months and a year from the potential postdoc's projected graduation date was acknowledged as the ideal time to look for and lock down a postdoctoral position. Any earlier than that, and it becomes uncertain whether a project will still be funded by the time a postdoc arrives. (Professor Fierke, the most experienced member of the panel, noted that the one year maximum is an unfortunate consequence of recent changes in the funding climate.) Any later, and job applications get jumbled up with thesis requirements, which can make for a hectic, stressful, and ultimately less effective final semester.<br />
<i>[<a href="https://www.blogger.com/blogger.g?blogID=1971936738593606253#top" target="_blank">back to top</a>]</i> <br />
<br />
<a href="https://www.blogger.com/null" name="Q9"></a><i><b>Q9: How much independence does a postdoc have to pursue new ideas/discoveries (perhaps off the path of the grant)?</b></i><br />
The panel members had somewhat differing opinions on this subject. Professor Ruotolo jumped at the question, explaining that the postdoctoral phase is one of the best times for researchers to explore "lateral space" in science. In his lab, exploration of new discoveries is met with excitement and encouragement. However, Professor Lehnert pointed out that this kind of creativity is limited by the money, and that he would ask postdocs to find a balance between pursuing new ideas and ensuring that enough progress is made on established projects to keep the funding coming in. At the end of the day, primary investigators have to get their grants renewed to keep the lab running, and postdocs have to be part of that.<br />
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Professor Fierke stressed the importance of having a conversation with the PI about how much of the research a potential postdoc will be able to take with them, and having that conversation as early as possible. Particularly if the postdoc wants to seek an independent research position at a high-level institution such as an R1 school, tensions can arise when a postdoc comes across an idea that they might use to found their own lab, but the postdoc's PI wants to hold onto it. The best way to avoid that tension is to communicate clearly, early, and often.<br />
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<a href="https://www.blogger.com/null" name="Q10"></a><i><b>Q10:</b></i> <i><b>Are there disadvantages inherent to doing a postdoc outside of the USA
if your Ph. D research was conducted there, or vice versa?</b></i><br />
Professor Ruotolo, whose postdoctoral research was conducted at the University of Cambridge in the United Kingdom, was very enthusiastic about recommending that students considering postdocs outside of their country of origin at least try to make it happen. Ruotolo's advisors in the United States were worried that he would have a difficult time getting a job back in the USA if he took a postdoc position at Cambridge due to the lack of a strong network. To remedy that concern, Ruotolo recommended that students seeking postdocs in other countries look at their potential PI's track record for placing researchers in jobs, whether the students are interested in working back in their country of origin or in the foreign country in which they want to do their postdoc. "The advantages of trying far outweigh the disadvantages," he said.<br />
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Professor Schindler echoed his sentiments and added some of her own. She recommended that students looking to transition from the USA to elsewhere in the world specifically seek out postdoc advisors with strong ties to the USA. As with any career search, networking plays a big role, and the stronger the network overlap is on either side of the ocean (Atlantic <i>or</i> Pacific), the easier the career search will be.<br />
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<i><b>The Conversation Continues</b></i><br />
The CPDO seminar was very motivating and contained great advice for graduate students starting their postdoc searches or considering whether to postdoc at all. However, this seminar just scratches the surface of the conversation happening now in chemistry on postdoctoral researchers, tenure-track faculty, and the job climate for newly-minted chemistry doctorates in general. As with a new research project, there is a wealth of information out there, and it falls to us as students to find it, process it, and use it to make the best choices we can. Of course, seminars like "Ascending the Summit" are great places for that research to start.<br />
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<i>For more perspective on this issue, you might start with <a href="http://www.chemistry-blog.com/2010/07/18/finding-a-postdoc-position-is-a-difficult-journey-but-here-are-15-tips-to-help-you-along-the-way/" target="_blank">this post</a> from Chemistry Blog, <a href="http://proflikesubstance.blogspot.com/2010/02/in-defence-of-postdoc.html" target="_blank">this post</a> from Prof-Like Substance, and <a href="http://marshdispatch.blogspot.com/2012/08/advice-for-grad-students-and-post-docs.html" target="_blank">another post here</a> (and linked posts) from Anna Armitage. Update 2/3: I found <a href="http://www.gpchemist.org/graduateandpostdoctoralchemist/december_2014#pg24" target="_blank">another good article</a> at ACS Graduate & Postdoctoral Chemist.</i><br />
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<i><b>Was this information useful to you? Does it
contradict your own advice or experience? The comment section is wide
open for further discussion on this important topic!</b></i>Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com0tag:blogger.com,1999:blog-1971936738593606253.post-11497063109529397722015-01-06T12:24:00.002-05:002015-01-06T12:31:48.659-05:00Chemistry Literature Feature Vol. VII<b><i>Have you seen a good paper lately? Written one? Send it in and have it featured here! </i></b><a href="mailto:treetownchem@gmail.com">treetownchem@gmail.com</a><br />
<br />
In 2015's very first Chemistry Literature Feature, we'll take a look at a lot of interesting, technique-based studies for new types of analyses. We'll see mass spectrometers that can track drugs through fingerprints, detection of tiny protein intermediates that might lead to Alzheimer's, real-time tracking of single proteins through cells, and more. But first, a little snapshot of what it's like to be a first-year grad student:<br />
<br />
<i><b>Overheard at Michigan:</b></i><br />
<blockquote class="tr_bq">
<i>"I mean, there's a lot to take in here. This is the first time that I've had to think about what a volt actually </i>is.<i>"</i></blockquote>
<i><b>Analytical -</b></i> <i>Mass spectrometry imaging of fingerprint sweat on nanostructured silicon</i><br />
In <a href="http://treetownchem.blogspot.com/2014/12/astrochemistry-in-action-rosetta.html#ms" target="_blank">mass spectrometry</a>, analytes must be ionized before they can be detected. The energies used in ionizing techniques can be quite high - high enough to destroy the molecule entirely. So-called "soft" ionization techniques <a href="http://www.the-scientist.com/?articles.view/articleNo/16661/title/Maldi/" target="_blank">such as MALDI</a> have been developed to avoid complete decomposition of analyte molecules, but these are most useful for very large molecules such as proteins. For small molecules such as illicit drugs, extra compounds needed for soft ionization techniques can actually confound analysis. <a href="http://pubs.rsc.org/en/content/articlepdf/2015/cc/c4cc08762c" target="_blank">This study ($)</a>, recently published in Chemical Communcations (RSC) uses a relatively new ionization technique called DIOS, or <b>d</b>esorption <b>i</b>onization on (porous) <b>s</b>ilicon, to analyze for the presence of drug molecules in human sweat. Using their technique, the authors are able to create 2D maps of the fingerprints of smokers and non-smokers, confirming the presence or absence of nicotine (or nicotine metabolites) and determining its distribution throughout the fingerprint.<br />
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<i><b>Chemical Biology - </b>Single-molecule tracking in live</i> Vibrio cholerae <i>reveals that ToxR recruits the membrane-bound virulence regulator TcpP to the toxT promoter</i><br />
Cells are immensely complicated. To figure out how they work, scientists of all disciplines have invented scores of techniques in order to grow the toolbox at humanity's disposal for understanding why cells make food or cause diseases. In <a href="http://onlinelibrary.wiley.com/doi/10.1111/mmi.12834/abstract;jsessionid=3DCA1973469F56AF594F1309DAAC95D1.f02t01" target="">this paper ($)</a>, published in Molecular Microbiology (Wiley), the authors use <a href="http://blogs.scientificamerican.com/observations/2014/10/08/ability-to-see-single-molecules-gets-chemistry-nobel/" target="_blank">single-molecule fluorescence microscopy</a> to study the movements of three critical proteins through <i>living</i> cholera cells. Two mutant cell lines lacking one or another of these critical proteins are studied as well. The findings suggest that cholera toxin is only produced through a complex interaction involving these three critical proteins. One membrane-bound protein reaches out and "recruits" a second from the cell's cytoplasm, and the protein dimer then binds to a third membrane-bound protein to form the toxin-producing complex. Interrupting this interaction could lead to new cholera treatment therapies.<br />
<i>-University of Michigan research conducted in <a href="http://sites.lsa.umich.edu/biteen-lab/" target="_blank">Dr. Julie Biteen's group</a></i><br />
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Chemical Biology readers may also be interested in the Physical chemistry paper.<br />
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<b><i>Inorganic -</i></b> <i>Calculation of Ionization Energy, Electron Affinity, and Hydride Affinity Trends in Pincer-Ligated d<sup>8</sup>-Ir(<sup>tBu4</sup>PXCXP) Complexes: Implications for the Thermodynamics of H<sub>2</sub> Addition</i><br />
Hydrogenation chemistry and its reverse, dehydrogenation, are big business in the chemical industry. Catalysts that can <a href="http://www.dailytargum.com/article/2012/11/u-researcher-wins-award-for-studies-on-alternative-energy" target="_blank">reliably and selectively rearrange carbon feedstocks</a> into long-chain hydrocarbons suitable for use as fuel are constantly under development. An important part of the operation of these catalysts is their ability to bind and release a molecule of hydrogen. In a <a href="http://pubs.acs.org/doi/abs/10.1021/ic5015829" target="_blank">recent study ($)</a> published in Inorganic Chemistry (ACS), the authors seek to understand how a specific class of iridium catalysts binds hydrogen. This can be extremely difficult to determine experimentally, so the authors turned to <a href="http://www.shodor.org/chemviz/overview/ccbasics.html" target="_blank">computer modeling</a>, which is commonly used to understand phenomena that are too small, too fast, or too expensive for experimentalists to see. Their findings reveal that the addition reaction can be understood relatively simply as a sequential addition of a hydride (H<sup>-</sup>) and a proton (H<sup>+</sup>), and physical insight into the activity of these complexes is offered.<br />
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<i><b>Materials - </b>Water in Ionic Liquids at Electrified Interfaces: The Anatomy of Electrosorption</i><br />
Ionic liquids, or salts that are liquid around room temperature, have received a great deal of attention in chemistry recently. They are under study for everything from <a href="http://pubs.acs.org/cen/topstory/8113/8113notw7.html" target="_blank">solvents for chemical reactions</a> to <a href="http://phys.org/news/2011-04-scientists-ionic-liquid-batteries.html" target="_blank">liquid media for ion batteries</a>.<i> </i>However, because ionic liquids are so highly charged, they tend to absorb water very quickly from the air and hang on to that water rather tenaciously. According to the abstract of <a href="http://pubs.acs.org/doi/full/10.1021/nn505017c" target="_blank">this paper ($)</a> published in ACS Nano, "[c]omplete removal of water from [...] ionic liquids is nearly impossible." Instead, the authors turn to molecular dynamics calculations to understand how water behaves within an ionic liquid, particularly near the surface of an electrode experiencing an applied voltage. Their findings suggest that water migrates quickly to the charged surfaces, particularly positively charged ones. This observation may inform future observations as ionic liquids are used for wider and wider applications.<br />
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<b><i>Organic - </i></b><i>Thiophosphoramides as cooperative catalysts for copper-catalyzed arylation of carboxylates with diaryliodonium salts</i><br />
In organic chemistry, which is concerned with building highly specialized small molecules step-by-step, an arylation reaction is one in which a benzene ring (or modified benzene ring) is attached to the substrate of interest. The authors of <a href="http://pubs.rsc.org/en/content/articlelanding/2014/cc/c4cc08604j#!divAbstract" target="_blank">this study ($)</a>, recently published in Chemical Communications (RSC), observed that the yield of copper-catalyzed arylation reactions was increased in the presence of a strong hydrogen bond donor. Their findings demonstrate that a thiophosphoramide reagent, which contains an N-P=S central group, works together with the traditional copper catalyst to provide the highest yields of the final arylated product. They demonstrate this method and explore functional group tolerance for a few small molecules and also for larger steroids.<br />
<i>-University of Michigan research conducted in <a href="http://www.umich.edu/~nagornyp/index.html" target="_blank">Dr. Pavel Nagorny's group</a></i><br />
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<i><b>Physical - </b>Intermediates caught in the act: tracing insulin amyloid fibril formation in time by combined optical spectroscopy, light scattering, mass spectrometry and microscopy</i><br />
Large, fiber-like clusters of proteins called <a href="http://www.alz.org/braintour/plaques.asp" target="_blank">amyloid fibrils have been associated with Alzheimer's</a>, Alzheimer's and a number of other neurodegenerative diseases. However, recent thinking in the field suggests that it is not these large fibrils themselves, but their smaller precursors that are the culprits in these diseases. The catch: the large fibrils are very easy to detect. The smaller clumps of only a few proteins ("oligomers") that lead to the formation of the fibrils are not. With so little known about this subject, the authors of <a href="http://pubs.rsc.org/en/content/articlelanding/2015/cp/c4cp03072a#!divAbstract" target="_blank">this study ($)</a> in Physical Chemistry Chemical Physics (RSC) studied insulin, which forms fibrils under certain conditions <i>in vitro</i>. Using a wide range of characterization techniques, the authors are able to describe the oligomerization process using insulin as a model and suggest that these smaller intermediates are directly connected to the formation of larger fibrils. Their methodology lays the groundwork for future studies on proteins whose fibrils are connected with disease states.<br />
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Physical chemistry readers may also like the Inorganic chemistry paper.<br />
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<span style="color: #999999;"><i>ACS - American Chemical Society<br />RSC - Royal Society of Chemistry</i></span><br />
<span style="color: #999999;"><i>$ - subscription required to access</i></span>Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com0tag:blogger.com,1999:blog-1971936738593606253.post-11819008984078806682014-12-15T16:48:00.000-05:002015-01-05T18:53:46.034-05:00Astrochemistry in Action: The Rosetta Observation<div style="text-align: justify;">
Last Wednesday, the <a href="http://www.esa.int/Our_Activities/Space_Science/Rosetta/Rosetta_fuels_debate_on_origin_of_Earth_s_oceans" target="_blank">European Space Agency (ESA) released the results</a> of measurements conducted by the Rosetta space probe, currently in orbit of a 2.5-mile wide comet designated as 67P/Churyumov-Gerasimenko. The measurements are the newest development in the quest to determine the origins of Earth's water - specifically, <a href="http://www.smithsonianmag.com/science-nature/how-did-water-come-to-earth-72037248/?no-ist" target="_blank">whether it was delivered by impacts from comets or asteroids</a>. The findings revealed that the chemical composition of the water on the comet 67P was significantly different than that found in Earth's oceans.</div>
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"Wait, what? Isn't water H<sub>2</sub>O, no matter where you find it?" If you find yourself wondering how comet water could be different from Earth water, or if you're interested in how chemistry can be applied <i>in space</i>, read on.</div>
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<i><b>Isotopes: Not All Atoms Are Created Equal</b></i></div>
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Atoms are composed of three basic subatomic particles: positively-charged protons, negatively-charged electrons, and neutrons, <a href="http://chemistry.about.com/od/chemistryjokes/ig/Chemistry-Cat/Chemistry-Cat-Neutrons-Drink-Free.htm" target="_blank">which have no charge</a>. Atoms of different elements always have different numbers of protons, and atoms of the same element always have the same number of protons. Electrons are much messier, but they don't play much of a role in this story, so we'll leave them for another day.</div>
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<table cellpadding="0" cellspacing="0" class="tr-caption-container" style="float: left; margin-left: 0px; margin-right: 0px; text-align: left;"><tbody>
<tr><td style="text-align: center;"><a href="http://4.bp.blogspot.com/-Xe7YwqX6QQ0/VI9Ob87IqZI/AAAAAAAAAO4/k27CeiowRbA/s1600/h_vs_d.png" imageanchor="1" style="clear: left; margin-bottom: 1em; margin-left: auto; margin-right: auto;"><img border="0" src="http://4.bp.blogspot.com/-Xe7YwqX6QQ0/VI9Ob87IqZI/AAAAAAAAAO4/k27CeiowRbA/s1600/h_vs_d.png" height="189" width="200" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">Hydrogen (H) and deuterium (D) both<br />
form water, but they are made of<br />
different stuff on the subatomic level.</td></tr>
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Neutrons add to the mass of an atom without changing its chemical identity. Atoms of the same element can have different numbers of neutrons. The simplest (and most relevant) example is the difference between hydrogen (H) and deuterium (D). The average hydrogen atom contains only a proton and an electron. Deuterium, on the other hand, has a proton, an electron, and a neutron, so it is heavier than a regular hydrogen atom, but because it still has only one proton, it still acts like hydrogen. Hydrogen and deuterium are called <b><i>isotopes</i></b> of one another - same element, different mass.</div>
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You may have heard the word "isotope" connected with radioactivity, such as the famous <a href="http://en.wikipedia.org/wiki/Plutonium-239" target="_blank">plutonium-239</a> used in nuclear bombs, or carbon-14 used for <a href="http://hyperphysics.phy-astr.gsu.edu/hbase/nuclear/cardat.html" target="_blank">radiocarbon dating</a>. Radioactive isotopes are unstable and decompose at predictable rates. However, there are plenty of stable, non-radioactive isotopes that do not decompose on their own. Hydrogen and deuterium are two examples. A very important consequence of their stability: once a sample containing hydrogen and deuterium is isolated from its environment, the ratio of hydrogen to deuterium will never change.</div>
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Stable isotopes have (<a href="http://chemwiki.ucdavis.edu/Physical_Chemistry/Quantum_Mechanics/06._One_Dimensional_Harmonic_Oscillator/Kinetic_Isotope_Effects" target="_blank">almost</a>) the same chemistry as one another. Hydrogen can react with oxygen to form water, and so can deuterium. H<sub>2</sub>O, D<sub>2</sub>O, and HDO all exist, and all are colorless, odorless, tasteless liquids at room temperature. On Earth, about <a href="http://en.wikipedia.org/wiki/Deuterium" target="_blank">16 of every 1,000 hydrogen atoms</a> are actually deuterium. So, if these three kinds of water are so similar to each other, how do scientists figure out the difference?</div>
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<a name="ms"></a><i><b>The Measurement: Mass Spectrometry</b></i></div>
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<tr><td style="text-align: center;"><a href="http://4.bp.blogspot.com/-ByIKCufCa0Y/VI9QDKe6hGI/AAAAAAAAAPQ/3nSTVn0AuoA/s1600/gcms_cropped_um.png" imageanchor="1" style="clear: right; margin-bottom: 1em; margin-left: auto; margin-right: auto;"><img border="0" src="http://4.bp.blogspot.com/-ByIKCufCa0Y/VI9QDKe6hGI/AAAAAAAAAPQ/3nSTVn0AuoA/s1600/gcms_cropped_um.png" height="211" width="320" /></a></td></tr>
<tr><td class="tr-caption" style="text-align: center;">A mass spectrometer at the University of Michigan<br />
Department of Chemistry. This instrument also uses a gas<br />
chromatograph (GC) in conjunction with the MS to identify<br />
complex mixtures of compounds.</td></tr>
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One very common method for determining the amount of an isotope present in a sample is to measure the mass of a molecule of that sample using a technique called <i><b>mass spectrometry</b></i>, often abbreviated MS.<i> </i>In mass spectrometry, molecules are hit by a high-energy spark of electricity to charge them up. Then, the molecular ions (charged molecules) are flown through a tube in the presence of an electric or magnetic field. The field is adjusted to allow only ions of a certain mass-to-charge ratio to pass through to the detector, which measures how many of the ions got through. Different mass-to-charge ratios are permitted through the tube one-at-a-time as the instrument continually adjusts the field strength. In this way, an analyst can measure the relative amounts of chemicals of different masses within the original sample. Mass spectrometry can be coupled with other separation or chemical analysis techniques to give even more information about the sample.</div>
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The ESA's Rosetta probe contains <a href="http://sci.esa.int/rosetta/35061-instruments/?fbodylongid=1650" target="_blank">two very sophisticated mass spectrometers</a>. Since there is no easy way to bring the water on the comet to Earth for analysis, the ESA brought the mass spectrometer to the comet. The readings that were sent back to Earth showed that the water on comet 67P contains three times more deuterium than the average value in Earth's oceans. Since deuterium is stable, and since the comet is an isolated system that does not exchange water with other bodies in the solar system, the findings suggest that water from comet 67P and related comets was not the primary source for Earth's water.</div>
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<i><b>Problem Solved! ...Right?</b></i></div>
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Of course not! Science is <i>never</i> over!</div>
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The Rosetta measurement is just one piece of an extremely large and complicated puzzle. It is strong, but not conclusive, evidence that Earth's oceans could not have come from cometary collisions. For starters, Rosetta has only measured the composition of the comet's outer layer, so the deeper water could potentially be different. Secondly, 67P is only one comet among many. According to Dr. Nicholas Dauphas at the University of Chicago, <a href="http://news.nationalgeographic.com/news/2014/12/141210-rosetta-comet-water-space-science/" target="_blank">quoted by Dan Vergano at National Geographic</a>, this "is a very exciting study that raises more questions than it answers."</div>
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One intriguing facet of the Rosetta measurement, though, is its simplicity. Even though the ESA spent millions on launching the probe to comet 67P in an <a href="http://www.cnn.com/2014/11/13/world/comet-landing/index.html" target="_blank">unprecedented feat of aeronautics</a>, the chemistry that the probe examined in these measurements is fairly basic. The next time you're sitting in General Chemistry picturing a chemist toiling behind a benchtop somewhere in a sterile lab, maybe try picturing that scene <i>in space</i>.</div>
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Everything is cooler in space.</div>
Jimmy Branchohttp://www.blogger.com/profile/07705071756791719656noreply@blogger.com2