if pyridine wasn’t so stinky. Maybe one could use picoline?

This is from ACIE 1978, 17, 569, a review article on the powers of aminopyridines, such as DMAP (4-dimethylaminopyridine)[1]:

The enormous increase in reaction rate [of alcohol acylations, 10000 times over pyridine] is illustrated by the following comparison. Equimolar amounts of anhydrous or 96% ethanol (29 mL, 0.5 mol) and acetic anhydride (47 mL, 0.5 mol) are mixed in two Erlenmeyer flasks with stirring. To the first flask is added pyridine (8 mL, 0.1 mol). Within 3-4 min the reaction mixture begins to boil. When a solution of DMAP (0.6 g, 0.005 mol) dissolved in a small amount of ethanol is added to the second flask, the solution begins to boil spontaneously.

[1] I failed an esterification. I wanted to use a strong base to ensure completeness, and decided that triethylamine should work just as well as DMAP. After this I felt the need to educate myself on how important DMAP is. And now I’m educating you. What do they say? If you can’t practice something, you teach it…

Ever wondered why they say “there’s chemistry between them”? It should be photochemistry.

A couple of people absorb a quantum of horny, called sauvignon. They are promoted to a singlet excited state. From there, they can

1. Undergo internal conversion (emissionless relaxation): sometimes a cup of coffee means… a cup of coffee.
2. Fluoresce. Hetero sex. SCORE!!! Relax to ground state.
3. Cross over to a triplet state. They’ll lay on their backs and relax a bit.
4. In triplet state, they’re still excited, but they’re going to wait for more partners to show up to engage in group sex (photosensitization, radical reactions).
5. Phosphoresce: relax from triplet to ground state. Homo sex. Quantum forbidden does not mean impossible!

More definitions:
Extinction coefficient: measures the couples’ affinity for sauvignons.
Hangover: relaxation to elevated vibrational states.

P.S. Conceived while writing an answer for the physical organic chemistry final that I TA’d. The problem: why does irradiation norbonene+benzophenone results in Paternò–Büchi reaction, while irradiation of norbornene+acetophenone results in [2+2]-dimerization of norbornene? For a concise intro to photochemistry, the best book to go is Chapter 7 of the March’s Talmud.
P.P.S. Two years later, updated the bio!

From my friend’s advisor, originally from a Phys. Rev. Lett. editor.
Hint for future reviewers of sodium hydride oxidations: use the answer below!

I cannot review this paper as it is wrong and I did it first.

This paper should be rejected for the following reasons:
1. No one cares about this anymore
2. Anyone who could referee it is probably dead
3. All who read it will wish they were

… the revised version is greatly improved … there are now only a large number of grammatical errors rather than a huge number.

I beg your pardon. My office was painted and repaired a couple of weeks ago and that involved moving out more or less entirely. I have no idea where his manuscript is, or if I received it. For what it is worth, the title does sound slightly familiar.

I apologize for the delay in reviewing this paper. I inherited a 127 student electrical and computer engineering course plus lab this January because the professor assigned to teach it unexpected passed away. My department head attends every lecture to make sure I do a good job.

From authors:
This is an example of the fact that scientific progress usually proceeds incrementally, sometimes in unbearably small steps. We believe that our Paper represents one of those steps.

I was wondering if I could find out what the latest status of our manuscript is. I told my mother about my first submittal to Physical Review Letters, and she won’t stop bothering me about it. She keeps calling to see if it’s been accepted or not; I’ve tried telling her it’s with the editors, and but she’s getting tired of hearing that. I realize you have been unearthing yourself from a large amount of snow, and that no doubt has been a hindrance. Any more recent news on the manuscript is greatly appreciated.

… our paper has no conclusion, because we wanted to save space.

You asked for justification for a Rapid. We are pleased to tell you that all the authors agree that this should be a Rapid.

[1] Paul over at ChemBark does such a nice job covering chemical faux-pas in media with his What’s Wrong With This Picture series. But most of the pictures shown are American. Today, a labmate showed me another example from 2009, this time in the city of Constance in Germany, proving once and for all that blatant chemical ignorance is not confined to the good ol’ U.S. of A.

The city of Constance is on Lake Constance, a large lake on the borders of Germany, Austria, and Switzerland. To promote its university’s science department, the city put up signs promoting “Die Stadt am H₂O,” or “The City on the H₂O,” or, if you haven’t guessed yet, “The City on the Water.” The sign included an outline of the lake filled with little schematic drawings of molecules of water.

Very cute. But look a little closer at the water molecules…

So apparently it’s not actually the City on the H₂O, but rather the City on the CH₂O. Which I imagine smells like cancer.

[1] Literally, “We can do anything. Besides chemistry.” It’s a take on “Wir können alles. Ausser Hochdeutsch” (We can do anything. Besides (speak) High German), a slogan from the south German state of Baden-Württemberg, boasting its economic growth as well as their inhabitants’ refusal to speak the dialect of German spoken in the north. I think it’s the German equivalent of “Don’t Mess With Texas.”

They never tell you that you forget your own… what’s the word…?

language.

I could have browsed a hundred expat blogs, read a thousand expat forum posts, filtered through a million dos-and-don’ts, and never had I heard that the command of your mother tongue is reduced to that of a moderately gifted third-grader- the kind that gets extra credit for using a word with more than three syllables. I thought, despite my numerous character flaws, that my command of the English language was worthy of a gold star or two. I played with words and grammar like I played doctor- and I played to win. I could turn a phrase into a dick joke, or a dick joke into another dick joke. I was the jockstrap on the nutsack of Americanized, 21st century, Generation Y English. I was master of my own linguistic domain.

Turns out that didn’t mean a goddamned thing after I left the homeland. Here, away from home, away from my influences and my peers, they only act to obfuscate. I’m Superman in a kryptonite mine; Wonder Woman at a urinal. My powers are useless- and if anything, they’re detrimental to non-native English speakers understanding me at all. I thought English- my English, and by that I mean dick jokes- was universal. Turns out my English is not a universal language, and the language I speak now, while resembling the language I spoke in America in many ways, is slower, more articulate, less idiomatic- but it is not my native language. I never used to have to think about the things I said until now. If you think this is a good thing, well, you’re missing the point. I miss not having to think.

But if you think I have it bad, just think about the poor saps who attempt to speak German to me. God bless them, those poor souls. I can barely speak English now, I feel sometimes, and I’m expected to learn a new language? Nein, danke. Mein Deutsch ist schlecht.

I am an American living in Switzerland. Linguistically, this is the equivalent of Sarah Palin at a Mensa meeting. The Swiss are polyglots- they learn at least two or three languages growing up- and one of them nowadays is almost always English. Not only that, but in the German areas of Switzerland, they effectively learn two German languages- their spoken German (the rather melodic Schwyzertüütsch) and written German (which is the German I learned in high school).[1] But I know exactly one language with any fluency. Yes, I took German in high school, but Germany is pretty far away, so there wasn’t much opportunity to practice. I could have taken Spanish, but we didn’t have a gardener growing up, so not much point there.

So, when I joined my new group in Switzerland, I was quite literally the only monoglot in the group. Sure, I might be a postdoc, I might know certain areas of chemistry like a boss, but my ignorance of languages looms over me at all times. Everyone else in the group has another language they can turn to when they feel the need to communicate in a more raw, honest way- something that gives them an identity. English is the work language. But their work language- that is my only, my personal language. I feel naked, in a way. Naked and dumb. Seems strange, I guess, but there it is.

Fortunately, nobody expects me to learn a new language. The working language at the institute is English. The postgrad courses are in English. Everyone here is fluent in English. In fact, sometimes I think the Swiss prefer if I didn’t learn a new language. The following situation takes place on a daily basis:

Swiss cashier: “Grüezi!”
Excimer: “Grüezi, kann ich zahlen, bitte?”
SC: “Ja! jelgüüagegohääfkelgrioøhnwgjhioewgiowjyi032j0yleisli?”
E: *cocks head* “Wie, bitte?”
SC: *immediately switches to perfect English* “Will you be paying with credit card?”
E: “Umm.. yes?”

This is the dreaded “What in the living hell did you just say” moment- the one where I’m forced to come face-to-face with my own ignorance in a real-life situation and have an “educational moment” with a cashier when the line behind is ten old Swiss women deep[2]. Fine, that comes with the life of a foreigner. You play the foreigner game, you lose, you move on. However, the next situation, which is far more common for me, is even more irritating:

Excimer: “Grüezi! *says something in perfect spoken German because he totally heard someone who is actually fluent in German use it in this particular situation and for Chrissakes, my accent isn’t that bad is it?*”
Swiss Worker: *immediately switches to English, apropos of NOTHING* “Sure, I would be more than happy to help you find that.”

Well, okay, great, please help me find that particular product I was looking for, I’ll be over here REELING in my shitty German-riddled angst. Where did I fuck this up? How did they even know I’m American? I mean, yes, I’m a bit overweight, which is the calling card of the Anglophones, but it’s not like I’m wearing a t-shirt with the American flag on it or anything. I don’t understand. They seem have a sixth sense about these things, and even when I try to fit in, it’s not good enough. And it’s a Swiss thing- the Germans don’t do this, at least when I’ve been in Germany, and the French sure as hell don’t (unless they’re waiters, because Americans tip well).

But I get by. I learn. I take courses (or make a solid attempt to). I attain a more solid feeling for non-verbal communication, when I learn that someone is angry at me because I took their fork. The world’s languages might have spread from the Tower of Babel, but Americans, well, I guess we were stuck in the tower basement. Eventually you have to go upstairs and see what it’s like outside. It’s confusing. It’s frequently irritating. But also enlightening.

By the way, if you were expecting a post about science, forget it- this language issue is way more interesting to me. “Why is there grease in my NMR sample” is universal. The happy dance when you get a nice crystal structure is universal. Science is universal. And kind of boring, but in a nice, familiar way. And when you’re that far away from home, you’ll take any familiarity you can get.

[1] It’s actually fairly interesting why young Swiss speak English so well, especially compared to the surrounding countries. I had this discussion with several Swiss people in my group. Movies at the cinema in Switzerland are not dubbed, only subtitled, unlike in France and Germany where they are dubbed. Because of the Swiss preference to not dub, things like American and British movies and pop music have led to a surge of interest in learning English among younger people. In cities like Zurich you’d be hard-pressed to find a Swiss person under 25 who didn’t speak good English.
[2] Rule #1: Do NOT mess with old Swiss women. They will give you the look of death and send you an angry letter. And you do not want to get either.

The following gem appeared in my inbox this morning:

My name is Vinko Rajic , I can use telepathy , I am maybe the only person that can use telepathy all the time , send
and receive voice and video on distance of few kilometer. It works all the time and 100% correct.

I think it is important for science and human kind to make research on my brain and find out how this works.
My telepathy manifest itself exact like  “Schneider’s first-rank symptoms”.
Please send email to other scientists that could know about that.
I think it would be extremely important to find out what kind of waves transmit my thoughts.

I couldn’t resist sharing.  Oh, and by the way, he included a link.

Now even Matt Stone and Trey Parker, creators of South Park, are getting into the International Year of Chemistry spirit too, with a bulletin board of real actual molecules in their latest episode, “Ass Burgers.” I won’t give away what they’re talking about, but can YOU decipher what all the molecules are???

IYOC tag added by moi for sheer hilarity factor

First person to email me (excimer at coronene dot com) with all the correct answers wins a FREE bar of Swiss Chocolate! Yum! (I can only send it to people in Europe and North America, sorry guys, live somewhere else next time!)

WE HAVE A WINNER! Alex B. of Germany won the free Swiss chocolate because German trains are never on time and it would take forever for him to come down to Switzerland to get it himself. Also, because he was the first to give the correct answers:

1. Caffeine
2. Chlorogenic acid
3. Benzene
4. Retinol
5. some benzophenone-looking thingy
6. I don’t even know wtf is going on with that bicyclic thing on the right
7. sucrose
8. matt and trey are not known for their chemistry know-how

Congrats!

  I have two reasons for this post:

    1. The “preparing and studying materials thought impossible” nature of this year’s Nobel Prize.
    2. “Unclicking the Click” paper that describes mechanical reversal of The Click Reaction (azide–alkyne cycloaddition) by sonication. A question I thought of after reading the discussion here: what kind of the mechanical forces are in action during sonication (I mean, quantitatively)? Judging by this Wikipedia image, cavitation is quite a powerful thing. So powerful that it’s been thought to enable nuclear fusion on a benchtop, albeit most (all?) of these bubble fusion experiments could not be replicated.

  But today I’m asking a different question: what is the strongest possible material theoretically possible? Consider a fiber composed of identical linear bonds that are as strong as N≡N triple bond, spaced the same distance from each other as in alpha-nitrogen solid (face-centered cubic). We will pull on the material in order to effect the break right down the middle of the elementary lattice cube. In doing so, we are breaking two bonds per lattice (1 molecule per face, 4 faces, each shared between two cubes, 1*4/2=2). The bond will be considered broken when we achieve the displacement d of r*([2.5*2^–1/6)] – 1] = 1.307 Å, where r is normal bond length of 1.065 Å — in other words, stretch a bond 2.227 times, to 2.37 Å for N-N bond. This move along the Leonard-Jones potential takes care of 98.3% of the energy necessary to break a chemical bond. So,

we are solving for yield, Y, which is the force F required to break the material of a given cross-section s:
Y = F/s;
our cross-section is the area of one elementary lattice, a cube with edge a=5.661 Å:
s = a²;
the force required is, in simplified form, energy E you put into the system divided by displacement d=1.307 Å that this force achieves (I am not sure I’m correct here):
F = E/d;
the energy equals to bond dissociation energy of two dinitrogen bonds, found from known BDE value B=942 kJ/mol and Avogadro number A=6.02×10²³ mol^–1:
E = 2*B/A;
finally,
Y = 2*B/(A*d*a²) = [2*9.42×10⁵ J]/[(6.02×10²³ mol^–1)*(1.307×10^–10 m)*(5.661×10^–10 m)*(5.661×10^–10 m)] = 74.7 GPa.

  The strongest material in terms of ultimate strength listed on Wikipedia is carbon fiber, at 5.65 GPa.

  This means that all the materials left to discover are within one order of magnitude away from current record. Otherwise this fiber has to be composed of continuous array of bonds as strong as N≡N bond (which is the second strongest bond, right behind C≡O bond). We are very close to the limit of (what we know to be) possible.

  This is true for a lot of areas. We’re at the limits of human physical abilities: the new records are incremental increases to the old ones, at tremendous expense. We’re at the end of usable periodic table. The long-sought island of stability requires the building blocks with a very high neutron:proton ratio, which would be extremely unstable themselves. We’re not too far from the limit of the resources that are so far essential to human life on earth: irrigable soil, water, and fossil fuels. We’re at the limits of rocketry, unable to go much further than our star system on traditional combustion.

  The only thing that’s limitless is one thing that contains it all: the Universe. Not only is it limitless, not only is it ever-expanding, it is also expanding with acceleration. Being able to wrap your head around it is well worth the Nobel Prize.

Some good news!  Grad students (and a few postdocs) at my university recently worked to implement a change in the maternity and childbirth leave policy!  Now, if we end up pregnant, we don’t have to take a leave of absence and lose our health insurance!  (This was the old policy. I can’t imagine being uninsured and very pregnant or with an infant! Whose idea was THAT?!)  I don’t think too many of us are rushing to get knocked up as a result of the policy change, but it’s VERY very reassuring to know that we have options should the unthinkable happen.[1]

CBC readers know I tend to post about science (and, uh, unrelated fluff) rather than how being a woman has impacted my career.  This is, in large part, because I’ve been lucky enough to avoid having my gender affect my work.  (Here’s hoping this continues!)  I owe this good fortune in large part to men who get it. Often, men are demonized in grrrrl-science discussions.  Not specific men, who sometimes deserve to be called out for egregious wrongdoings, but men in a general sense, as though there is a great penis-conspiracy afoot.  We should never forget that some guys are tireless advocates for changes that benefit us all.[2]  On this note, I’d like to thank Frank Leibfarth for his role in getting the changes at UCSB implemented.  Knowing men like Frank makes me very hopeful for the future for women in academic science.

[1] I’m allergic to babies.  Don’t worry.

[2] Anything that makes it easier for us to have families (and, for that matter, lives outside the lab) is good for scientists in general.  Period.  No one who isn’t batshit insane with fantasies of being chained to the bench should argue otherwise.

Pentacene, polymorph I (single crystal) viewed down the c axis.

(I should note that this was a pretty difficult and detailed piece, and one with a lot of important little intricacies, and Greg did an amazing job with it.)