March 31, 2014
March 30, 2014
A couple of weeks ago, Roy Periana (Scripps Florida) published this paper in Science detailing his latest work on C-H activation of alkanes. Honestly, I don’t understand why this was published in Science; the biggest issue is that this reaction uses stoichiometric amounts of thallium or lead! If you read the paper, Periana cleverly skirts around that rather glaring issue…kudos to him for his clever rhetoric. The other issue is that doing electrophilic reactions/C-H activation with late transition or d10 metals is not that difficult; Periana’s initial successes were with catalytic mercury in sulfuric acid, and later with Au in selenic acid. Since Tl(III) and Pb(IV) are isoelectronic with Hg(II), I’m not surprised by this latest report.
C&EN’s hype of this paper, though, just made me facepalm. These two sentences are almost comedy gold:
“[…] a research team including Brian G. Hashiguchi and Roy A. Periana of Scripps Research Institute Florida and Daniel H. Ess of Brigham Young University has discovered that inexpensive main-group thallium and lead complexes work well at converting the typically unreactive alkanes in natural gas into alcohol esters […]”
Uh, but Tl(TFA)3 is $336/25g (Strem), and this is only for technical grade product! I can’t find pricing information for Pb(TFA)4, since it is not commercially available. Reading the SI for this paper reveals that the authors synthesized the Tl and Pb complexes! C&EN needs to get their facts straight before making claims that these are “inexpensive”.
“Periana says the team is in discussions with several companies and entrepreneurs and would ideally like to jointly develop the technology with a petrochemical company or spin off a start-up company. […]”
Who, I ask WHO is going to start a company based on a process that uses stoichiometric amounts of thallium or lead? Thallium, like arsenic, is incredibly toxic, and there is absolutely no way the EPA would greenlight it. Governments worldwide have gone to a lot of effort to remove lead from gasoline since it is known to be a neurotoxin; starting a company like this, based on a process that would potentially use tons of those metals, would be counterproductive.
I hope the chemistry community collectively facepalmed like I did upon reading this tripe by C&EN; if not, well, then here is one reason why people these days don’t really respect chemists anymore…
March 27, 2014
C&EN has an article about Prof. Stephen J. Lippard, recipient of the 2014 Priestley Medal. I feel privileged to say that there is only 1 degree of separation between us; one of my good friends is now doing a postdoc with Prof. Lippard at MIT. His Priestley Medal address is enlightening, and both articles contain some choice quotes:
“Science doesn’t work a 40-hour week. It can’t stop on Friday afternoon at 5 o’clock if that experiment is percolating. Sometimes you just can’t stop yourself from going in on Saturday morning or at midnight or on Sunday to see what’s happening […]“
“Chemistry experiments set up on Friday afternoon may often not wait until Monday morning to be worked up and extended. Some experiments require attention late into the evening or even a return to the laboratory long after normal business hours. […] Unlike many professions, experimental chemistry cannot be done from the comfort of one’s home via the Internet.”
This is all too true. Unfortunately, scientists these days (chemists especially so), are underpaid and underappreciated by society (relative to doctors, lawyers, bankers, and MBA’s) when one considers the time-intensive and inherently risky nature of our work.
March 24, 2014
This is the current state of organic chemistry research today; the field has matured so much, and existing areas are being farmed to such an extent that research groups are publishing basically identical work independent of each other (although I do not know that for sure, I give the authors the benefit of the doubt). As one of my coworkers mentioned, this is why the time for obtaining a PhD in organic chemistry has been increasing over the last few decades; increased competition results in many people around the world also working in your area of research, and potentially working on exactly the same thing you are working on!
This is also a reflection of the current “fluorine bubble” in organic chemistry research today. Due to the hype associated with fluorine, a lot of groups are now entering the area and rediscovering the wheel, so to speak. While there have been some nice breakthroughs recently (by Tobias Ritter and Melanie Sanford), most of the work done by newcomers in fluorine chemistry is overhyped.
March 19, 2014
It’s not always that I find a paper that makes me jump off my feet in excitement, but this might actually be it. The chemistry being described is pretty run-of-the mill (generation of benzyne by deprotonation-elimination in liquid ammonia), but……it is written in verse.
Unfortunately, the editor adds a note: “[…] Because of the somewhat increased space requirements and possible difficulty to some of our nonpoetically inclined readers, manuscripts in this format face an uncertain future in this office.”
March 11, 2014
Good news! This can now be shared publicly:
I had submitted this for the IndianRaga Fellowship last month, and since it was a blind audition, did not share the recording with anyone else. Now that the first round (which this was submitted for) is over, it can be identified with me.
Many thanks to my sister for putting the thalam accurately! The challenge in preparing this recording was mainly in structuring a complete thani (solo) within the 7 minute time constraint. Fortunately I have a lot of experience in doing so from playing numerous concerts in Chennai, and for whatever reason, Misra chapu is the easiest one for me to structure for a short time. It is all too easy to lose track of time when playing something like Adi thalam or Misra Jampa.
I’ve always had a soft spot for Misra chapu. It seems deceptively simple at first, with the 3+4 (or 1.5+2 structure, depending on how you look at it), but it allows for enormous scope and can get very complicated. In chatusram itself, you can split it not just as the usual 6+8, but 7+7, 5+9, 10+4, 12+2 (and these can be noncommutative as well, in the sense that playing 9+5 will sound different from 5+9). Tisram in misra chapu also leads to several new ideas. The base can be kept as 7+7+7, but 9+3+9 is also possible, and 6+3+6+6, and 6+5+5+5, 5+7+9, etc. This is the basis for kannaku (calculations) in carnatic music, and as one can see, it is all just arithmetic! Of course, the bottom line is aesthetics. Beauty in form is paramount. The most complicated calculations are worthless if there is no elegance in how it is perceived by the ear.
The late mrudangam vidwan Palghat Raghu sir was also very fond of Misra chapu, and drew a lot of inspiration from the solos of Palani Subramania Pillai. Unfortunately, recordings of Palani are scarce, but one can get an idea of how he played from listening to his star student, Trichy Sankaran sir. All of these vidwans laid the groundwork for a lot of the splittings I mentioned in the previous paragraph, establishing them and showing their scope.
March 5, 2014
This is from a symposium I attended last year at UCI. Since the JOC organizers were looking for volunteers, I shamelessly decided to comment on the chemistry being presented that day. I promise that I am normally much more coherent than I appear in that video! Being forced to talk remotely intelligently on topics I had just heard fleetingly a few hours ago is not an easy task.