musings on music and life

April 26, 2012

Pictures!

Filed under: Carnatic Music — sankirnam @ 9:05 pm

Kiran and I did not coordinate our colors beforehand; it happened to be a coincidence.

To the best of my memory, the song list was:

1. Varnam – Swararanjani – Adi – Vinjamuri Varadaraja Iyengar

2. Shri Mahaganapathi – Gaula – Misra Chapu – Muthuswami Dikshitar

3. (I dont remember the song, but it was a fast-paced Adi thalam composition of Muthaiah Bhagavathar)

4. Saadinchane – Arabhi – Adi – Thyagaraja

5. Enthavedukondu – Saraswathi Manohari – Adi – Thyagaraja

6. Narasimha – Bilahari – Misra Chapu – Vinjamuri Varadaraja Iyengar

7. Vote of thanks

8. Ni Namarupamulaku – Saurashtram – Adi – Thyagaraja

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April 20, 2012

the future of organic synthesis

Filed under: Chemistry Jobs — sankirnam @ 10:04 am

With the declining job market for chemists, a lot of people who were classically trained as organic chemists have been forced into other sectors of the economy in order to put food on the table. Evidence for the lack of employment opportunities is here: http://www.reddit.com/r/chemistry/comments/s1780/the_chemistry_job_market_is_brutal_just_ask_these/. For those who don’t read Reddit, this is a thread about the chemistry job market, including a video by ACS interviewing students about their estimated employment prospects (it’s not very encouraging). The fact that so many chemists are being displaced today makes one think that the field has matured to the point where synthesis is a trivial endeavor. But is that necessarily true?

Since the development of organic chemistry as a discipline in the 1800’s, chemists were concerned with the most fundamental of questions, “Can we make this type of bond?”. Later, this became “Can we make this type of structure?”, once the diversity of structures in natural products was discovered. Natural product total synthesis was kickstarted by Woodward’s (more on Woodward in a later post) synthesis of quinine in the 1940’s, and came to a grand culmination with Kishi’s synthesis of palytoxin in the 1990’s. The studies on natural product total synthesis enabled the synthesis of incredibly complex molecules to be approached in a rational manner, and also had the side benefit of the development of numerous novel reaction methodologies (e.g. E. J. Corey’s discovery of TBS protection, the development of the Nozaki-Hiyama-Kishi reaction, among others). Since that time, the field has matured some more, but the exponential breakthroughs of the 20th century have slowed down. There have still been some noteworthy developments, however, such as the development of the field of organocatalysis, and the recent explosion of interest in the chemical community in organofluorine chemistry.

In a recent Nature paper last year, Prof. Macmillan (now at Princeton) stated, “Organic chemists are now able to synthesize small quantities of almost any known natural product, given sufficient time, resources and effort”. This is very true; in my experience, there are very few boundaries left for organic chemists to tackle. Classical and modern synthetic methods allow the synthesis of almost any molecule conceivable; and new molecules and reactions are being discovered every day. In this sense, organic synthesis is no longer something difficult; it is no longer valuable to make molecules just for the sake of making molecules. What is lacking, however, is a complete understanding of how reactions work. While organic synthesis has plowed along, developments in physical organic chemistry have not been so rapid. Our understanding of reaction mechanisms, conformational analysis, and stereocontrol is still at a very basic level. Fundamental studies in these areas would greatly assist our ability to develop stereospecific reactions. Efforts to replace precious metals (such as Ru, Pd, Pt, Rh) with cheaper alternatives would also go a long way towards making chemistry sustainable for the future.

In my opinion, the future of organic synthesis no longer lies in simply making molecules; research into better understanding of reactions and catalysis is where its at.

April 16, 2012

on digital music archival

Filed under: Uncategorized — sankirnam @ 12:43 pm

Another interest of mine that has developed over the past several years is the collection, digitizing, and archival of classical Carnatic music. This is something I do out of my own interest, for no profit, since a lot of the recordings that I have obtained over the years were obtained at no charge. Similarly, when I share recordings with others, I do not charge them anything. Digital distribution of music, especially Carnatic music, has been dramatically changed by the internet. Since Carnatic music is still a relatively niche art form, it has not been as dramatically affected by Napster and other file sharing services as western mainstream music. Nonetheless, online communities have sprung up dedicated to sharing non-commercial recordings. An example is: http://www.sangeethapriya.org/

Archiving music is not a trivial exercise, however. A lot of the time, concerts are distributed without proper file tagging or artist information. Completing both of these takes time, and deducing the performing artists is not that easy. It takes a trained ear, with lots of experience to do just that (identify the violinist and mrudangist in a recording). I am very good at identifying the percussion artists, and reasonably good at identifying violinists. Even then, this exercise still takes time and careful listening. I have a large number of unlabeled concerts that require such information, and it is difficult to find volunteers who have the skill and time to do this sort of processing. If you are willing to help, let me know. 

The rush in digitizing old music archives also merits discussion. The most popular format used for digital audio storage is .mp3. Mp3 has the advantage in that it is now a near-universal format, even though there are other superior audio codec formats available. The mp3 format is a “lossy” format, in that the file size is compressed from the original. This is achieved by two methods: by using existing file compression methods (like those used in .zip and .rar file formats) and by cutting out bits of the audio file. The latter is actually what contributes most to the reduced size of mp3 files compared .wav or raw audio files. The parts of the audio usually eliminated are frequencies below 50 Hz and above 15 KHz (those outside the range of hearing for most humans). The amount of trimming done to the audio is dictated by the bit rate, with higher bit rates having less audio loss (and correspondingly larger file sizes).

The rush in digitizing music resulted from the fact that analog recordings made on spool tapes or magnetic audio tapes can degrade over time. Therefore, permanent solutions were desired and since mp3 is the most popular format, most audio files are in that format. However, amateur digitizers should be aware (most are not) about the “lossy” nature of mp3. While .mp3 files are fine for casual distribution and listening (listening tests reveal that most people cannot tell the difference between a 128 kbps mp3 and the uncompressed file), digital masters should be saved in a lossless format. While this would entail the necessity of having massive hard drives, declining hard drive prices in recent years are making this more and more practical. The advantage of having lossless master copies is the ability to compress to whatever bitrate is desired without sacrificing too much quality (remember that converting one mp3 to another mp3 results in a further loss of quality – the effects multiply). A tool that allows you to do just that is here: http://www.dbpoweramp.com/dmc.htm

 

April 10, 2012

Carnatic music at Caltech!

Filed under: Carnatic Music — sankirnam @ 8:32 am

This was a performance I participated in 2008 at Caltech. The other performers, Naresh (flute) and Shankar (violin) were students there at the time. Chetashri (Dwijavanthi) and Rama ninne (Huseini) were played. This served as a nice demonstration for students unfamiliar with Carnatic music.

April 6, 2012

First concert review

Filed under: Carnatic Music — sankirnam @ 11:24 am

If I had started this blog earlier, I would have linked this earlier. One of my concerts in December was reviewed in the Hindu. This is interesting because there were only a handful of people in the audience (this is usually the case for junior concerts), and I had no idea a critic was there!

This was the first review for me, even if it was only one line, and I came out relatively unscathed. Hopefully this is the first of many more (good!) reviews to follow…

http://www.thehindu.com/todays-paper/tp-features/tp-editorialfeatures/article2759453.ece#.Tv0oobgCirI.gmail

April 5, 2012

On carbocations and George Olah

Filed under: Chemistry — Tags: , — sankirnam @ 10:52 am

Most people who have studied biology or medicine in any depth in college often have to take an organic chemistry course. During that time, students typically learn about various types of reactions and their mechanisms, including those of acid-catalyzed or acid-promoted reactions. Almost all of these reactions involve positively-charged, “onium ion” intermediates. The species involved can include positively charged oxygen atoms (oxonium ions), nitrogen atoms (ammonium or nitrenium ions), phosphorous (phosphonium ions), sulfur (sulfonium ions), iodine (iodonium or periodonium ions), chlorine (chloronium ions), bromine (bromonium ions), mercury (mercurinium ions), and, of course, carbon (carbocations).

Understanding the significance of carbocations in organic chemistry requires a little perspective. In the early part of the 20th century, physical organic chemistry was beginning to become a thriving field. The introduction of physical methods into chemistry (especially spectroscopy) gave chemists new, extremely powerful methods of characterization of compounds. Chemists desired not only to come up with new transformations, but to apply these physical methods in understanding the steps involved as well. The reigning dogma (propounded by Sir. C. K. Ingold), was that in order to know if an intermediate lay on the reaction pathway, it should be isolated and characterized. What Ingold did not know, that is taken for granted today, is that stability and reactivity are opposing properties. That is, if something can be isolated, it is generally not very reactive. Conversely, the more reactive something is, the more difficult it becomes to isolate.

Thus, after Meerwein and Whitmore introduced the theory of the involvement of carbocations as intermediates in acid-catalyzed organic reactions, attempts were made by numerous chemists to isolate or observe them. The triphenylmethyl cation was able to be isolated and studied (this cation is extremely stable due to the large delocalization of charge into the phenyl rings); this is even done in undergraduate labs today! Solutions of the triphenylmethyl cation in sulfuric acid are extremely stable and have a bright yellow color. However, other carbocations could not be isolated despite numerous attempts, and so chemists had to resort to solvolytic methods for their study. In a solvolysis reaction, the carbocation precursor (with a good nucleofugal (leaving) group) is refluxed in a polar solvent. The product(s) are then isolated and the structure of the carbocation intermediate determined based on the product distribution. This may seem like a crude way of doing things (and in retrospect, it is), but it still allowed some brilliant deductions to be made, attesting to the quality of the minds of the people who were involved in these studies.

Key among these initial investigators was Saul Winstein, who was at UCLA. Winstein is especially noteworthy in that he advanced the concept of the “non-classical” carbocation (although the person who actually coined the term is John D. Roberts). Non-classical carbocations can loosely be described as pentavalent, delocalizing charge through σ rather than π interactions. Winstein also came up with numerous other concepts now in the parlance of organic chemistry such as ion pairing, internal return, anchimeric assistance, and homoaromaticity, among others. He was a brilliant chemist and (in my opinion) undoubtedly would have shared the Nobel Prize with Prof. Olah had it not been for his untimely demise in 1969.

At around the same time this was going on, other developments in acid-promoted organic reactions were taking place. Friedel-Crafts chemistry (which is routinely taught to undergraduates these days) was developing into a field of industrial importance, and initial studies on hydrocarbon isomerization were being carried out (most notably by P. D. Bartlett at Harvard). All of these lay the stage for the rather climactic entrance of George Olah into the world of carbocation chemistry.

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George Olah had started his career in the Technical University of Budapest and in a few short years had carved out a reputation for himself as a creative organofluorine chemist. In his biography, he recalled having to literally work on a balcony of the chemistry building, because his former boss was unwilling to grant him any lab space! He also mentioned that it was not possible to procure a lot of the reagents that he needed for his research, such as HF, FSO3H, and BF3, and he actually had to make those himself. Things turned around however, and Olah fled Hungary during the 1957 revolution with his family and migrated to Canada, where he started work for the Dow Chemical Company. There, he was able to pursue his research interests with earnest and became known as a giant in the field of Friedel-Crafts chemistry. It was also at this time that Olah became interested in tackling the chemistry of carbocations, since those are well-known intermediates in Friedel-Crafts reactions. Olah had the intuition to realize that carbocations would be extremely strong Lewis acids, and that their isolation would therefore require discovering even stronger Lewis acids than those known at the time. He then systematically screened all the high-valent metal fluorides known and eventually came across antimony pentafluoride, SbF5. Antimony pentafluoride is a colorless, fuming, extremely viscous liquid, and is still one of the strongest known Lewis acids to this day. Olah found that addition of t-butyl fluoride to excess antimony pentafluoride resulted in a solution of the t-butyl cation (paired with SbF6- or Sb2F11- counterions). This discovery marked a watershed in the field of carbocation chemistry. Up to that point, carbocations were thought of as simply being too energetic or unstable to isolate; Olah’s discovery enabled the direct observation (by NMR spectroscopy) of these otherwise transient species! As the Nobel committee was to later comment, “George Olah gave the cations of carbon long life”. This longer life was several orders of magnitude; carbocations could go from just hanging around for milli- or microseconds to several hours.

Olah later moved to the Western Reserve University in Cleveland, and was one of the people who oversaw the confederation with the neighboring Case Institute of Technology to become Case Western Reserve University, as it is known today. There, he extended his work to the chemistry of superacids. Bronsted superacids are defined as acids stronger than 100% sulfuric acid. Examples are chlorosulfonic acid (ClSO3H), fluorosulfonic acid (FSO3H), trifluoromethanesulfonic (triflic) acid (CF3SO3H), and the newly discovered carborane acids. It is known that the strength of liquid Bronsted acids can be increased by addition of a Lewis acid; this improves the charge delocalization in the counterion and thereby increases the effective proton activity (or acidity). Olah thus combined his prior experience with fluorosulfonic acid with antimony pentafluoride and came up with the acid mixture FSO3H-SbF5, which later became known as “Magic Acid” due to it’s ability to dissolve candle wax. This accidental observation led to new discoveries in superacidic hydrocarbon chemistry. Olah proposed that in superacid solutions, alkanes are protonated along C-H or C-C σ bonds, in a 3-center, 2-electron fashion. These then break down to yield either H2 or trivalent carbocations. This is simply a consequence of the extreme acidity of these systems; they are strong enough to protonate the weakest bases possible, σ bonds. This hypothesis was borne out through a series of papers with careful mechanistic studies. The applications of this chemistry are enormous; the industrial cracking of high-molecular weight hydrocarbons into lighter fractions is carried out over solid acid catalysts (usually zeolites) and is a multibillion-dollar industry; understanding the mechanistic details of these processes is therefore of great importance.

Olah was also well-known for his involvement in the norbornyl (or non-classical) ion controversy, where he took the opposite stance against H. C. Brown. Thanks to his discoveries enabling the direct observation of carbocations at variable temperature, Olah was able to prove, through careful NMR experiments, that the norbornyl ion has a bridged (or nonclassical) structure. The controversy was well-documented, and a lot of old-time chemists remember those days vividly.

Recently, Olah has been involved in promoting the “Methanol Economy” as a way of ensuring a sustainable future. I’ll mention more about this later.

For readers, I apologize for not including structures; this is just a consequence of my laziness and also due to the fact that almost everything mentioned here can be looked up in seconds on Wikipedia anyway.

April 2, 2012

science is broken, part 1

Filed under: Chemistry Jobs — sankirnam @ 11:14 am

I just saw this letter in last week’s C&EN, and thought I would talk about it: http://cen.acs.org/articles/90/i13/Aspire-Science.html

I’ve seen so many articles lately in Science lamenting that there are so few undergraduates (in the US) studying science. The reason is extraordinarily simple; it boils down to a cost/benefit analysis. Most undergraduates quickly realize that the enormous amount of time studying something difficult (such as science) could be put to better use studying something easier with better rewards. Case in point: one of my friends was a bio major (he’s very intelligent, and had scored in the 98th percentile on the MCAT) and was in the process of interviewing for medical school, when he performed this cost/benefit analysis. He realized that he was much better at economics than at bio (as evidenced by the better grades he got in the former with significantly less studying required on his part), and so decided to go into finance instead. He has now been hired at an investment bank with a starting salary that I would never be able to get in the chemical field.

This explains why, when you walk into any research lab in any university in the US, the labs are always staffed by foreign students and postdocs. Only people from poor countries will find value in coming here and living in poverty (by US standards) for several years. The average graduate stipend of approx. $1800/month is barely anything by American standards (Jorge Cham makes the point very succinctly here: http://www.phdcomics.com/comics/archive.php?comicid=1215), but for foreign students, this is a lot of money, and gives them to chance to come to America, which, as most of them have been thinking since childhood, is the greatest country on earth and the land of infinite opportunity.

Even then, after living off a measly stipend for several years earning a degree of questionable utility, the employment opportunities are nary to be found. For these same foreign students, they are still happy to take opportunities working as postdocs in academic labs, working 80-90 hours a week for $30-40k per annum, since that is still a lot of money where they come from. Some of the lucky few of these postdoctoral scholars get academic positions; the fate of the others is unknown. It is because of this that academia has been described as a giant pyramid scheme. Professors need to keep hiring fresh graduate students as extremely cheap, hardworking labor, and don’t give a second thought to their futures when they graduate. The academic job market quickly became saturated, as more people received PhD’s than there were positions available. In the last decade, with the advent of globalization, the industrial job market  (in the US) has also been spiraling downward.

That is why, whenever I see youngsters choosing to major in scientific disciplines such as mathematics, physics, chemistry, biology, or other related fields, I try my utmost to dissuade them from doing so. The life of a scientist is no longer well-paying and glamorous like it used to be a few decades ago. As of right now, the only fields of study which can lead to jobs able to support a middle-class lifestyle (approx. 100k/year salary) are finance, computer science, and electrical engineering.

Research in most institutions is funded by federal programs, such as NIH, NSF, DOE, DARPA/ARPA, and others. Recently, most of these programs have stopped funding “curiosity-driven” or fundamental research and instead chosen to fund only “application-oriented” research. This is not a good sign, in my opinion. Historically, the health and prosperity of a civilization could be gauged by its ability to support such “curiosity-driven” studies that supposedly had no immediate applications. An example is the flourishing of philosophy (Plato, Socrates, Aristotle) at the height of the Greek civilization, Newton’s discoveries of calculus and classical mechanics during Restoration-era England, and even the United States’ successful landing on the moon during the period of post-WWII prosperity.

More in the next…

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