musings on music and life

April 14, 2016

Farewell, Kobe Bryant

Filed under: Uncategorized — sankirnam @ 1:01 am

There’s nothing I can say about Kobe Bryant that isn’t already in the annals of NBA history. He was such a huge part of my adolescence; I regularly watched Lakers games during middle school, high school, college, and whenever I could during graduate school. Kobe is another one of those rare individuals where I feel grateful just to be alive at the same time he is; I know for a fact that I will be telling future generations that I had the privilege to see his playing live (both on TV and directly at the Staples Center)!

I remember watching his record-breaking game against the Sonics in 2003 where he set NBA records for 3-pointers (12 in one game, 9 consecutively), another game against Houston that same year where he scored 50+ points and posterized Yao Ming on a sprained ankle, and the record-setting 81-point game in 2006 against the Raptors, among others. He led the Lakers to 5 NBA championships and has a host of NBA titles to his credit. Of course, good times come with the bad, and even the best players are not immune to that. Kobe was involved in a scandal in 2003-2004 in which he was accused of having unconsensual sex  with a girl in Colorado, and this followed the gut-wrenching loss of the Lakers in the 2003 NBA finals to the Detroit Pistons, in which the Lakers squad featured Kobe, Shaquille O’Neal, Gary Payton, and Karl Malone. The “dark years” of 2004-2008 featured a Lakers team that was trying to rebuild and rediscover its identity, and Kobe, the lone superstar, trying valiantly to rally the team against all odds to a playoff berth season after season. With Pau Gasol on the roster, the Lakers made it to the NBA finals 3 more times, from 2008-2010, with championships in 2009 and 2010. Unfortunately, the Lakers were swept by the Dallas Mavericks in the second round of the 2011 playoffs, which was a rather unfortunate sendoff for coach Phil Jackson, who led the Lakers to all of their NBA championships (Phil Jackson remains the most successful player/coach of all time, holding the NBA record for the most combined championships (13) as a player and a head coach).

Still, Kobe has that rare combination of athleticism and mental focus that makes him such a deadly athlete and competitor. I remember discussing the differences between Kobe and Michael Jordan with my friend once, and he pointed out that while Jordan had massive hands (“as big as frying pans”) that allowed him to palm the ball rather easily in order to dunk and do layups, Kobe did not have that genetic advantage; and yet, Kobe was just as deadly an opponent as Jordan was! Jordan may have had his “flu game”, but he never had an 81-point game like Kobe! Kobe Bryant is also renowned as a great “clutch” player, able to come through for the team in the last few critical moments in order to clinch victory, and this was seen tonight in the final game of his career.

Farewell, Kobe, and thanks for all the memories.

#MambaOut

2016-04-13 22.14.19

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November 13, 2014

amphoteros

Filed under: Chemistry, Uncategorized — Tags: — sankirnam @ 8:19 pm

I’ve been following Prof. Andrei Yudin’s blog for a while, and wanted to mention it here since he recently discussed an article by Prof. Karl Christe (one of my committee members). Prof. Yudin got his PhD with my advisor approximately 20 years ago, and after completing a postdoc with Prof. K. Barry Sharpless (Scripps), became a very successful professor at the University of Toronto. He initially did some interesting work with fluorinated BINAP and BINOL complexes and investigated their catalytic activity. However, his real claim to fame is his discovery of the rich chemistry of aziridine aldehydes.

One of the long-standing challenges in organic chemistry is the synthesis of compounds that contain complementary reactive groups in the same molecule. One example of this type of molecule is an unprotected amino aldehyde. Amines and aldehydes readily condense to form imines and/or hemiaminals depending on the conditions, and that is why one will never see small molecules containing free -NH2 and -CHO groups in the same structure. Prof. Andy Myers (Harvard) has synthesized N- and C– protected amino aldehydes as precursors for the in situ generation of free amino aldehydes.

Prof. Yudin elegantly demonstrated that if the amine is in the form of an aziridine (3-membered ring), then there is a kinetic barrier for imine formation, and thus unprotected (-NH) amines can exist along with an aldehyde functionality in the same molecule. These aziridine aldehydes can be accessed from DIBAL-H reduction of aziridine esters. They exist as homodimers and it is possible to chemoselectively access amine or aldehyde reactivity with the appropriate reagents and conditions.

Prof. Yudin continues his work with other intriguing amphoteric molecules and has also demonstrated novel applications for these new compounds, including their use towards the synthesis of cyclic peptides.

November 11, 2014

Gems from 1992

Filed under: Carnatic Music, Uncategorized — sankirnam @ 7:54 pm

I’ve long been obsessed with the recordings of TNS’s North American concert tour in 1992. It should be no surprise; TNS was the reigning Carnatic vocalist at that time, and the concerts in that tour reflect his absolute command over swara and laya. His voice was also in full form in all of those concerts, and the brigha-laden sangathis he was was able to create on the spot just leave one shaking his or her head in silent awe.

There’s another reason for my obsession, which is probably the biggest factor here. It is that this was my guru’s first concert tour of the US; he had the privilege of accompanying the top vocalist at that time for over 20 concerts when he was in his early 20’s! Narayanan sir’s playing style back then was also fundamentally different from his style today. All of the recordings of these concerts demonstrate his mastery over the use of the kappi mrudangam, and are an amazing demonstration of the traditions and legacy of Thanjavur Upendran sir.

I think these tracks speak for themselves in the quality of the vocal and mrudangam artistry, as well as the chemistry that TNS and Narayanan sir had in those concerts.

 

 

 

 

 

October 6, 2014

Random thought

Filed under: Carnatic Music, Uncategorized — Tags: , — sankirnam @ 9:09 pm

I was just thinking about this while listening to a recording of a Classical Carnatic concert I had attended in Chennai years ago:

The way most mrudangam vidwans are trained, and the way most mrudangam vidwans become popular as accompanists, is by anticipating and reproducing the structure of the song (as performed by the main artist) on the mrudangam as closely as possible. What that means is that as much as we give primacy to sarvalaghu as a mode of accompaniment, closely matching the sangathis, swaram, and niraval is what really scores points. Of course, the logical conclusion from this is that the most successful concerts are those in which the mrudangam vidwan has frequently performed with the main artist. For most serious Carnatic rasikas, this is so obvious that it does not even bear mentioning. GNB-Palghat Raghu, KVN-Palghat Raghu, SSI-UKS, U. Srinivas-Thanjavur Upendran, and even Sowmya-Neyveli Narayanan sir are some of the most enduring combinations in Carnatic music history.

So while this is all fine and dandy, the thought on my mind was specifically this: “If we are specifically trained to accompany only Carnatic pieces, how then can you fit the mrudangam into the wider scope of international music?”. Granted, even in a traditional Carnatic concert you always have to be prepared to play for pieces you have not heard before, but whenever that happens, the overall impact will never be the same as if you were accompanying a piece you are familiar with. Most mrudangam artists would not feel comfortable playing for jazz pieces without extensive and thorough rehearsals, but can play at ease for Carnatic concerts impromptu. I feel like whenever you play for a piece with extensive rehearsal, the charm of what makes the mrudangam unique as an instrument is lost; this is primarily because in a Carnatic concert, almost 90% of the concert is unrehearsed. The krithis may be familiar, but the improvisational aspects (such as raga alapana, kalpana swara, niraval, thani, Ragam Thanam Pallavi) are more or less on the spot.

I remember showing my friend (who had no background in Indian music) a recording of Karaikudi Mani’s Sruthi Laya as a way of easing him into Carnatic Music, and after listening to it for a few minutes, he immediately IM’ed me and remarked “this is way too rehearsed…is real Carnatic Music like this?”.

Maybe I am just spoiled after hearing too many live Carnatic concerts and directly experiencing the raw, unfiltered creativity of the world’s top percussionists firsthand…

September 9, 2014

Long-lived CF3-

Filed under: Chemistry, Uncategorized — Tags: , , — sankirnam @ 10:15 am

This paper from my lab has been getting a lot of press lately and so I figured it would be timely to discuss it here today. This paper represents the accomplishment of one of the holy grails of organofluorine chemistry – namely, the characterization of the CF3 anion as a long-lived species in the condensed phase. This paper effectively dispels one of the long-standing myths in organofluorine chemistry, that the anion is too kinetically unstable to be observed as a distinct species due to fast α-defluorination to generate difluorocarbene.

The project was initially conceived by my friend Dr. Fang Wang, who is now a postdoc working for Stephen Lippard at MIT. Prof. Ralf Haiges carefully prepared the NMR samples on his vacuum line, and Fang and Zhe Zhang conducted the NMR experiments and synthetic reactions. Fang and Dr. Martin Rahm also carried out quantum calculations at all stages of the project. In fact, the idea that CF3 could be observed as a distinct species first came from the results of initial quantum calculations, which showed that the barrier to defluorination was rather high (approx 17 kcal/mol).

Thus, by carefully preparing the NMR samples with rigorously anhydrous reagents (TMSCF3, 18-crown-6, KOtBu)  and solvents (THF) it is possible to generate solutions containing appreciable amounts of “free” CF3; these can be characterized by 13C and 19F NMR at low temperature (-80 ºC).

Prior evidence for the intermediacy of “free” CF3 in synthetic reactions came from work in our lab conducted towards another publication. It was found that KHMDS (potassium bis(trimethylsilyl)amide) was the base that worked best for deprotonating fluoroform. Other alkali metal bases were not as effective. Thus, it was also proposed that under the right conditions, K+ CF3 could be trapped and observed in the condensed phase. Unfortunately, we have been unable to get a crystal structure of the CF3 salt so far.

C&EN recently highlighted this work, and Angewandte Chemie made it a cover issue!

EDIT: Highlight by Prof. Gilmour in Angewandte Chemie

August 1, 2014

Double Iron

Filed under: Chemistry, Uncategorized — Tags: — sankirnam @ 5:55 pm

Interestingly enough, the following two papers were published the same day (today) in JACS:

Fe3

Fe2

Now, there are some subtle differences, but the chemistry is pretty much the same. The reason I noticed this is because iron catalysis is a favorite topic of mine (although I am currently not doing any research on it, I actively follow the literature on this topic).

EDIT: Silas Cook yesterday (Aug 4) published an almost identical article in Angewandte Chemie

March 19, 2014

Chemical poetry

Filed under: Chemistry, Uncategorized — Tags: — sankirnam @ 8:27 pm

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.”

Party poopers.

February 26, 2014

The secret of scent

Filed under: Books, Uncategorized — Tags: , — sankirnam @ 7:16 pm

I recently finished reading Luca Turin’s The Secret of Scent, and wanted to get my thoughts down before they faded to nonexistence. The book is very compelling, being that the subject matter is about human olfaction. The mechanism of how humans and other animals detect odor is still up for grabs, and there are several competing theories, such as the “lock-and-key” mechanism, or shape-based detection. The author’s central thesis is that the nose operates through a mechanism known as quantum electron tunneling, and he gives a detailed history of the development of the theory. The book is aimed at laymen, and is written for a nonscientific audience. As a chemist, I was very impressed by Turin’s coverage of the basics of organic chemistry, given that all the popular fragrance molecules in use today are small organic molecules! It is noteworthy that Turin is not an organic chemist by training; he got his PhD in biophysics. Turin posits that the odor of molecules as detected by the nose can be correlated with their IR (infrared) frequencies, and one of the biggest pieces of evidence he describes is the similarity of the smell of decaborane and thiols (B-H and S-H bonds both have IR frequencies around 2500 cm-1). Any organic chemist will be all too familiar with the vile smell of divalent sulfur compounds, such as H2S, thiols, thiolate salts, disulfides, and sulfides. However, the moment the sulfur is oxidized, the smell vanishes. Sulfoxides and sulfones do not smell bad at all. Recently, I have been working with aryl-SF5 compounds as part of my graduate research work, and those smell very pleasant, often reminiscent of their -CF3 analoges! Thus, according to Turin’s theory, they should have similar IR frequencies, which I am unfortunately too lazy to look up.

Turin explains that deuterated and non-deuterated molecules smell different when properly purified (by GC methods) and that the smell can be distinguished by trained individuals (he writes about his attempt to demonstrate this with acetophenone and acetophenone-d8). This is due to the isotope effect, which is most pronounced with D-H substitution, since deuterium is twice the mass of protium.

He also attempts to explain the difference in odor between the enantiomers of carvone, suggesting that the C=O stretch in one enantiomer may not be detected as well as other (which is entirely feasible when one considers that molecules in the nose are detected in a protein receptor, which is an inherently chiral environment). His experiment to prove this theory involves mixing simple ketones (such as acetone or MEK) and one enantiomer of carvone to see if the smell matches the other.

The above experiments call for reproduction by interested individuals, and it is noteworthy that Dr. Turin has wriiten about these experiments in detail in a book intended for laymen. His passion for the subject shines through every paragraph in the book.

That being said, here’s another shameless plug (for fluorine and fluorine chemistry). Selective fluorination may be another way to intelligently design new fragance molecules. While it is known that C-F bonds, due to their inherent polarity, are stronger than C-H bonds (and thus vibrate differently), organofluorine compounds are also often more volatile than their nonfluorinated counterparts. This could be useful for designing new “headnote” fragrances, which are the smells one initially detects when applying perfume; they only last for a few minutes or so.

November 15, 2013

Baby

Filed under: Uncategorized — sankirnam @ 3:21 pm

Just wanted to do a quick shoutout of my friend’s short story that recently got published: http://southernpacificreview.com/2013/11/12/baby/. Wouldn’t be doing this if it wasn’t good; it is worth a read.

July 24, 2013

Thanjavur Upendran

Filed under: Carnatic Music, Uncategorized — Tags: — sankirnam @ 10:05 pm

My guru Neyveli Narayanan sir is conducting his annual function in the memory of his guru Thanjavur Upendran soon:

upendran2013

I have been meaning to talk about Thanjavur Upendran (or Upendransir as my guru calls him) for a while now, and the apropos time has finally come.

upendran

The photo above is accurate; Thanjvaur Upendran was a left-handed mrudangist, but to my knowledge did not face the same hardship that Palani Subramania Pillai faced. Nonetheless, he had a very bright career as a Carnatic musician, which was cut short by his untimely demise at the age of 52. His memory is kept alive today by his students (most prominently my guru). Other students of Thanjavur Upendran include Thanjavur K. Murugabhoopathi and Thanjavur Kumar. I should also mention that Upendransir’s grandson, Thanjavur Praveen Kumar, is an outstanding upcoming young mrudangist. Oftentimes the gift for music skips a generation or two; there are numerous cases of not the children, but the grandchildren of famous musicians also having a gift for music.

Thanjavur Upendran developed an extremely distinct, unique style. He was well known for his finesse in accompaniment, which led to him being extremely in demand throughout his career. He played for all the famous musicians of his era, such as M. Balamuralikrishna, D. K. Jayaraman, Maharajapuram V. Santhanam, Dr. S. Ramanathan, T. R. Subramaniam, T. R. Mahalingam (flute Mali), N. Ramani, and Chittibabu, among others. He also accompanied female artists, including the Sikkil Sisters (flute) and M. L. Vasanthakumari. He was very meticulous in tuning his instruments – he was a fickler for perfection of the sruthi and only ever used kappi mrudangams. I’ve learned some of these aspects along the way; when checking the sruthi, the chapu, dhin, and nam strokes must all be aligned. Most vidwans do not check all three of these. The meetu must also be at the same sruthi; in fact sometimes Upendransir (and my guru) tune the mrudangam on the meetu alone! His style of accompaniment was very sensitive, and he was always quick to adjust his approach to that of the main artist; he was very popular with veena artists due to this reason.

This is a video of a concert from Mysore with D. K. Jayaraman (vocal) and M. Chandrashekaran (violin).

Above all, he is remembered today for his personality moreso than his music. I have read stories by so many of today’s mrudangam vidwans (including Tiruvarur Bhaktavatsalam and Mannargudi Easwaran, among others) who acknowledged the help and encouragement they got from Thanjavur Upendran at the slow points in their careers. I still remember when I met the late Thiruvengadu Jayaraman (my sister was taking vocal lessons from him), he had remarked “You are Narayanan’s student? Good. He was Thanjavur Upendran’s student… who himself was a true gentleman!”. Upendransir was very close with a lot of artists. In fact, he was the person who convinced Balamuralikrishna to settle in Chennai and initially used to accompany him a lot in concerts. Upendran later did the same with U. Srinivas, convincing him and his father to shift to Chennai from Andhra Pradesh. Upendransir used to take Srinivas to all the sabha secretaries as a kid and tell them to arrange his concerts, staking his reputation on him!

To describe Upendransir’s playing style and the resulting bani he established is tough. But, there are a few key points that can be made. I liken Thanjavur Upendran to his contemporary S. Kalyanaraman. Both were unsung innovators in Carnatic Music; I often tell my students “what Kalyanaraman was to vocal music, Thanjavur Upendran was for mrudangam!”. As far as I can tell with what little I have learned and what research I have conducted, Upendransir was the only mrudangist to actually incorporate tavil kannaku and other aspects in his style. This was because his father-in-law was none other than the legendary tavil vidwan Valangaiman Shanmughasundaram Pillai! The tavil influence came in the form of sollus based on meetu strokes to mimic the sound of the tavil, as well as the development of sankirna nadai. Most mrudangam vidwans shy away from playing sankirnam because the calculations often end up with non-integral values for each beat (4.5 as opposed to 3,4,5,7 or 8 per beat). But Upendransir formulated the nadai in an aesthetically pleasing format for mrudangam, cleanly developing 2 speeds and various korvais and nadais for each. There are stories that Upendransir and the late kanjira vidwan G. Harisankar used to explore sankirnam in their thaniavarthanams for up to 30 minutes! Alas, with both of them passing on, sankirnam has again fallen into disuse.

This is a thani from a concert of TNS from 1975. Upendran starts the thani with tisra gathi and then skilfully blends into sankirnam, playing the keezh kalam (lower speed, 4.5 per beat) for several minutes. This is an example of tavil kannaku (calculation). The development of this speed of sankirnam using farens phrases is distinctive and is his trademark. He concludes the sankirnam section with the standard adi thalam mohara. Then, he uses 9’s to convert to kandam (3+3+3+1)! This is especially interesting. After the kandam section is concluded, he goes back to chatusram (4 per beat), and then back to tisram, and he plays the standard adi thalam mohara in tisram followed by one of his signature korvais.

There are also some interesting moharas and korvais composed by Upendransir based on the phrase “thalangu thom” or “tha thalangu thom”. Some of these were composed specifically to highlight the strengths of the mrudangam – none of the other ‘upa’pakkavadya instruments have the chapu sound, and so when these are played, the mrudangam will be the highlight. They are also very misleading; it’s difficult to tell where they start or end, and so the main artist must be very confident, alert, and have a strong laya sense.

Besides his music, there is a personal connection for me as well. Upendransir was good friends with Madurai T. N. Seshagopalan. After Thanjavur Upendran’s untimely demise, TNS took an interest in my guru’s career, bringing him to the US on two concert tours in 1992 and 1994. Many years later, when I did my arangetram, we had invited TNS sir to come. Initially he was noncommittal, but that day I got a huge shock when he arrived early! Not only that, but he stayed through the whole thing and also gave a very nice speech with some words of encouragement which I still cherish to this day. This illustrates the power of Thanjavur Upendran’s friendship and lasting influence in the Carnatic music circle.

Most of what I have mentioned here is what has been told to me over the years by my guru Neyveli Narayanan; as I mentioned before, he maintains the memory of his guru through his playing style and this annual function.

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