Once again, it is getting to that time of year where people randomly remember that Sweden and Switzerland are not the same country. In that vein, my picks for this year’s Nobel Prize in Chemistry are unchanged from 2 years ago.
September 29, 2014
September 19, 2014
It is very shocking and saddening to note the passing of Shri. Uppalapu Srinivas (affectionately called “Mandolin Srinivas” by his legions of fans) earlier today. This is a terrible loss not just for Carnatic Music, but Indian music as a whole.
Mandolin Srinivas was a true child prodigy, as he basically taught himself to play Carnatic music on the mandolin at the age of seven! He gave his first concert in Chennai shortly thereafter, and in the early 80’s, moved to Chennai and settled in Vadapalani at the insistence of Thanjavur Upendran sir. Upendransir was one of the people who actively promoted Mandolin Srinivas during that time, organizing hundreds of his concerts all over India, and staking his own reputation on a young boy!
(Concert of U Srinivas, M. S. Govindaswamy, and Thanjavur Upendran sir in Mysore, 1984)
This is a speech in Tamil by Madurai T. N. Seshagopalan during the intermission of a U. Srinivas concert in Bombay. Since TNS was in the city that day, Thanjavur Upendran sir insisted that he attend the concert and hear a young star!
As TNS sir says in the above speech, the genius of Mandolin Srinivas lay not just in his complete command over the Carnatic music system, but also in his ability to adapt the music to a new instrument, the mandolin. Every instrument has its limitations, and all musicians strive to squeeze out as much as they possibly can within those constraints.
This is a rendition of “Tatvameruga Tharama” from a 1985 Bombay concert with Lalgudi G. J. R. Krishnan and R. Ramesh. The first thing to note is that Srinivas is possibly the only musician who can do ragam in Garudadvani for over a minute without it becoming overly repetitive; the ragam only has so much scope, after all. His style is also unique, in the sense that he frequently uses staccato notes. In this ragam it is unavoidable, but he does it in various other ragams too. These kinds of phrases would sound very strange when sung, but sound amazing on the mandolin. The other thing is that his thalam control is absolute. It is very easy to lose track of the thalam, especially with this style of kalpana swarams, and even more so at this speed!
From the beginning, U. Srinivas had the privilege of having top accompanists in his concerts. Srinivas-Sikkil Bhaskaran-Thanjavur Upendran was a very common combination, and then later other combinations like Srinivas-Sikkil Bhaskaran-Palghat Raghu and Srinivas-A Kanyakumari-Raja Rao also became popular. Upendransir also used to organize concerts of Srinivas with tavil as well, and notewothy combinations included Valangaiman Shanmughasundaram-Upendransir-G. Harisankar (kanjira) or T. H. Vinayakram (ghatam). In fact, one of my guru’s first major concerts was a Srinivas concert organized by Upendransir!
(Neyveli Narayanan sir, T. H. Vinayakram, Sikkil Bhaskaran, U Srinivas, and Perumpallam Venkatesa Pillai (Tavil))
I always have a special place in my heart for Srinivas’ concerts from the 80’s. There is something special in his playing, making all of those recordings timeless classics.
Srinivas also performed in the group “Remember Shakti” and in various jazz and fusion music groups all over the world. I remember the first live concert of his that I attended in 1996 in Sydney, Australia, with Delhi Sunder Rajan and Srimushnam Raja Rao. I had the good fortune to hear him live again many times, but the last performance of his that I attended was at Bharat Kalachar during the 2012 December season. I still remember he played Anuragamuleni (Saraswathi) and the main piece was Nagumomu; I can still recall certain phrases he played in Abheri. Of course, it was with none other than Trichy Sankaran sir on mrudangam!
I mentioned earlier that Srinivas was a child prodigy; this is reflected in the fact that he received the Padma Shri award from the Indian National Government at the young age of 29! I’m keenly aware of this fact since I am nearing that age myself…
I’ll conclude with this track:
This is from a concert in the Cleveland Thyagaraja Aradhana, 1990, with Sikkil Bhaskaran and Palghat Raghu sir. Since Paramaathmudu is believed to be Thyagaraja’s last composition, I think it is fitting to end with Srinivas’ rendition of this piece…
September 9, 2014
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