musings on music and life

August 24, 2015

Next concert, 8/30/2015

Filed under: Carnatic Music — Tags: — sankirnam @ 11:06 am

Concert+Flyer-page-001

This is my last concert in the US before I head off to India for the next few months! If you are in town, please come.

August 17, 2015

Yves Saint Laurent Kouros

Filed under: Colognes — Tags: — sankirnam @ 11:07 am

I got this cologne as a birthday present for myself this year, and after only wearing it twice, I have fallen completely in love with it. I had sampled it previously in airports at duty-free shops, but there is nothing that compares to actually wearing a cologne – it is not just about a smell (or combination of smells), but the combined olfactory and emotional experience that wearing a cologne gives you. You simply don’t get this from sniffing swatches of paper.

YSL-Kouros

Kouros is one of the early creations of the legendary perfumer Pierre Bourdon, who later achieved everlasting fame with the creation of Davidoff Cool Water in 1988. It has a very abstract, musky smell, described by Luca Turin (Perfumes: The A-Z guide) as:

[…] the tanned skin of a guy with gomina in his hair stepping out of the shower wearing a pre-WWI British dandified fragrance: citrus, flowers, musk. It has that faintly repellent clean-dirty feel of other people’s bathrooms, and manages to smell at once scrubbed and promissory of an unmade bed”.

Turin’s description is very apt – I am reminded of a bathroom when I smell this, but not in a bad way. The idea of the bathroom in this cologne is not overpowering, but it is there, and it is not the idea of a dirty bathroom either; there are no indolic notes that I can detect (which would otherwise remind one of an uncleaned bathroom). To see what I mean, apply this cologne when you are in a bathroom. The bathroom will smell absolutely fantastic! In fact, I think YSL should also consider making this same scent into a bathroom air freshener.

Roja Dove (The Essence of Perfume) states about Kouros that:

The animalic, leathery base, sweetened with Jasmine, is what gave the scent its sensuality and originality. It was launched as the first fragrance to celebrate the beauty of the naked male form, a theme that was going to be picked up by many [fragrance] houses either side of the Atlantic”.

This marketing strategy was indeed reprised in the 1988 launch of Davidoff Cool Water and a number of Calvin Klein fragrances.

But one also has to remember that this cologne was launched in 1981, and as such some people may perceive it as a bit dated. In my opinion though, it has stood the test of time. I’m not sure if it has been reformulated or not since it was launched, but either way, it is still a great cologne. For an EDT, it is very strong – it lasts over 12 hours on my skin. It is moderately priced too; a 100 mL EDT bottle costs around $40-45 on Amazon.

August 15, 2015

Next concert, 8/23/2015

Filed under: Carnatic Music — Tags: — sankirnam @ 11:40 am

S-Namboothiri-ohm-aug23-page-001

August 14, 2015

CBS catalysis…and trifluoromethylation shenanigans

Filed under: Chemistry, Classics in Organic Chemistry — Tags: — sankirnam @ 12:20 pm

In order to wash the previous paper from our minds, it is often good to step back and read some of the really important  manuscripts from decades past. One example is the classic 1987 JACS paper by Corey on the enantioselective reduction of ketones, which after this publication, came to be known as the “CBS” method, after the authors (Corey, Bakshi, Shibata).

In the introduction, Corey, Bakshi, and Shibata state that Itsuno had already discovered that mixtures of borane and chiral vicinal amino alcohols (derived from enantiopure amino acids) were very effective for the stereospecific reduction of ketones. However, Corey states that “reagent structure, scope, and mode of reduction has remained at a primitive level, limiting both application and further development“. Thus, they isolated the complex formed from borane and (R)-1-phenylethanol as well as borane and (S)-diphenylprolinol by vacuum sublimation.

CBS catalyst

The complex derived from prolinol and borane turned out to be extremely active, and Corey reports reductions of around 95% ee with >99% conversion at room temperature! The simplicity and practicality of this paper should be noted; according to Google, it has at least 1,200 citations! The catalyst derived from prolinol soon became commercially available from several vendors, and is now popularly known as the “CBS catalyst”. Interestingly enough, this can also be thought of as one of the early modes of organocatalysis, but the term does not appear even once in this paper. The use of prolinol here laid the foundation for the future development of the Hayashi-Jorgensen catalyst, which is now an exceedingly popular organocatalyst.

Upon typing this, I became reminded of a similar incident that occurred in the fluorine chemistry community while I was doing my PhD. One of the developments in trifluoromethylation chemistry that occurred during that time was the discovery of a copper-catalyzed trifluoromethylation of aryl iodides by Prof. Hideki Amii. The proposed mechanism involved the intermediacy of phenanthroline-ligated copper(I) complex [(phen)CuCF3], but that complex was not characterized or isolated. Prof. John Hartwig (UIUC, now at Cal) soon published a paper where all he did was synthesize the [(phen)CuCF3] complex and use that as a trifluoromethylating agent! In his talks, Hartwig claimed that using the pre-synthesized complex in this manner greatly expanded the substrate scope beyond what Amii reported, although he always skirted around the issue that he had taken a reaction that was previously catalytic in copper and made it stoichiometric in copper! Hartwig soon started a company based on this chemistry, selling the [(phen)CuCF3] complex, which is now known as “Trifluoromethylator“.

But really, is this any different than what E. J. Corey did in 1987 with Itsuno’s chemistry? I’m not trying to justify or defend Hartwig’s research, but there is a precedent for this kind of stuff, from a Nobel Laureate, no less. Having some distance from fluorine chemistry at this point gives me a valuable outsider’s perspective now, without which I would not have come to this realization.

August 12, 2015

Sweet sweet acetate cocktails

Filed under: Chemistry — Tags: — sankirnam @ 12:36 pm

I remember that this paper was trending when I was at the NOS a few weeks ago. Everyone I talked to was extremely derisive about this paper, and upon examining it myself, I share the same sentiments.

acetate_cocktail

Ugh.

Firstly, there is no real novelty in this reaction – why was it accepted by JACS? The authors are just trying to do a template-directed meta-selective C-H arylation using the norbornene (NBE) template, with an amine as a directing group. Gaunt did a similar meta-selective C-H arylation back in 2009, except he used a pivalamide as the directing group, and diaryliodonium salts as the arylating agents under Cu(I)-Cu(III) catalysis. The authors are trying to do a Pd-catalyzed meta arylation in this case.

One of the major issues with doing C-H activation in a Pd(II)-Pd(IV) catalytic cycle is that it is an oxidative process, and therefore one needs a terminal oxidant, otherwise no reaction will occur. In academia, the most popular choices are Ag salts, due to their solubility and ability to selectively conduct outer-sphere electron transfer with other metals. BUT… as one can see above, this reaction uses superstoichiometric amounts of silver – 4.5 molar equivalents! So while this reaction may be fine in microscale in the research laboratory, it will never be scaled up. This is what I call the “Jin-Quan Yu” approach, since a lot of his chemistry also uses excess amounts of silver salts as oxidants.

But the “acetate cocktail” part…wow. This really shows that the unfortunate post-docs or graduate students who developed this reaction really have no idea what is going on. They just “Hail Mary’d” it, threw in everything possible to make it work, and prayed for the best. I remember Prof. Karl Christe (who was on my PhD committee at USC), made a very memorable statement after sitting through a mediocre PhD defense:

When the reaction doesn’t work, add some Lewis Acid. 

If it still doesn’t work, add some Lewis Base.

If it STILL doesn’t work, add some dirt and pray!

August 10, 2015

Assassin’s Creed 1 screenshots

Filed under: Video Gaming — Tags: , , — sankirnam @ 12:09 pm

I re-played Ubisoft’s Assassin’s Creed a few months ago for the sake of nostalgia. The game still holds up very well, and even though it is quite old by today’s standards (2007), the graphics do not seem that dated at all. I’ve gotten into the habit of taking screenshots whenever I’m playing through PC games these days, because it serves as a diary of sorts, and looking at the screenshots often conjures up emotions I may have had at the time while playing through. Taking screenshots is very convenient when playing games through Steam, since it provides a one-button shortcut for doing so (usually F12).

Some of these screenshots can also serve as very nice desktop backgrounds, and since they are all high-res (1920*1080), the scenery shots are perfect for this purpose. My only gripe is that Steam saves these images as highly compressed JPEG files, and the compression can sometimes be evident (jagged edges, color gradients becoming less smooth, etc.). Steam should also include a utility for users to adjust the level of compression when saving screenshots.

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August 6, 2015

Inequality

Filed under: Books — Tags: — sankirnam @ 11:36 am

I’m now making my way through The Price of Inequality; although I am not done with the book, I can say that so far it has been very interesting. Economics books can be notoriously dry, but since I am very interested in the subject (for many reasons), I am able to power through. Inequality in incomes and wealth disparities in the USA are getting worse every year – for an excellent visual illustration, see this video:

Shocking. Stiglitz attributes this to the policies that the rich (in particular the 1%) have enacted to keep their coffers overflowing. He singles out the Republicans for constantly endorsing tax cuts as well as fiscal and monetary policies that favor the rich. Stiglitz states that the insane wealth disparity we see today started with the Reagan tax cuts, which were based on Supply-Side Economics and the (now largely discredited) Laffer Curve. The wealth that was supposed to “trickle down” from the rich did not do so; they used whatever they were able to save from the tax cuts to further line their pockets. Until I read this book, I did not realize that the Reagan tax cuts lowered the top marginal tax rate from 70% to 28%!!

Aladdin-disneyscreencaps.com-5032

Inequality in wealth is not good for the overall health of a country. Government policies are supposed to be able to prevent such things, by “redistributive” methods such as taxation and socialized healthcare. In earlier decades, the terms “socialism” and “communism” had negative connotations, as the US was neck-deep in the Cold War with the USSR. Nowadays, the word “redistribution” has also achieved similar status, which is due to the inordinate power the rich now have thanks to economic policies favoring them. This NYT op-ed article about the aftermath of Hurricane Sandy has a few choice quotes illustrating the consequences of inequality (even though this is from 2012, it is still relevant):

“It’s manifestly silly (and highly polluting) for every fine home to have a generator. It would make more sense to invest those resources in the electrical grid so that it wouldn’t fail in the first place.”

“Is crime a problem? Well, rather than pay for better policing, move to a gated community with private security guards!

Are public schools failing? Well, superb private schools have spaces for a mere $40,000 per child per year.

Public libraries closing branches and cutting hours? Well, buy your own books and magazines!

Are public parks — even our awesome national parks, dubbed “America’s best idea” and the quintessential “public good” — suffering from budget cuts? Don’t whine. Just buy a weekend home in the country!

Public playgrounds and tennis courts decrepit? Never mind — just join a private tennis club!”

To see the extreme of income inequality, look at South Africa, where the rich live in mansions surrounded by high walls topped off with barbed wire, and protected by armed guards. Already we can see the beginnings of this in the various gated communities in suburbs in America. We don’t have to let things get as bad as they do in South Africa before we realize we have a problem here. Unfortunately, the passing of necessary preventative measures is stymied by the gridlock in Congress.

So what is my interest in all this? I’ve always been interested in studying economics; when I was an undergraduate, I actually wanted to double major in it, but then decided not to, simply so I could graduate early. This is something I regret to this day – while I may have graduated in a little over 2 years, I missed out on a lot of key experiences essential to undergraduate life, and so when I think back on it, my undergrad years seem like a very boring extension of high school. Anyway, part of the reason for the lousy job market for chemists (which I am experiencing first-hand) is inequality. CEO’s and other big corporations have become obsessed with furthering profits on a quarterly basis, rather than focusing on improving the underlying R+D, which has a much longer timeframe. And so, one of the ways that CEO’s and other executives can maintain quarterly profits is by continually slashing R+D. This seems like a classic “chicken and egg” conundrum – if one keeps slashing R+D, one will not have products to sell in the future, but at the same time, one has to sell the existing products to make money for R+D. At the same time, while salaries for the average worker or scientist have not noticeably improved (in some measures, PhD chemist salaries are decreasing by constant dollars and PPP), executive salaries are skyrocketing. Simultaneously, globalization has made the job market incredibly competitive and salaries are on a race to the bottom. US universities take in large number of foreign students every year for PhD work, and companies here also preferentially hire foreign workers or H-1 visa holders, because they can be paid less.

To finish off, here are some illustrative passages from the book:

In a world of globalization, creating market value had become entirely separated from creating employment. […] And even when there is investment in the United States, it’s not necessarily investment related to job creation: much of the investment is in machines designed to replace labor, to destroy jobs

[…] social protection can make for a more productive society. Individuals can take on more high-return, high-risk activities if they know there is a safety net that will protect them if things don’t work out.” *This is a similar argument used for keeping the tenure system in universities, interestingly enough.

[…] too many of those at the top don’t want to contribute their fair share to the “public goods” that are necessary if our society, and economy, are going to function.” *Similar to what is stated in the article I linked to above.

[…] if employers don’t pay workers a decent wage, if a society provides so little opportunity that many people become alienated and demotivated, then that society and its economy won’t work well.

[…] free mobility of labor without tax harmonization is an invitation to a race to the bottom” *This is especially relevant today given the buyouts and M&A’s of big corporations in order to relocate to tax havens, where they can pay lower tax rates, at the expense of the American worker.

EDIT (3/9/2016): I just finished watching this excellent movie by former Secretary of Labor Robert Reich on this very topic. It is really well made, and Robert Reich makes some very good points over the course of the documentary. I do have one major point of contention, however. One of Reich’s arguments is that education is the key to strengthening the middle class and improving the economy, and he points out that higher education massively expanded in the United States from 1950-1970 (thanks mainly to the GI Bill). It is pointed out that inequality has increased since the 1980’s and that the ‘economy’ has been doing much worse since then. However, while most other economic indicators may have been going downhill, education rates still increased; today, we have the best educated and most highly qualified workforce in the history of our species on the planet! Yet millennials and people in my generation are still struggling to find gainful employment. There are plenty of PhD’s who are either unemployed, underemployed, or desperately looking for work. If education is the magical panacea to long-term economic stability, then why do the most educated individuals in this country struggle for employment? Superficially, Reich shows that economic downturns are correlated with lower college enrollment, but I’m not sure that’s the case; I’m sure there are statistics that show otherwise. It could be this superficial (and otherwise incorrect) consideration of the relationship between economic growth and higher educational enrollment that has led to the expansion of the H-1B program, and the displacement of otherwise qualified, highly-skilled domestic workers from their jobs.

 

Edit 2 (5/16/2016): An excellent discussion by John Oliver on this very topic!

August 5, 2015

C&EN layoffs

Filed under: Chemistry Jobs — Tags: — sankirnam @ 11:49 am

I heard about these through Chemjobber; he has written a moving piece on this sad state of affairs.

As someone who is frantically applying for jobs and trying to get his foot in the door in the chemical industry, these layoffs do affect me. Even if I do not know the laid-off employees personally, the positions they once had are usually eliminated completely, never to be refilled. This drastic downsizing of jobs in a lot of companies in the formerly active chemical sector is something that I feel needs to be addressed by government intervention or a political lobby in the interest of chemists.

August 3, 2015

learning to code…FizzBuzz

Filed under: Coding — Tags: — sankirnam @ 9:51 am

I’m back from a bit of a hiatus… while I’m still not gainfully employed, I’ve been keeping myself busy with a variety of things. Lately, I’ve been learning to code on Codeacademy – I highly recommend this website for other beginners like myself since it is interactive and the lessons are planned out very well, with a gradual introduction of new concepts and periodic refreshers and reviews where necessary.

I’ve been doing the Javascript lessons on Codeacademy, and along the way I had to do the famous FizzBuzz exercise. For those who don’t know:

“[…] questions I call “FizzBuzz Questions” named after a game children often play (or are made to play) in schools in the UK. An example of a Fizz-Buzz question is the following:

Write a program that prints the numbers from 1 to 100. But for multiples of three print “Fizz” instead of the number and for the multiples of five print “Buzz”. For numbers which are multiples of both three and five print “FizzBuzz”.

Sounds pretty trivial on the surface, right? I mean, anyone can do this on pen and paper, but it takes a little bit of programming knowledge to write code that accomplishes this. The scary part?

The majority of comp sci graduates can’t. I’ve also seen self-proclaimed senior programmers take more than 10-15 minutes to write a solution.” (Source)

Wow. And these people will still be able to get jobs that pay salaries far, far beyond what competent PhD chemists make, due to the robust job growth and demand for computer scientists/programmers.

In any case, here’s my solution (for numbers 1-20):

for(var i=1; i<21; i++) {
if(i%3 === 0 && i%5 === 0) {
console.log("FizzBuzz");
} else if (i%5 === 0) {
console.log("Buzz");
} else if (i%3 === 0) {
console.log("Fizz");
} else {
console.log(i);
};
}

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