NOLA ACS Meeting. Tuesday

Tuesdays meetings included an awards symposium extravaganza in the organic division. F. Dean Toste was the recipient of the Elias J. Corey Award for Original Contribution in Organic Synthesis by a Young Investigator. Illuminati of the likes of Trost, Sarpong, and Grubbs gave their talks in honor of the awardee. Toste’s talk was on his work in the area of Au(I) catalysis. These gold (I) catalysts show an extraordinary propensity for coordination of alkynes and facilitating nucleophilic addition to the triple bond.

The reactivity of Au(I) is attributed to relativistic effects causing contraction of the 6s orbital and destabilization of the 5d orbitals. The result is a large aptitude for pi->M coordination and relatively low M->pi* backbonding.

Relative to Pt and Rh, gold is cheap. 

NOLA ACS Meeting. Monday.

The talk by Frederic Stanley Kipping Awardee T. Don Tilley was worth the time to see. This UC Berkeley chemistry prof has accumulated a substantial list of results on in the organometallic chemistry arena, much of it with the use of silanes.

The ACS Awardee in Organometallic Chemistry, G. Parkin of Columbia University, was equally interesting. Parkin described his work with kinetic isotope effects and had some caveats for those attempting to draw mechanistic conclusions from such studies. The reaction temperature used in the study can give a positive effect, no effect, or a negative effect. Hmmm.

George Whitesides (GW) gave a talk entitled “Questions about questions about the origins of life”.  It was actually a kind of homily summarizing his summaries. Ok. Let’s see if I can do better than that.  GW has been ruminating on the origins of life and has come to the conclusion that neither the physicists or the biologists are equipped to solve the problem. 

The first matter that he paraded before the audience was this- is it enough to say that the world is bifurcated into two domains- alive and not alive? Is it binary or continuous? GW thinks it is continuous.  It just occured to me that prions may be a good present day exception to the assertion that it is binary. But what really matters is the question of whether life was continuous or binary during the peribiotic period while life was forming.

GW suggested that it is important for us to find examples of chemical fossils.  These would be chemical compositions left intact from that era. The problem of the origin of life cannot be answered by simple extrapolation backward from present biology because the peribiotic conditions in which life arose have not been present for several billion years. We are far from understanding the chemical and redox makeup of the peribiotic world.

The origin of life arose from reaction networks that afforded molecular species that could self amplify or self replicate in an anoxic, reductive environment.

The question of the mechanistic origins of life is vastly different from the question of the mechanistic evolution of life.

Both are chemical phenomena and a mechanistic picture of both will ultimately be assembled by chemists of one sort or other.

NOLA ACS Meeting. Sunday.

Spent a good deal of  time in the INORG section talks. The Cotton Symposium talks have brought many friends and alumni of the Cotton Experience. Tobin Marks kicked off the symposium this morning with his usual overwhelming flood of results. Listening to a Marks talk is like trying to sip from a fire hose.  What always impresses me about the talks by Marks, Bergman, et al., is the large amount of kinetic and thermodynamic data presented to support the proposed mechanisms. 

The talk on the functional mobility of ribosomes by Yonath was just amazing. The Yonath group has been able to use heteropolymetallates to aid in the understanding of the conformational changes in the mechanism of transfer RNA mobility across the ribosome. 

My background did not include kinetic studies and I have always regretted this. The path to understanding is with kinetics and thermodynamics experiments, not just a simple report of yields and conditions. Once before they bury me, I want to do this.

The Kipping Symposium Honoring T. Don Tilly offered some interesting talks as well. Gelest  had a sponsoring role in this symposium.

Chemical Insult

I’m not an apologist for the chemical industry. Chemical industry has a checkered past in many ways. The pesticide, petrochemicals, and mining industries have left a deep and abiding foul taste in the mouths of many communities. In a previous era, heavy industry has fouled rivers, lakes, air, and ground water. It has lead to illness, death, and loss of livelihood to many people.

But in the modern era much of this wanton issuance of hazardous industrial material into the air and waters has been halted or greatly diminished. And it is not because industry suddenly found religion. The “regulatory environment” became so compelling a liability cost factor that industry set its mind to engineering plants into compliance. 

I would make the observation that today, the major chemical health issues before us are not so much about bulk environmental pollution by waste products. Rather, I would offer that the most important matter has to do with the chronic exposure of consumers to various levels of manufactured chemical products. High fructose corn sweeteners, veterinary antibiotic residues, endocrine disrupters, smoking, highly potent pharmaceuticals, and volatiles from polymers and adhesives to name a few.

Modern life has come to require the consumption of many things.  A modern nation must have a thriving chemical industry to sustain at least some of its need for manufactured materials. It is quite difficult and isolating to live a life free of paint and plastics or diesel and drugs. Choosing paper over plastic at the supermarket requires a difficult calculation of comparative environmental insults. Pulp manufacture vs polymer manufacture- which is the least evil? I’m not sure.  

The path to a cleaner and safer life in these modern times is surely a life that pursues fewer consumables. Less throw-away stuff.  Less calorie intake and greater calorie expenditure. Reduced consumption of foods engineered by modifiers and additives.

Given the expectation of multitasking in our culture, it is increasingly difficult to arrange to prepare fresh foods. Meal preparation time eats into commuting time.

Now that I think it through, maybe it’s our culture that is killing us? Maybe our adverse exposure to deleterious substances is an artifact of a cultural requirement for increased productivity.

At the outset, I said I was not an apologist for the chemical industry. But I am not a Luddite either. Modern material science (which includes chemistry) has brought aid against a great many of the hazards and inconveniences of life. As we pass through the age of increasing population and peak oil we must adjust our expectations of the benefits of manufactured goods in the betterment of our lives. Linear extrapolations such as “more = better” begin to fail at high levels of consumption. That is the lesson that I’ve taken.

Good Morning, NOLA. Pass Me Some Advil.

The math of Bourbon Street is painfully evident this morning. 1 Hurricane = 1 hangover. The sliders with the hot peppers didn’t help, either. I should probably start thinking about chemistry again. Bourbon Street is a very naughty place. The prospect of beads can cause ordinarily prudent people to expose their anatomy. A fellow can get into serious trouble here.

Speaking of pain, I’m reminded of a recent dinner conversation with an astrophysicist. This fellow is a senior player in the astrophysics circuit. He has been involved in the development and use of many “science packages” that are now hurtling through the vacuum of space.

Like physicists often do, he took delight in reminding me that chemistry is derived from physics. When asked why a chemist was interested in astronomy, I blurted out that I thought there was a goodly bit of chemistry happening in the universe and much for a chemist to try to understand. Between bites of beef medallions and the chomping of his bearded jowls, he shot a patronizing glance over his glasses at me and suggested that it was all ultimately physics. 

Ah, a reductionist! Not wanting to make a scene, I let this comment float into the ether where it belonged. But I would offer that if one had a headache and needed to wait for a physicist to invent and make some aspirin, you’d still be waiting.

NOLA ACS

Th’ Gaussling is heading for fabulous New Orleans, LA, to that gathering of eagles we call the National ACS Meeting. It’s an extravaganza. Chemistry overlords and underlings awkwardly walking about in their wrinkled dress-up clothes.  Undergrads on their first professional trip, lugging plastic bags loaded with trade show trinkets.  It’s an orgy of PowerPoint presentations disclosing all of the latest “firsts” and “remarkable” results. 

The National ACS meeting is a harmonic convergence of the illustrious grandees of the First Tier of universities together with those perched in lesser stations.  Th’ Gaussling, a 2nd rate molecule merchant, will be staying within hurling distance of Bourbon Street.  NOLA is a place where it is still cool to play the tuba.  Ya gotta love a place like that.

Solar Warming

Here is an interesting analysis of solar min/max data. I can’t vouch for the kind of analysis that was performed. But it is interesting to see. The effects of variations in the solar flux on global temperatures seems to be neglected in discussions I run into. Among other things, these folks suggest that a lesser known 66 year solar cycle may come into play.

One commentor in a previous post suggested that we are approaching the end of the current interglacial period. He said that recent interglacial periods were characterized by polar cap melting followed by entry into the glacial side of the cycle.

Even if the solar output was constant, the interplay of the ocean heat reservoir with the atmosphere, greenhouse gases, vulcanism, asteroids, and the earth’s albedo is complex enough.  Heap on top of that the subtle thermal modulation by the sun and you have a really complex problem.

Global warming could reduce to an equation where one of the components of the sum derives from anthropogenic greenhouse emissions. 

I keep having this thought that Al Gore is eventually going to have a long talk with Tipper about returning the medal to Sweden.

The Corporation

LinkTV has been running a documentary called The Corporation. I find it rather thought provoking and would recommend it to others.

The quote that sticks with me is from a business ethics seminar I took. Our prof said “sometimes it is dumb to be too smart” in business.  Witness the pesent banking disaster.  Some of our B-school geniuses have devised instruments of finance that are so convoluted and complex that the mechanism and magnitude of failure was not widely appreciated.

What has always puzzled me is that conservatives who profess open scorn and distrust of big government are somehow able to accept the privatized power of big business.  Big government extracts the wealth of our labor and disperses it in ways that are not economically efficient. But at least there are constitutional means of remedy.  If you do not like the way a business operates, you are free to quit buying their widgets.

Big business extracts wealth from labor and resources and disperses it to shareholders.  Government pays for national infrastructure to support business activity and business practices tax avoidance. Government has gotten too big and business has learned to game the tax system.  Taxpayers are left to subsidize both big government and corporate welfare.  The system is wildly out of balance.

The essence of power is in the ability to allocate resources. Governments and businesses are centralized organizations that have large resources to allocate. Consumers are dispersed and disorganized units that have microscopic resources to allocate.  The consumers biggest leverage is the ability to make politicians fearful with respect to their re-election prospects.

Russian Oil Production in Apparent Decline

According to an article by Greg Walters at Bloomberg.com, crude oil output in Russia is expected to decrease for the first time in 10 years.

“Two years ago, we said the growth rate was falling, and we said this was bad for Russia, remember?” Trutnev said in televised remarks after a government meeting in Moscow today. “Now we’re saying the production rate is falling this year. This is not a bogeyman, unfortunately, this is real,” Trutnev said, without giving a specific forecast.

The petroleum problem in Russia seems to stem from the lack of investment in exploration in combination with exorbitant taxes on the industry.

Gail the Actuary has an interesting post on the post-peak-oil economy. Gail is a contributor to The Oil Drum Discussions.  It’s all kind of gloomy.  Time for a nice glass of Bordeaux.

NIH Manditory Open Access

According to C&EN, the NIH has issued a rule that publications resulting from NIH funded research be submitted to PubMed Central for posting.  Naturally, organizations with copyright interest in published research is  less than enthused by this ruling.

What has happened over the last century is that a sizeable publishing industry has grown up around the publication of periodicals specializing in scientific research.  In exchange for release of copyrights, authors get free or nominally priced access to publishing and distribution of their work. For their part, publishers tap into a continuous stream of refreshed content that is virtually free of charge. 

Counterbalancing the low cost of content are the sad facts of subscriptions.  Many (most) journals suffer from low distribution numbers, so the zero cost of content helps to keep overhead down, but publishing and distribution costs cannot benefit from the economy of scale.

The special interests seem to be sitting in watchful waiting, but they have raised the issue of copyright. Their concern is that they are being forced to distribute their property by the strong arm of NIH without the chance for reimbursement.  This could resolve to a property rights battle and as such, I can’t imagine that the NIH would prevail in the courts.