Anatomy of a Heel Hook

A knowledge of anatomy can make you a more effective martial artist.
Here's an example how:

If you were to head a campaign to activate change in Canada, what would your issue and platform be? -- An Essay

If I were to head a campaign to activate change, a shift to scientific consensus-based legislative decisions towards creating a sustainable future would form the basis of my platform.

In speaking of the discrepancy between scientific consensus and political will, Science editor Bruce Alberts stated that, "there is only one effective solution for this type of problem: Scientists must make both science education and community outreach a much more central part of the scientific culture" (1), echoing my own conclusions. Therefore, in my campaign I would encourage government to consult with Canadian scientists, and for scientists to engage in a responsible dialogue with their elected officials, communities and the media. The more clearly we understand issues the better we can focus on developing sustainable environmental, economic and social programs.

Along with Alberts, I agree that "it is crucial that both sides of any argument pay close attention to what science knows" (1). By having experts-in-the-field engage in an educational campaign that teaches the key points of important issues to the public, reconciling what is best for policy makers and what is best for those subject to those policies becomes a more realistic goal. This is due in part to the objectivity inherit to the scientific method, which allows it to side-step the accusation of partisanship. At the same time, in situations where there is a strong scientific consensus such as in the case man-induced climate change, scientists should become more vocal: scientists should supply Canadians with objective data at the same time as they advocate that the facts be used to set coherent national goals.

This scenario is, however, only achievable where there is willingness on the part of government to listen to scientists. For this reason, the recent reports of the muzzling of scientists in Environment Canada and the Department of Fisheries and Oceans by the Harper government are particularly concerning (2, 3). Margaret Munro, a National Writer for Postmedia News on science and research warns that, "researchers, who used to be free to discuss their science, are now required to follow a process that includes 'media lines' approved by communications officers, strategists and ministerial staff in Ottawa". When politicians only listen to scientists insofar as it supports the party's interest, it becomes all the more important for scientists reach for public support. It is public scrutiny, after all, which makes government more responsible.

An increase in public outreach by scientists has been strongly and uniformly urged by such notable academics such as Dr. Joe Schwartz (Office for Science and Society, McGill), Dr. Ben Goldacre (The Guardian News), and Dr. Peter Agre (nobel laureate). In answer to the demand, there has been an encouraging upsurge in numbers of science writers -- often graduate students who blog about research-related topics -- in the past few years. Outstanding examples include "Not Exactly Rocket Science" by Ed Yong, "In the Pipeline" by Derek Lowe, and -- a new and notable -- "My Pet Hypothesis" by Peter Kublik. In addition, long-standing organizations like "Lets Talk Science" are working to engage youth in hands-on physical and life science activities, and McGill's Office for Science and Society is dedicated to disseminating scientific information specifically to the public, and new organizations like Quebec's "Science & Policy Exchange" annually collect government officials, students, and leaders in industry and science for a round-table discussion of the issues affecting the province (4).

In order to achieve scientific consensus-based policy decisions, it is necessary for scientists to engage in a public education campaign, and, with this goal in mind, I would ask that researchers become more proactive in seeking out and contributing to public outreach initiatives (if they do not already do so). By training in biomedical communications I hope to eventually assist in these endeavours by acting as a liaison between scientists and the public.

References
1. Alberts, B. (2010). "Policy-making needs science." Science 330(6009): 1287.
2. Munro, M. (2011). Ottawa silences scientist over West Coast salmon study. The Vancouver Sun. Vancouver, Postmedia News.
3. Mitchell, A. (2010). Harper's Humiliating Muzzle on Scientists. The Tyee.
4. "Science & Policy Exchange: Science and Policy issues affecting Quebec." from http://www.sp-exchange.ca/.

Technology is neutral

The Haber process is a good example of how a benign invention can cause harm: nitrogen fixation technology that was initially applied to fertilizer production, shifted to explosive manufacturing during WWI as the major application.

While technology is neutral, people definitely are not, which is, I think, a pretty good argument against the right to bear arms, or nations nuclear weapons. …Today. Back in the old west, however, you may have legitimately needed to defend yourself against zombie aboriginal peoples:

“The Stand” was my second assignment of Bobby Chiu’s digital painting course (www.schoolism.com). My homework was to colour in a black and white painting provided by Bobby (inset). In theory, I can now colour anything; old photos, low resolution scans, and, most importantly to me, homemade black and white paintings like “Flex”. Although I tried to stay within the lines, you can see where I was sloppy by the telltale “halo” edging bald cowboy’s hair rim. That mistake, and maybe poor colour choices, got me 4 out of 5 stars for this second assignment.

The educational tie-in to this painting, I’ve decided, is – to continue on the theme of the Haber process – explosives, specifically the propellant used in these cowboys’ firearms, gunpowder. Most authoritative modern views attribute the discovery of gunpowder to 9th century AD Chinese who, in their search for the potion of immortality, may have stumbled across the right ratio of potassium nitrate, sulfur and carbon (15:3:2, respectively, by weight (3)) to make a bang (1). The philosopher John Bate referred to the three components of the mechanical mixture as, “the body” (charcoal), “the life” (sulfur), and “the soul” (potassium nitrate) (2).

“The Body”
Carbon (C), is obtained in the form of charcoal, which is almost pure carbon. The timber is selected carefully: dogwood for rapid-burning small grains (shotguns), willow and alder for slower-burning coarse grains (blasting), and beach and birch make discount gunpowder for everyday usage (cap guns?), all of which has led to substantial deforestation in many parts of the world (1).

“The Life”
Sulfur (S) is a yellow solid known biblically as brimstone, and probably got its reputation of “raining upon the wicked” because the deposits easiest to mine were in volcanic regions (2). …And it smells terrible when it’s burned. My brother came across sulfur blocks while on a tour in Chile:

although, if hue is any indication, this rock is quite low in sulfur content.

“The Soul”
Potassium nitrate, (KNO3, or saltpeter, from the Latin “sal petrae” literally meaning, “salt of the stone”), occurs naturally as a white efflorescence where there is an abundance of nitrogenous organic matter, typically from decomposing animal or vegetable matter. Unsurprisingly then, a rich source of saltpeter is sewage waste. Since maintaining sufficient supplies of saltpeter for explosives production was a matter of national security, especially during wartime (which was a lot of the time in Europe), extreme measures were taken in the past to ensure supply. In 1626 England, King Charles I commanded his subjects to, “keep and preserve in some convenient vessels or receptacles fit for the purpose, all the urine of man during the whole year, and all the stale of beasts which they can save” (2). And in the following decade, he additionally decided that house and barns floors were to “lie open with good and mellow earth, apt to breed an increase of saltpeter” (2); a couple of gut-churning laws that would certainly violate public health code today. The result was that house and barn floors produced thick crusts rich in nitrates, which were dug up, converted to potassium nitrate through counter ion exchange in water, and then purified by recrystallization, in essence.

Although black powder is made up of three components, it has been described as working together like a single compound (4). Saltpeter undergoes a rhombic to trigonal solid-solid transition at 130 C, which ‘loosens’ the solid, effecting to make it more reactive and ignitable (4). In addition to acting as a fuel, the finely ground charcoal provides a high surface area for adsorption of gases given off during early chemical reactions that are consumed in subsequent reactions (4). On the other hand, the soft sulfur melts at relatively low temperatures and exhibits a pseudo-plastic behaviour that ‘glues’ the powder together, so that it lowers the activation energy, and functions as a unit (4). The overall process can be summed up broadly as

The overall reaction is

To put the equation into perspective, note that the reaction produces 8 moles of gas from 12 moles of solid black powder, which corresponds to 3L of gas per gram of black powder. Furthermore, the temperature of the reaction can be calculated from standard heats of formation to be -1688 kJ/mol, or a theoretical flame of 3070 K (2800 C, 5000 F) (4). Underscoring why you don’t want to try this at home. Ideal for lobbing into a hoard of zombies, though.

Many other facts and fascinating anecdotes from the history of gunpowder can be found inside these following references:

1. Brown, G. I. (1998). “The big bang: A history of explosives.” Sutton Publishing Limited
2. Brown, S. R. (2005). “A most damnable invention: Dynamite, nitrates, and the making of the modern world.” Viking Canada
3. von Maltitz, I. (2003). “Black powder manufacturing, testing & optimizing.” American Fireworks News
4. Russell, M. S. (2000). “The chemistry of fireworks.” Royal Society of Chemistry Paperbacks

Little Miss and Mr Elements

For distribution around your chemistry department, or to your favourite chemistry geeks on ♥ Valentine's day ♥.  Made in Photoshop.

Clean or The Clear

The most common controversy of the Olympics is testosterone and its derivatives. Tetrahydrogestrinone, THG or “The Clear”, is an anabolic androgenic steroid derivative of testosterone that was provided to a handful of 2004 Athens Olympians by their coach.  Interestingly, Patrick Arnold, the chemist credited with developing the designer steroid THG, was an amateur bodybuilder, suggesting his original motivation.

In September, the morning after a homecoming party and a long distance phone call made while drunk to an estranged best friend who gives excellent advice, I signed up for an online digital painting class offered by this man.  Bobby Chiu is an incredibly skilled digital artist whose work I follow via cgsociety.com, an online forum for computer graphics artists. (Specifically, see http://digital-bobert.cgsociety.org/gallery/.)  Considering the going rate of art classes from the local community center it was a splurge, but the quality of instruction did make it worth it.  The flexing bodybuilder vide infra was my first assignment, "visualizing through darkness".  I was provided a pencil line drawing, and taught by Bobby how to paint over it in Photoshop using only a hard-edged, round brush.  At the time, I was pleased as punch with my muscle-head.

The muscle growth and increase fat-free mass achieved through anabolic steroid use is endorsed not only by dirty track coaches, but also in some cases by the medical community.  Since the early 1990’s, anabolic-androgenic steroids (AAS) have played a little mentioned, but vital role in offsetting the lean body mass wasting in HIV/AIDs, cancer [1], and severe burn patients [2], when it was discovered that muscle erosion in those conditions was associated with increased mortality rates [3]. 

Testosterone (T) exerts its effects by binding with high affinity to the androgen receptor (AR), inducing a conformational change of the entire ligand binding domain, compacting it.  Several key hydrogen bonding interactions between T and the AR were identified by X-ray crystallography [5] (image made in PyMOL):

When switched on by testosterone, the receptor moves to associate with testosterone responsive DNA sequences, recruits transcription machinery and increases expression of those genes [4].  After puberty, there is more circulating T than androgen receptors capable of binding it [6].  The surplus T serves to reduce the catabolic activity (breakdown of fats, lipids, protein and sugars into their fundamental units) of glucocorticoids by displacing them from their receptor.  The combined, physiological results are an increase in muscle size, strength and fat-free mass [6], among other things that can be read about elsewhere [7].

To conlude, I’m greatly anticipating a clean, show of Canadian strength in the 2010 Winter Olympics, especially between the pipes.  Ra Ra!

References

1. Basaria, S., J. T. Wahlstrom, et al. (2001). "Anabolic-androgenic steroid therapy in the treatment of chronic diseases." Journal Of Clinical Endocrinology & Metabolism 86(11): 5108-5117.
2. Hart, D. W., S. E. Wolf, et al. (2001). "Anabolic effects of oxandrolone after severe burn." Annals Of Surgery 233(4): 556-564.
3. Kotler, D. P., A. R. Tierney, et al. (1989). "Magnitude of body-cell-mass depletion and the timing of death from wasting in AIDS." Am J Clin Nutr 50(3): 444-447.
4. Tsai, M. J. and B. W. Omalley (1994). "MOLECULAR MECHANISMS OF ACTION OF STEROID/THYROID RECEPTOR SUPERFAMILY MEMBERS." Annual Review Of Biochemistry 63: 451-486.
5. Askew, E. B., R. T. Gampe, et al. (2007). "Modulation of androgen receptor activation function 2 by testosterone and dihydrotestosterone." Journal of Biological Chemistry 282(35): 25801-25816.
6. Wu, F. C. W. (1997). "Endocrine aspects of anabolic steroids." Clinical Chemistry 43(7): 1289-1292.
7. Brower, K. (2002). "Anabolic steroid abuse and dependence." 1-11.

Current Trends in Chemistry Fashion

A real chemistry grad student wearing molecule shoes from Aldo:




It's relieving to know that there are clothing designers even geekier than (some) of us.
Also, that a science degree can apparently be used toward a career in fashion design.

Reactions under water cities.

The Cannizzaro reaction (1) was mentioned in an older textbook that I’ve been reading (2). It turns out that my not having heard of the Cannizzaro before, and the 1961 publication date of the textbook didn’t mean I had found an Atlantis, (there is, in fact, even a Wikipedia entry on this reaction), but I still found it interesting enough to dig further.

The Cannizarro is a disproportionate, hydride transfer reaction. One molecule of reactant reduces another, itself becoming oxidized, and the result is that two different products are formed, ergo benzaldehyde:


Scheme 1
The synthetic utility is limited by the 50% maximum possible yield. Also, since the aldol reaction is faster, the Cannizzaro won’t occur where there are enolizable hydrogens.

To determine whether the hydride source for benzaldehyde reduction was another molecule of benzaldehyde or water, the reaction was carried out in D2O by (3), who found that deuterium was not incorporated into benzyl alcohol. Accordingly, the mechanism involves three steps, OH- nucleophilic addition, rate limiting, carbon-to-carbon hydride shift, and a rapid proton transfer.

Scheme 2
A hydride shift occurs instead of alkoxide nucleophilic addition.

The proposed mechanism agrees with the rate expression


and a DFT study of the reaction (4) which found the phenyl groups were able to reasonably position such as to avoid crowding each other, and the end products were very stable (exothermic, -36.28 kcal/mol).

The mechanism can be rationalized by considering the two opposing properties of the carbonyl group. On one hand, the electronegativity of oxygen polarizes the electron distribution (~2.5 debye), placing a partial positive charge on the carbonyl carbon and making it susceptible to nucleophilic attack. On the other hand, the carbonyl C=O has a large bond energy of 730 kJ/mol, compared to C=C 614 kJ/mol, and C=N 615 kJ/mol. In fact, the π-bond is stronger than the σ-bond (C-O 360 kJ/mol). The strength of the bond works to oppose the loss of C=O. So while attack of the oxygen anion of intermediate 1 on PhCHO seems reasonable, the resultant ether can’t convert to form C=O; instead, the hydride anion is released in order to form benzoic acid, a carbonyl containing compound.

In application, the Cannizzaro reaction has narrow synthetic utility, but should be remembered as source of byproducts whenever compounds containing aldehydes are treated with OH-/RO- bases.

(1) Cannizzaro, S. (1853). "Ueber den der Benzoësäure entsprechenden Alkohol". Liebigs Annalen 88: 129–130
(2) Peter Sykes, “A Guidebook to Mechanism in Organic Chemistry” 4th Ed.
(3) FREDENHAGEN AND BONHOEFFER, 2. phys. Chem., A181, 379 (1938).
(4) Yamabe, S. 2009, 7, 951