Quantifying intermolecular interactions: guidelines for the molecular recognition toolbox

Molecular recognition events in solution are affected by many different factors that have hampered the development of an understanding of intermolecular interactions at a quantitative level. Our tendency is to partition these effects into discrete phenomenological fields that are classified, named, and divorced: aromatic interactions, cation-pi interactions, CH-O hydrogen bonds, short strong hydrogen bonds, and hydrophobic interactions to name a few.1 To progress in the field, we need to develop an integrated quantitative appreciation of the relative magnitudes of all of the different effects that might influence the molecular recognition behavior of a given system. In an effort to navigate undergraduates through the vast and sometimes contradictory literature on the subject, I have developed an approach that treats theoretical ideas and experimental observations about intermolecular interactions in the gas phase, the solid state, and solution from a single simplistic viewpoint. The key features are outlined here, and although many of the ideas will be familiar, the aim is to provide a semiquantitative thermodynamic ranking of these effects in solution at room temperature.     

Variations on the warped deformed conifold

The warped deformed conifold background of type IIB theory is dual to the cascading SU(M(p+1))×SU(Mp) gauge theory. We show that this background realizes the (super-)Goldstone mechanism where the U(1) baryon number symmetry is broken by expectation values of baryonic operators. The resulting massless pseudo-scalar and scalar glueballs are identified in the supergravity spectrum. A D-string is then dual to a global string in the gauge theory. Upon compactification, the Goldstone mechanism turns into the Higgs mechanism, and the global strings turn into ANO strings. To cite this article: S.S. Gubser et al., C. R. Physique 5 (2004).

Résumé

La configuration de fond pour la théorie de type IIB donnée par le conifold voilé déformé est duale à la cascade de théorie de jauge SU(M(p+1))×SU(Mp). Nous montrons que cette configuration donne une réalisation du mécanisme de (super-)Goldstone où la symètrie baryonique U(1) est brisée par la valeur moyenne dans le vide des opérateurs baryoniques. Les boules de glue pseudo-scalaires et scalaires de masse nulle résultantes sont identifiées dans le spectre de supegravité. Une D-corde est alors duale à une corde globale dans la théorie de jauge. Après compactification, le mécanisme de Goldstone devient un mécanisme de Higgs, et une corde globale devient une corde ANO. Pour citer cet article : S.S. Gubser et al., C. R. Physique 5 (2004).     

Effect of the counterion on the rate of electron transfer in dendrimer films

The electrochemical behavior of a film composed of a redox-active dendrimer was studied as a function of the type of counterion available during its reduction and reoxidation. The rate of permeation/migration of counterions into the film appeared to be the bottleneck to electron transfer through the film. Because the dendrimer is rather hydrophobic, increasing the hydrophobicity of the counterion increased the rate and extent of electron hopping within the films.     

Bifunctional, conjugated oligomers for orthogonal self-assembly: selectivity varies from planar substrates to nanoparticles

A diphenylacetylene containing two different end groups (isonitrile and thioacetate) was synthesized, showing that the chemistry used to install each end group is compatible with that of the others. The isonitrile group binds preferentially to platinum, and the thiol group binds preferentially to gold. However, the selectivity was different when nanoparticles were compared to planar substrates.     

Investigations into a free radical-mediated 1,2-imino migration

The radical reactions of a series of bromides 9a-c and selenides 12-15 have been investigated to determine the factors that are important for a successful radical-mediated 1,2-imino migration.     

Carbenoid induced irreversible ring opening of naphthopyrans

Contrary to expectation rhodium carbenoids do not undergo cycloaddition to the 2H-pyran unit of the isomeric naphthopyrans 3 and 5. With 3, a naphtho[2,1-b]pyran-8-ylacetate, 4 is formed and a novel merocyanine dye 6 results from a cycloaddition across the C-5-C-6 double bond of the naphtho[1,2-b]pyran 5. Tethering the carbenoid to the naphtho[1,2-b]pyran system 5, as in 10, results in a similar mode of addition and affords the intensely coloured tetracycle 11.