A rapid method for calculating derivatives of solvent accessible surface areas of molecules

A novel method to calculate the derivatives of solvent accessible surface areas is presented. Unlike earlier analytic methods, which require the molecular topology and the use of global Gauss-Bonnet theorem, this method requires only the fractional accessibilities of surface arcs. We developed an efficient numerical algorithm to calculate the surface arcs by creating a uniform set of points on the circles of intersection between surface atoms. A hierarchical point density doubling scheme led to a logarithmic dependence of Central Processing Unit (CPU) time on the number of points used. This algorithm calculated area derivatives for a 1000-atom protein in 1.5 s on an SGI INDIGO² which were within 2% of the analytic area derivatives calculated with the program ANAREA. This algorithm scales linearly with the number of atoms for large molecules and is easily parallelizable. © 1995 by John Wiley & Sons, Inc.     

Graded Witt ring and unramified cohomology

It is proved that for a smooth affine curveX over a local ring or global field, the graded Witt ring ofX is isomorphic to the graded unramified cohomology ring ofX. IfX is projective and has a rational point, the same result holds if and only if every quadratic space defined on the complement of a rational point extends toX. Such an extension is possible, for instance, if the canonical line bundle onX is a square in PicX.     

Reactivity and selectivity of the N-acetyl-Glu-P-1, N-acetyl-Glu-P-2, N-acetyl-MeIQx,and N-acetyl-IQx nitrenium ions: comparison to carbocyclic N-arylnitrenium ions

The model ultimate carcinogens 1a-d, related to the metabolites of the food-derived carcinogenic heterocyclic amines Glu-P-1, Glu-P-2, MeIQx, and IQx, spontaneously decompose in neutral aqueous solution to generate the heterocyclic nitrenium ions, 2a-d. The less reactive esters 1a and 1b also undergo acid-catalyzed ester hydrolysis to generate the corresponding hydroxamic acids at pH <2, while the more reactive 2c and 2d are prone to rearrangement in nonaqueous solvents. The reactions of the nitrenium ions with AcO(-), HPO(4)(2-), N(3)(-), and 2'-deoxyguanosine (d-G) were characterized in aqueous solution by using a combination of competitive trapping methods and product isolation and identification. The reactions with N(3)(-) and d-G generally follow patterns previously established for carbocyclic nitrenium ions, but the reactions with AcO(-) and HPO(4)(2-) are unusual. Similar reactions have previously only been reported for heterocyclic 1-alkyl-2-imidazolium ions. The N(3)(-)/solvent selectivities of these ions (5.1 x 10(6) M(-1) for 2a, 2.3 x 10(6) M(-1) for 2b, 1.2 x 10(5) M(-1) for 2c, and 5.2 x 10(4) M(-1) for 2d) are comparable to those of highly selective carbocyclic nitrenium ions. If k(az) for these ions is diffusion limited at ca. 5 x 10(9) M(-1) s(-1) the aqueous solution lifetimes of these ions range from 10 micros (2d) to 1 ms (2a). These ions are also highly selective for trapping by d-G, but comparisons to other nitrenium ions show that they are 10- to 50-fold less selective for trapping by d-G than they would be if both the N(3)(-) and d-G reactions were diffusion limited. This is not a consequence of their heterocyclic structures. Several carbocyclic ions show similar behavior. The relatively inefficient trapping of 2c and 2d by d-G may account for the observation of the unusual minor N-2 d-G adduct that is isolated for both of these nitrenium ions, but has not previously been observed for the reactions of other nitrenium ions with monomeric d-G.     

Condensed thymine films at the mercury/water interface: Part V. Phase transitions

The topography of the various phase transitions in a supersaturated thymine solution is described. Most transitions leading from a non-condensed to a condensed film involve nucleation and growth, via a metastable intermediate surface state, as do some transitions between condensed films. The latter have unusually high Avrami slopes and, sometimes, involve multiple intermediate states. Other transitions exhibit exponential transients. Of the three pit regions observed, that at the most positive potentials is present only in super-saturated solutions, is clearly associated with three-dimensional phase formation, and does not lead to a well-defined steady-state interfacial capacitance. Most transitions leading to a non-condensed final state exhibit exponential transients.     

Rhodium catalyzed,one-pot,three component redox-neutral process towards fused ring heterocycles

A three component, rhodium-catalyzed isomerisation/1,3-dipolar cycloaddition reaction is described for the synthesis of fused ring heterocycles as endo/exo isomers, with the formation of three new bonds and four stereocenters.     

Preparation,characterization, and thermal studies of γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> and CuO dispersed polycarbonate nanocomposites

Polycarbonate with γ-Fe₂O₃ and CuO dispersions were carried out by solvent casting method to make polycarbonate-γ-Fe₂O₃ and polycarbonate-CuO composite films. These films were characterized for the molecular structure through FTIR spectroscopy and crystallinity by X-ray diffraction (XRD) measurements. The morphology of polycarbonate-γ-Fe₂O₃ was found to be different from that of polycarbonate-CuO composite films based on the scanning electron micrograph (SEM) images. The thermal traces of composites are different from that of pure polycarbonate which indicating the catalytic decomposition when compared with virgin polymer which is oxidative decomposition. An understanding of the structure, morphology, and thermal behaviour of the composite films are envisaged in the present study.     

Regioselective photodimerization of cinnamic acids in water: Templation with cucurbiturils

Cinnamic acids upon irradiation in solution undergo geometric isomerization while dimerizing to different dimers in the crystalline state. Controlling the nature of the dimer formed upon irradiation remains a challenging task. We have aligned a variety of cinnamic acid molecules in a head-head fashion employing cucurbit[8]uril, a weakly water soluble host as a template. The water solubility of cucurbit[8]uril is enhanced by inclusion of water soluble cinnamic acids and positions the olefins in an arrangement that favors the formation of syn head-head cyclobutanes in near quantitative yields. This methodology works in both solid state as well as in aqueous solution. Irradiation of cinnamic acid complexes with gamma-cyclodextrin has been carried out as a comparison. We find that while cucurbit[8]uril functions well both in solid state and aqueous solution, cyclodextrin works best as solid complexes only. Consistent with the postulated requirement of large cavities for templating olefins to dimerization, irradiation of complexes of cinnamic acid with cucurbit[7]uril resulted in only the corresponding cis isomers.