Crystal structure prediction of flexible molecules using parallel genetic algorithms with a standard force field

This article describes the application of our distributed computing framework for crystal structure prediction (CSP) the modified genetic algorithms for crystal and cluster prediction (MGAC), to predict the crystal structure of flexible molecules using the general Amber force field (GAFF) and the CHARMM program. The MGAC distributed computing framework includes a series of tightly integrated computer programs for generating the molecule's force field, sampling crystal structures using a distributed parallel genetic algorithm and local energy minimization of the structures followed by the classifying, sorting, and archiving of the most relevant structures. Our results indicate that the method can consistently find the experimentally known crystal structures of flexible molecules, but the number of missing structures and poor ranking observed in some crystals show the need for further improvement of the potential. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009     

Comprehensive inter‐laboratory calibration of reference materials for δ18O versus VSMOW using various on‐line high‐temperature conversion techniques

Internationally distributed organic and inorganic oxygen isotopic reference materials have been calibrated by six laboratories carrying out more than 5300 measurements using a variety of high‐temperature conversion techniques (HTC) a in an evaluation sponsored by the International Union of Pure and Applied Chemistry (IUPAC). To aid in the calibration of these reference materials, which span more than 125‰, an artificially enriched reference water (δ¹⁸O of +78.91‰) and two barium sulfates (one depleted and one enriched in ¹⁸O) were prepared and calibrated relative to VSMOW2 b and SLAP reference waters. These materials were used to calibrate the other isotopic reference materials in this study, which yielded:

Investigation of the reaction of α-thioamides, α-esters and α-nitriles with N-halosuccinimides

Investigation of the reaction of α-thioamides, α-esters and α-nitriles with NBS and NCS is described. The scope of this stereoselective oxidative transformation to the β-haloacrylamides, β-acrylates and β-acrylonitriles has been determined. A mechanistic rationale to explain the observed differences in reactivity between the amide, ester and nitrile series is proposed.     

C-H activation in bithiazole ring with thallium(III) ion

Two novel organometallic complex of 2,2′-dimethyl-4,4′-bithiazole (dm4bt) ligand (L) with formula [Tl(dm4bt)₂(NO₃)(H₂O)] (1) and [Tl(dm4bt)₂(NO₃)(DMSO)] (2) have been synthesized and structurally characterized by elemental analysis, FT-IR, ¹H NMR spectra and X-ray crystallography. These complexes also display the first transoid conformation in bithiazole ligands in which C-H bond activation in bithiazole ring is observed with Tl(III) ion.     

Maximum principles for a fourth order equation from thin plate theory

This paper focuses on a nonlinear equation from thin plate theory of the form Δ(D(x)Δw)−(1−ν)[D,w]+c(x)f(w)=0. We obtain maximum principles for certain functions defined on the solution of this equation using P-functions or auxiliary functions of the types used by Payne [L.E. Payne, Some remarks on maximum principles, J. Anal. Math. 30 (1976) 421-433] and Schaefer [P.W. Schaefer, Solution, gradient, and laplacian bounds in some nonlinear fourth order elliptic equations, SIAM J. Math. Anal. 18 (1987) 430-434].     

Selenodiazole-fused diacetamidopyrimidine, a selective fluorescence sensor for aliphatic monocarboxylates

A designed sensor, selenodiazole-fused pyrimidine ring having two acetylamino groups at 2,4-positions has been synthesized for selective recognition of aliphatic monocarboxylate anions over a wide range of other anions. The recognition study has been carried out by UV-vis and fluorescence methods. A significant bathochromic shift of the fluorescence intensity of the receptor in the presence of carboxylate makes the receptor a discriminating sensor for aliphatic monocarboxylates.     

Oxygen as a site specific probe of the structure of water and oxide materials

The method of oxygen isotope substitution in neutron diffraction is introduced as a site specific structural probe. It is employed to measure the structure of light versus heavy water, thus circumventing the assumption of isomorphism between H and D as used in more traditional neutron diffraction methods. The intramolecular and intermolecular O-H and O-D pair correlations are in excellent agreement with path integral molecular dynamics simulations, both techniques showing a difference of ?0.5% between the O-H and O-D intramolecular bond distances. The results support the validity of a competing quantum effects model for water in which its structural and dynamical properties are governed by an offset between intramolecular and intermolecular quantum contributions.     

Measuring the complete force field of an optical trap

The use of optical traps to measure or apply forces on the molecular level requires a precise knowledge of the trapping force field. Close to the trap center, this field is typically approximated as linear in the displacement of the trapped microsphere. However, applications demanding high forces at low laser intensities can probe the light-microsphere interaction beyond the linear regime. Here, we measured the full nonlinear force and displacement response of an optical trap in two dimensions using a dual-beam optical trap setup with back-focal-plane photodetection. We observed a substantial stiffening of the trap beyond the linear regime that depends on microsphere size, in agreement with Mie theory calculations. Surprisingly, we found that the linear detection range for forces exceeds the one for displacement by far. Our approach allows for a complete calibration of an optical trap.