Field optimized initial state based control of photodissociation

A new scheme for controlling photodissociation through preparation of a variationally optimized linear superposition of field free vibrational eigenstates is applied for selective control of IBr and HI dissociation. The dependence of photodissociation on various field parameters and initial conditions is examined to investigate the mechanistic basis of selective control. The parametric equations of motion approach for determining vibrational dynamics as a function of field parameters without having to solve the time dependent Schrödinger equation explicitly for each field parameter separately is outlined and its use to identify field characteristics which will provide the requisite population mix represented by the optimal linear superposition of vibrational states is advocated.     

Diastereoselective formation of 2-aryl-3-arenesulfonyl 4-ethyl-1,3-oxazolidines: An X-ray crystallographic and H NMR study

N-Arylsulfonamides of (R)- and (S)-2-amino-1-butanol, on condensation with aromatic aldehydes produced diastereomerically pure 2-aryl-3-arenesulfonyl 4-ethyl-1,3-oxazolidines. The absolute configurations of one enantiomeric pair have been determined from two fully refined X-ray structures, supplemented by nmr data.     

The combination technique and some generalisations

The combination technique has repeatedly been shown to be an effective tool for the approximation with sparse grid spaces. Little is known about the reasons of this effectiveness and in some cases the combination technique can even break down. It is known, however, that the combination technique produces an exact result in the case of a projection into a sparse grid space if the involved partial projections commute.

The performance of the combination technique is analysed using a projection framework and the C/S decomposition. Error bounds are given in terms of angles between the spanning subspaces or the projections onto these subspaces. Based on this analysis modified combination coefficients are derived which are optimal in a certain sense and which can substantially extend the applicability and performance of the combination technique.     

Synthesis and characterization of a semiflexible liquid crystalline polyester with a broad nematic region

In this paper, we report on the synthesis and detailed characterization of a new semiflexible nematic liquid crystalline polyester which could serve as a 'model' polyester for a variety of physical and physico-chemical investigations. The polymer is a nematic liquid over a wide temperature range-from the glass transition temperature at ∼95°C to the isotropic transition at ∼240°C. We expect this polyester to be particularly useful for studying the effect of flow on the orientation of liquid crystalline polymers, as well as the production and removal of disclinations.     

Origins and structures of background ions produced by fast-atom bombardment of glycerol

Accurate mass measurements were used to assign elemental compositions and tandem mass spectrometry was used to characterize the peak-at-every-mass background ions produced by kiloelectron-volt-particle bombardment of neat fast-atom bombardment matrices. The majority of the background ions observed in the mass spectrum of neat glycerol was identified. On the basis of the experiments with glycerol, a theory for the formation of background ions is presented. Results are discussed according to the chemical and physical changes that ygoe;on-volt-particle bombardment produces in the matrix.     

Microbial Baeyer-Villiger Oxidation of Ketones by Cyclohexanone and Cyclopentanone Monooxygenase – A Computational Rational for Biocatalyst Performance

Summary. Recombinant Escherichia coli overexpressing Pseudomonas sp. NCIMB 9872 cyclopentanone monooxygenase (CPMO, EC 1.14.13.16) and Acinetobacter sp. NCIMB 9871 cyclohexanone monooxygenase (CHMO, EC 1.14.13.22) have been utilized in whole-cell Baeyer-Villiger biotransformations of prochiral bicycloketones. A significant difference in substrate acceptance and stereoselectivity was observed for bicyclo[3.3.0] and bicyclo[4.3.0] substrates. A plausible mechanism of these transformations was established by means of high level DFT/B3LYP calculations suggesting an essential difference in electronic requirements for a successful enzymatic conversion, which was similarly encountered in recombinant whole-cell mediated biooxidations. Some of the lactones produced in the biocatalytic Baeyer-Villiger oxidation represent key intermediates for the synthesis of indole alkaloids.     

Bending loss measurement using a fiber cavity ringdown scheme

A novel sensitive technique for the determination of losses in fiber cavities is presented. The method is based on the cavity ringdown scheme implemented in silica-based single-mode fibers. Bending losses of fiber cavities of different lengths have been measured showing all an oscillating behavior with respect to the curvature radius of the fiber as predicted by a theoretical model. The best minimum detectable absorbance per cavity pass achieved by this new method is 1.72×10⁻³ dB within a 10 m-long cavity. This limit suffices well for an accurate determination of optical bending losses even in bend-insensitive fibers. Furthermore, the comparison of the measured bending losses with a theoretical model allows the extraction of different fiber parameters. Good agreement has been found between the experimentally derived parameters and literature data.