Derivatives of (2R)-N-Glyoxylbornane-10,2-sultam and Their Use as auxiliaries in the diastereoselective spirocyclization of 2-substituted tryptamines

A crude hydrate 6 and a crystalline hemiacetal 7 of glyoxylamide 4 were prepared from crotonamide 5 (Scheme 2). Particularly hemiacetal 7 , but also 6 and the ‘dimer’ 8 (obtained from 7 ) may serve as homochiral auxiliaries. The structure of 8 was determined by X-ray analysis. By arenesulfonyl halides, tryptimines 12–14 of 4 were diastereoselectively transformed into spirotricycles 15–17 and 19 .     

An inner product lemma

Given the operator product BA in which both A and B are symmetric positive‐definite operators, for which symmetric positive‐definite operators C is BA symmetric positive‐definite in the C inner product 〈x, y〉C? This question arises naturally in preconditioned iterative solution methods, and will be answered completely here. Copyright © 2004 John Wiley & Sons, Ltd.     

Biopolymers for biocatalysis: Structure and catalytic mechanism of hydroxynitrile lyases

Hydroxynitrile lyases catalyze the reversible cleavage of α-cyanohydrins to yield hydrocyanic acid and the corresponding aldehyde or ketone. Besides its biological interest, this class of enzymes is also of relevance in industrial biocatalysis for the enantioselective condensation of HCN with a variety of aldehydes and ketones. Several distinctly different types of hydroxynitrile lyases (HNLs) are known, which must have originated through convergent evolution from different ancestral proteins. Three-dimensional structural data are known for three classes of hydroxynitrile lyases. Insights into the reaction mechanisms emerged from a combination of structural, enzyme kinetic, spectroscopic, and molecular modeling data. For all three types of HNLs, mechanisms involving acid–base catalysis were proposed. In members belonging to the α,β-hydrolase type, the amino acid residues of the catalytic triad presumably act as general acid/base, whereas for flavine adenine dinucleotide (FAD)-dependent HNLs a single histidine residue fulfills this function. In the third type of HNL—which is related to carboxypeptidase—acid–base catalysis involves the carboxylate of the C-terminal residue. The catalytic relevance of a positive electrostatic potential in the active site was suggested in some of the mechanistic proposals. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 479–486, 2004     

Shell model interaction between proton holes and between proton holes and neutron particles around 208Pb

An effective residual interaction between particles and holes for shell model calculations around ²⁰⁸Pb, derived from the interaction between free nucleons, is compared with the measured properties of proton-hole neutron states in ²⁰⁸Tl and the interaction between proton holes is adjusted to newly measured level energies in ²⁰⁶Hg. These interaction elements are particularly relevant for neutron-rich nuclei. The adjustment of two mixing elements reproduces the known γ-decay data in ²⁰⁸Tl. Received: 2 April 2002 / Accepted: 2 May 2002     

Effective Mode Volume of Nanoscale Plasmon Cavities

The controlled squeezing of electromagnetic energy into nanometric volumes via surface plasmon-polariton excitations in plasmonic nanoresonators is analyzed using the concept of an effective electromagnetic mode volume V _eff, while taking careful account of the plasmon-polariton dispersion and the electromagnetic energy stored in the metal. Together with the quality factor Q of the cavity resonance, this enables a comparison with dielectric optical cavities, where V _eff is limited by diffraction. For a Fabry–Perot type planar metallic cavity, a one-dimensional analytic model as well as a three-dimensional finite-difference time-domain simulation reveal that V _eff is not bounded by diffraction, and that Q/V _eff increases for decreasing cavity size. In this picture, matter–plasmon interactions can be quantified in terms of Q and V _eff, and a resonant cavity model for the enhancement of spontaneous Raman scattering is presented.     

A Variable Neighborhood Search for the Multi Depot Vehicle Routing Problem with Time Windows

The aim of this paper is to propose an algorithm based on the philosophy of the Variable Neighborhood Search (VNS) to solve Multi Depot Vehicle Routing Problems with Time Windows. The paper has two main contributions. First, from a technical point of view, it presents the first application of a VNS for this problem and several design issues of VNS algorithms are discussed. Second, from a problem oriented point of view the computational results show that the approach is competitive with an existing Tabu Search algorithm with respect to both solution quality and computation times.     

A geometric theory forL 2-stability of the inverse problem in a one-dimensional elliptic equation from anH 1-observation

This study provides a stability theory for the nonlinear least-squares formulation of estimating the diffusion coefficient in a two-point boundary-value problem from an error-corrupted observation of the state variable. It is based on analysing the projection of the observation on the nonconvex attainable set.This research was started while G. Chavent visited the Technical University of Graz. Support through the Steiermaerkische Landesregierung is gratefully acknowledged.