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     

Recent advances in the analysis of steroid hormones and related drugs.

The development during the last 15 years and the state-of-the-art in the analysis of bulk steroid hormone drugs and hormone-like structures and pharmaceutical formulations made thereof are summarized. Other steroids (sterols, bile acids, cardiac glycosides, vitamins D) as well as biological-clinical aspects and pharmacokinetic and metabolic studies are excluded from this review. The state-of-the-art is summarized based on comparisons of monographs in the latest editions of the European Pharmacopoeia, United States Pharmacopoeia and the Japanese Pharmacopoeia. This is followed by sections dealing with new developments in the methodology for the fields of spectroscopic and spectrophotometric, chromatographic, electrophoretic and hyphenated techniques as well electroanalytical methods. The review is terminated by two problem-oriented sections: examples on impurity and degradation profiling as well as enantiomeric analysis.     

Electrochemical reduction of 1-([(4-halophenyl)imino]methyl)-2-naphthols in aprotic media.

The electrochemical reduction of 1-([(4-halophenyl)imino]methyl)-2-naphthols on graphite electrodes was studied using cyclic voltammetry, chronoamperometry, constant-potential coulometry and preparative constant-potential electrolysis techniques. The data revealed that the reduction on graphite was irreversible and followed an EC mechanism. The diffusion coefficients and the number of electrons transferred were determined using the chronoamperometric Cottrell slope and the ultramicro disc Pt-electrode steady-state current. The number of electrons was also determined by bulk electrolysis. The compounds were subjected to constant-potential preparative electrolysis and the electrolysis products were purified and identified by spectroscopic methods. Based on these findings, a mechanism for the electro-reduction process is proposed.     

Synthesis of Novel Monomeric Dyes with Anthraquinone Residue

Two novel polymerizable dyes with anthraquinone residue have been prepared, and their structures were characterized by FTIR, ^1HNMR and EA.     

Augmented Lagrangian Algorithms Based on the Spectral Projected Gradient Method for Solving Nonlinear Programming Problems

The spectral projected gradient method SPG is an algorithm for large-scale bound-constrained optimization introduced recently by Birgin, Martínez, and Raydan. It is based on the Raydan unconstrained generalization of the Barzilai-Borwein method for quadratics. The SPG algorithm turned out to be surprisingly effective for solving many large-scale minimization problems with box constraints. Therefore, it is natural to test its perfomance for solving the sub-problems that appear in nonlinear programming methods based on augmented Lagrangians. In this work, augmented Lagrangian methods which use SPG as the underlying convex-constraint solver are introduced (ALSPG) and the methods are tested in two sets of problems. First, a meaningful subset of large-scale nonlinearly constrained problems of the CUTE collection is solved and compared with the perfomance of LANCELOT. Second, a family of location problems in the minimax formulation is solved against the package FFSQP.     

Harnack inequality for some classes of Markov processes

In this paper we establish a Harnack inequality for nonnegative harmonic functions of some classes of Markov processes with jumps. Mathematics Subject Classification (2000): Primary 60J45, 60J75, Secondary 60J25.This work was completed while the authors were in the Research in Pairs program at the Mathematisches Forschungsinstitut Oberwolfach. We thank the Institute for the hospitality.The research of this author is supported in part by NSF Grant DMS-9803240.The research of this author is supported in part by MZT grant 0037107 of the Republic of Croatia.     

Synthesis of paramagnetic BODIPY dyes as new double (spin and fluorescence) sensors

Paramagnetic pyrroline and 1,2,3,6-tetrahydropyridine derivatives of BODIPY and their diamagnetic analogs have been synthesized and characterized as novel redox double sensor and cation sensitive reagents.