Aliphatic hydroxylation and epoxidation of capsaicin by cytochrome P450 CYP505X

Microbial cytochrome P450 enzymes (CYPs) are able to mimic the metabolism of human CYPs. One challenge is to identify the respective drug metabolites and to compare substrate specificities to those of the human enzymes. In this study, a class VIII self-sufficient CYP from Aspergillus fumigatus (CYP505X) and variants of this enzyme were heterologously expressed in E. coli. The substrate scope of the variants was determined using active pharmaceutical ingredients (APIs) and (hetero)cyclic compounds. Capsaicin – the active compound in chili peppers – was oxidized most efficiently (4.36?μM/min) in a whole cell mediated biotransformation. The products were isolated, purified and their structures elucidated by 1D and 2D NMR. The two major metabolites showed modifications on the lipophilic side chain. Specifically, capsaicin was hydroxylated at position 8 to give (E)-8-hydroxy-N-(4-hydroxy-3-methoxybenzyl)-8-methylnon-6-enamide and epoxidized at the double bond to give N-(4-hydroxy-3-methoxybenzyl)-5-(3-isopropyloxiran-2-yl)-pentanamide.     

Controlled grafting of cellulose esters using SET‐LRP process

Here, we present the first example of application of single‐electron transfer living radical polymerization (SET‐LRP) process to a controlled grafting of cellulose esters, cellulose diacetate (CDA), and cellulose acetate butyrate (CAB). The cellulose ester macroinitiators with various functionality densities have been prepared by acylation of the backbones with 2‐bromoisobutyryl (BrIB) and dichloroacetyl (DCA) groups, respectively. Methacrylate monomers were polymerized using DCA‐functionalized macroinitiators in the presence of pentamethyldiethylene triamine as a ligand. At 30 °C, the reaction is rather slow, reaching about 10% conversion after 3 to 6 h of polymerization, whereas the higher temperature (60 °C) perceptibly speeds up the polymerization so that methyl methacrylate (MMA) conversion is ～30% after 5 h. Graft copolymers with random‐type and diblock‐type grafts having amphiphilic character were also synthesized. For acrylate grafting (BuA and t‐BuA), BrIB‐functionalized macroinitiators are more convenient in a combination with a low concentration of Cu(0) and Me₆TREN as a ligand and polymerization is detectably faster even at the lower temperature than that of MMA. Kinetic studies show “living” character of both the graftings. Important advantages of SET‐LRP, compared with classic ATRP, are (i) higher polymerization rate, (ii) lower extent of recombination of the growing grafts and (iii) negligible coloration of the products with catalytic residua, so that the prepared polymers do not require additional careful purification. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

The Spectrum of Singular Sturm-Liouville Problems With Eigenparameter Dependent Boundary Conditions and Its Approximation

We study the spectrum of singular Sturm-Liouville problems with eigenparameter dependent boundary conditions and its approximation with eigenvalues from a sequence of regular problems.     

The Mobile Phase Motion in Ascending Micellar Thin-Layer Chromatography with Normal-Phase Plates

JPC – Journal of Planar Chromatography – Modern TLC - The physical-chemical characteristics (surface tension and viscosity) of micellar mobile phases based on the cationic surfactant...     

Global existence for defocusing cubic NLS and Gross–Pitaevskii equations in three dimensional exterior domains

We prove global wellposedness in the energy space of the defocusing cubic nonlinear Schrödinger and Gross–Pitaevskii equations on the exterior of a nontrapping domain in dimension 3. The main ingredient is a Strichartz estimate obtained combining a semi-classical Strichartz estimate [R. Anton, Strichartz inequalities for Lipschitz metrics on manifolds and nonlinear Schrödinger equation on domains, arxiv:math.AP/0512639, Bull. Soc. Math. France, submitted for publication] with a smoothing effect on exterior domains [N. Burq, P. Gérard, N. Tzvetkov, On nonlinear Schrödinger equations in exterior domains, Ann. I.H.P. (2004) 295–318].     

Zur Kenntniss der Überwallungsharze

Ohne ZusammenfassungZum Schlusse sei es uns noch gestattet, den Herren Dr. F. Krasser, sowie Prof. A. Heimerl für ihre freundlichen Beiträge den wärmsten Dank auszusprechen.     

Beweis eines arithmetischen Satzes

Monatshefte für Mathematik -     

Analysis of exhaled breath from smokers,passive smokers and non‐smokers by solid‐phase microextraction gas chromatography/mass spectrometry

In this study, 38 samples of expired air were collected and analyzed from 20 non‐smoking volunteers, four passive smokers and 14 smokers (21 women and 17 men). Measurements were carried out using solid‐phase microextraction (SPME) as an isolation and preconcentration technique. The determination and identification were accomplished by gas chromatography coupled with mass spectrometry (GC/MS). Our data showed that ca 32% of all identified compounds in the breath of healthy non‐smokers were saturated hydrocarbons. In the breath of smoking and passive smoking volunteers hydrocarbons were predominant, but also present were more exogenous analytes such as furan, acetonitrile and benzene than in the breath of non‐smokers. Acetonitrile, furan, 3‐methylfuran, 2,5‐dimethylfuran, 2‐butanone, octane and decane were identified in breath of smoking and passive smoking persons. Copyright © 2008 John Wiley & Sons, Ltd.