Caged mitochondrial uncouplers that are released in response to hydrogen peroxide

Caged versions of the most common mitochondrial uncouplers (proton translocators) have been prepared that sense the reactive oxygen species (ROS) hydrogen peroxide to release the uncouplers 2,4-dinitrophenol (DNP) and carbonylcyanide p-trifluoromethoxyphenylhydrazone (FCCP) from caged states with second order rate constants of 10 (±0.8) M⁻¹ s⁻¹ and 64.8 (±0.6) M⁻¹ s⁻¹, respectively. The trigger mechanism involves conversion of an arylboronate into a phenol followed by fragmentation. Hydrogen peroxide-activated uncouplers may be useful for studying the biological process of ageing.     

High‐performance liquid chromatography/mass spectrometric and proton nuclear magnetic resonance spectroscopic studies of the transacylation and hydrolysis of the acyl glucuronides of a series of phenylacetic acids in buffer and human plasma

The use of high‐performance liquid chromatography/mass spectrometry (HPLC/MS) and proton nuclear magnetic resonance (¹H NMR) spectroscopy for the kinetic analysis of acyl glucuronide (AG) isomerisation and hydrolysis of the 1‐β‐O‐acyl glucuronides (1‐β‐O‐AG) of phenylacetic acid, (R)‐ and (S)‐α‐methylphenylacetic acid and α,α‐dimethylphenylacetic acid is described and compared. Each AG was incubated in both aqueous buffer, at pH 7.4, and control human plasma at 37°C. Aliquots of these incubations, taken throughout the reaction time‐course, were analysed by HPLC/MS and ¹H NMR spectroscopy. In buffer, transacylation reactions predominated, with relatively little hydrolysis to the free aglycone observed. In human plasma incubations the calculated rates of reaction were much faster than for buffer and, in contrast to the observations in buffer, hydrolysis to the free aglycone was a significant contributor to the overall reaction. A diagnostic analytical methodology based on differential mass spectrometric fragmentation of 1‐β‐O‐AGs compared to the 2‐, 3‐ and 4‐positional isomers, which enables selective determination of the former, was confirmed and applied. These findings show that HPLC/MS offers a viable alternative to the more commonly used NMR spectroscopic approach for the determination of the transacylation and hydrolysis reactions of these AGs, with the major advantage of having the capability to do so in a complex biological matrix such as plasma. Copyright © 2010 John Wiley & Sons, Ltd.     

Identification of Apigenin Metabolites in Rat Liver Perfusate by Column Switching High Performance Liquid Chromatography/Electrospray Ionization Mass Spectrometry

Summary.  A selective column switching high performance liquid chromatographic method has been used for the simultaneous determination of apigenin and metabolites in rat liver perfusate. This new method clearly separated apigenin and the metabolites with high resolution. The structures of metabolites were proposed based on selective ion recording and full scan analysis by electrospray ionization mass spectrometry. Corresponding author. E-mail: basly@pharma.unilim.fr Received May 15, 2002; accepted (revised) September 13, 2002     

Global stability of a two-species piecewise linear volterra ecosystem

This paper extends the results of Goh [1], and Takeuchi and Adachi [2,3] concerning the generalized linear Volterra model. We introduce a piecewise linear Volterra model for a two- species system. The solution of the steady-state problem is then shown to be equivalent to finding the solution to the Generalized Linear Complementarity Problem. We show when this nonnegative equilibrium is unique and globally asymptotically stable in the sense of Goh [1].     

Résolution des équations de dispersion–diffusion en présence de forts gradientsResolution of advection–diffusion equation in presence of sharp gradient

In order to resolve the convection terms in the simulation of coastal flows, we propose a numerical method based on the Total Variation Diminishing scheme completed with the Artificial Compression Method to reduce the artificial diffusion and to sharpen the tracer profile in strong gradient regions. This method was applied successfully at discontinuous regions, but out of these regions a limitation of its application is necessary. An application is made to estimate the width of the fresh water band in the Eastern English Channel. To cite this article: C. Sart et al., C. R. Mecanique 330 (2002) 159–165.     

Synthesis of enantiomerically pure functionalised trianglamine macrocycles by N-acylation and N-alkylation reactions

The N-alkylation and N-acylation reactions of trianglamine macrocycles are described leading to an efficient synthesis of enantiomerically pure functionalised hexa-amide and hexa-amine trianglamine macrocycles.