Hydrogenation of Aromatic Nitrogroups with Precious Metal Powder Catalysts: Influence of Modifier on Selectivity and Activity

The development of new improved catalysts for the selective hydrogenation of aromatic nitrogroups is still a field of high interest for the chemical industry. Hydrogenation of aromatic nitrogroups to the corresponding aromatic amines is one of the most important applications for precious metal powder catalysts (PMPC). In this paper various commercial PMPC technologies such as palladium, platinum, platinum modified with copper and platinum modified with vanadium on activated carbon powder supports were compared to each other in regard to activity and selectivity for hydrogenation of 1-chloro-2-nitrobenzene. In this reaction, catalysts comprised of vanadium modified platinum on activated carbon showed excellent activities and selectivities towards 2-chloroaniline. Catalyst performance was affected by the ratio of platinum to vanadium and the properties of the carbon. The role of vanadium as an effective modifier to avoid accumulation of hazardous aromatic hydroxylamines was explained.     

Model-based analysis of the feasibility envelope for autonomous operation of a portable direct methanol fuel-cell system

Portable power systems based on direct methanol fuel cells (DMFC) have to provide power in various environmental conditions: it is advantageous for such a power-supply system to be autonomous, i.e. able to operate without water refills for the methanol solution. It is shown that system autonomy depends mainly on environmental humidity, condenser temperature and air excess ratio: this result is valid in general for any DMFC, as cell parameters have only a marginal role. The environmental conditions in which a portable DMFC system may be autonomous are considered, delineating a feasibility envelope. Two methods are proposed to extend this envelope: operating with a diluted methanol reservoir, which improves the autonomy of the system only marginally and at the cost of a large loss in energy density, and system pressurisation, which delivers a more significant improvement in autonomy properties, but at the cost of system efficiency and simplicity.     

Acetale als neuartige Kraftstoffadditive aus Glycerin und Olefinen

Long chain olefins are converted into aldehydes by hydroformylation using synthesis gas CO/H₂ and further converted in an acid‐catalyzed conversion with glycerol in a one‐pot procedure. Yields are up to 95 %. The obtained mixtures of 5‐ and 6‐membered rings are potential fuel additives offering alternative use of glycerol from renewable resources. By optimization of reaction conditions such as catalyst precursor, ligand, pressure, temperature, solvent or catalyst/substrate ratio a highly selective hydroformylation towards linear acetals was achieved. For synthesis of larger amounts, glycerol was converted with alkenes on a 2‐L‐scale and with aldehydes on a 60‐L‐scale.     

Flame retardancy of glass fiber reinforced high temperature polyamide by use of aluminum diethylphosphinate: thermal and thermo‐oxidative effects

Glass fiber reinforced polyamide (PA) 6 T/DT flame retarded with aluminum diethylphosphinate (AlPi) was tested to assess its flame retardant properties. Models for the decomposition of PA 6T/DT with and without AlPi are presented. Thermal decomposition was measured by performing TGA with Fourier transform infrared (FTIR) spectroscopy and FTIR spectroscopy in the condensed phase. Fire behavior was studied using a cone calorimeter and flammability was tested with UL 94 and the limiting oxygen index. AlPi works as an effective flame retardant for glass fiber reinforced PA 6T/DT materials, acting in the gas phase. Also observed was condensed‐phase action, which occurs especially under oxidative conditions before the samples ignite. © 2013 Society of Chemical Industry     

Hyperlipidemic Conditions Impact Force-Induced Inflammatory Response of Human Periodontal Ligament Fibroblasts Concomitantly Challenged with P. gingivalis-LPS

In obese patients, enhanced serum levels of free fatty acids (FFA), such as palmitate (PA) or oleate (OA), are associated with an increase in systemic inflammatory markers. Bacterial infection during periodontal disease also promotes local and systemic low-grade inflammation. How both conditions concomitantly impact tooth movement is largely unknown. Thus, the aim of this study was to address the changes in cytokine expression and the secretion of human periodontal ligament fibroblasts (HPdLF) due to hyperlipidemic conditions, when additionally stressed by bacterial and mechanical stimuli. To investigate the impact of obesity-related hyperlipidemic FFA levels on HPdLF, cells were treated with 200 µM PA or OA prior to the application of 2 g/cm² compressive force. To further determine the additive impact of bacterial infection, HPdLF were stimulated with lipopolysaccharides (LPS) obtained from Porphyromonas gingivalis. In mechanically compressed HPdLF, PA enhanced COX2 expression and PGE2 secretion. When mechanically stressed HPdLF were additionally stimulated with LPS, the PGE2 and IL6 secretion, as well as monocyte adhesion, were further increased in PA-treated cultures. Our data emphasize that a hyperlipidemic condition enhances the susceptibility of HPdLF to an excessive inflammatory response to compressive forces, when cells are concomitantly exposed to bacterial components.     

Determination of free fatty acids in edible oils by 1H NMR spectroscopy

Here we describe a novel ¹H NMR assay for the determination of FFAs in edible oils. The analytical performance of the NMR assay is similar to that of the commonly used acid value (AV) method. A total of 120 edible oil samples were analysed by both approaches. Except for pumpkin seed oil, showing slight deviations, there was a good compliance between the results obtained from the two methods.     

New prodrugs of the antiprotozoal drug pentamidine

Pentamidine is an effective antimicrobial agent that is approved for the treatment of African trypanosomiasis but suffers from poor oral bioavailability and central nervous system (CNS) penetration. This work deals with the development and systematic characterisation of new prodrugs of pentamidine. For this reason, numerous prodrugs that use different prodrug principles were synthesised and examined in vitro and in vivo. Another objective of the study was the determination of permeability of the different pentamidine prodrugs. While some of the prodrug principles applied in this study are known, such as the conversion of the amidine functions into amidoximes or the O-alkylation of amidoximes with a carboxymethyl residue, others were developed more recently and are described here for the first time. These newly developed methods aim to increase the affinity of the prodrug for the transporters and mediate an active uptake via carrier systems by conjugation of amidoximes with compounds that improve the overall solubility of the prodrug. The different principles chosen resulted in several pentamidine prodrugs with various advantages. The objective of this investigation was the systematic characterisation and evaluation of eight pentamidine prodrugs in order to identify the most appropriate strategy to improve the properties of the parent drug. For this reason, all prodrugs were examined with respect to their solubility, stability, enzymatic activation, distribution, CNS delivery, and oral bioavailability. The results of this work have allowed reliable conclusions to be drawn regarding the best prodrug principle for the antiprotozoal drug pentamidine.     

The introduction of woody debris into a channelized stream: effect on trout populations and habitat

Large woody debris was explored as a method of restructuring channelized streams to improve salmonid habitat. Whole trees were inserted in sections along a 2 km reach of a channelized stream to determine if large woody debris: (1) increased the abundance and biomass of brown (Salmo trutta) and rainbow trout (Oncorhynchus mykiss); (2) had an effect on physical habitat features; and (3) provided trouts with additional habitat. Trout populations and stream morphology were monitored before and after the introduction of woody debris and compared to control sections lacking woody debris. Abundance and biomass of both brown and rainbow trout increased in the treatment section compared to the control. Maximum and standard deviation of fish total length increased in all sections during summer months. The number of individuals and the standard deviations of total lengths decreased in the control section in winter, but increased in the treatment section. Mean water velocities decreased and number and volume of pools increased in treatment sections. Brown and rainbow trouts sought woody debris structures for cover. We conclude that large woody debris can serve as a method of reconstructing channelized streams to improve salmonid habitat. Copyright © 2002 John Wiley & Sons, Ltd.