Simplifying the reaction system for the preparation of polyaniline nanofibers: Re-examination of template-free oxidative chemical polymerization of aniline in conventional low-pH acidic aqueous media

In this study, several polyaniline samples were prepared by oxidative chemical polymerization using only aniline, (NH₄)₂S₂O₈ and HCl in aqueous media at room temperature for morphological studies by SEM (scanning electron microscopy). The results show that polyaniline nanofibers can be obtained by template-free oxidative chemical polymerization in a conventional low-pH acidic aqueous medium (pH ～ 0) at room temperature. The study indicates that it is crucial to employ a mild post-polymerization processing procedure, such as dialysis, to preserve the as-formed morphology of polyaniline nanofibers. Our study also suggests that polyaniline could adopt the nanofiber structure as its intrinsic morphology when it is synthesized in a simple oxidative chemical polymerization system consisting of only aniline, (NH₄)₂S₂O₈ and HCl in an aqueous medium at room temperature.     

Trace elements in home-produced eggs in Belgium: Levels and spatiotemporal distribution

The purpose of this study was to evaluate the levels of arsenic, cadmium, lead, copper and zinc in home-produced eggs, soils and kitchen waste samples of private chicken owners in Belgium, and to determine spatiotemporal differences in trace element contents in eggs. Eggs were sampled in all provinces of Belgium in autumn 2006 and spring 2007. A total number of 59 private chicken owners participated in the study. Trace elements were determined by inductively coupled plasma-mass spectrometry except for mercury, which was determined by atomic absorption of mercury vapour. The mean fresh weight concentrations in eggs in autumn and spring respectively were < 8.0 and < 8.0 µg/kg for arsenic, 0.5 and < 0.5 µg/kg for cadmium, 116 and 74 µg/kg for lead, 0.43 and 0.52 mg/kg for copper, 20.3 and 19.2 mg/kg for zinc, and 3.15 and 4.44 µg/kg for mercury. Analysis of variance determined significant differences in some trace element concentrations in eggs among seasons and regions in Belgium. Average concentrations of arsenic, cadmium and mercury corresponded well with values measured in other countries, while copper and zinc concentrations were within the same order of magnitude as in other countries. Average lead concentrations were high compared to concentrations in eggs from other countries and correlated well with lead concentrations in soil, indicating that the soil is an important source. Other sources of trace elements in eggs might be home-grown vegetables and forage (grass and herbs), and indirectly, air pollution.     

Adapting rain data for hygrothermal models

Design for moisture control has now become an established part of building envelope design. Hygrothermal modeling tools, capable of simulating moisture transfer in materials, are a key element of the design process. There are three principle methods of moisture transfer in envelopes. They are, in order of magnitude, capillary action, vapour convection, and vapour diffusion. Wind-driven rain has the potential to deposit large amounts of liquid water on the exterior surface, as well inside walls through rain penetration, providing a significant source for moisture transport. Most hygrothermal models are capable of handling wind-driven rain impinging on or penetrating the surface of the envelope. Correct results presuppose the availability of reliable rain intensity data. Many data sets, however, do not record hourly rain intensities but qualitative intensities such as light, moderate, or heavy. This paper examines several methods for assigning quantitative values to weather observations available in Canada. Real data, such as data from rain gauges, is preferable although the latter have shortcomings. Differences in catch can be up to 50% depending on gauge type, size, and exposure. When only rain codes are available the values recommended by the local meteorological service can provide adequate estimates. In case where there is observer bias a better estimate can be obtained by adjusting the value for light rainfall. If very little information is available stochastic modeling of rainfall is possible though the accuracy, especially for individual months is low.     

Efficient Synthesis of Highly Active Phospha‐Isosteres of the Influenza Neuraminidase Inhibitor Oseltamivir

With a Hunsdiecker–Barton iododecarboxylation strategy, we converted the carboxylate group of the oseltamivir precursor into exemplary phosphonate monoesters. In all cases, K_i values towards influenza virus sialidase remained in the sub‐nanomolar range. We have thus made valuable structural space available for the design of novel oseltamivir‐based tools for influenza virus research.

     

Synthesis and Evaluation of 1‐(1‐(Benzo[b]thiophen‐2‐yl)cyclohexyl)piperidine (BTCP) Analogues as Inhibitors of Trypanothione Reductase

Thirty two analogues of phencyclidine were synthesised and tested as inhibitors of trypanothione reductase (TryR), a potential drug target in trypanosome and leishmania parasites. The lead compound BTCP ( 1 , 1‐(1‐benzo[b]thiophen‐2‐yl‐cyclohexyl) piperidine) was found to be a competitive inhibitor of the enzyme (K_i=1 μM ) and biologically active against bloodstream T. brucei (EC₅₀=10 μM ), but with poor selectivity against mammalian MRC5 cells (EC₅₀=29 μM ). Analogues with improved enzymatic and biological activity were obtained. The structure–activity relationships of this novel series are discussed.     

Improved Tricyclic Inhibitors of Trypanothione Reductase by Screening and Chemical Synthesis

Trypanothione reductase (TryR) is a key validated enzyme in the trypanothione‐based redox metabolism of pathogenic trypanosomes and leishmania parasites. This system is absent in humans, being replaced with glutathione and glutathione reductase, and as such offers a target for selective inhibition. As part of a program to discover antiparasitic drugs, the LOPAC1280 library of 1266 compounds was screened against TryR and the top hits evaluated against glutathione reductase and T. brucei parasites. The top hits included a number of known tricyclic neuroleptic drugs along with other new scaffolds for TryR. Three novel druglike hits were identified and SAR studies on one of these using information from the tricyclic neuroleptic agents led to the discovery of a competitive inhibitor (K_i=330 nM ) with an improved potency against T. brucei (EC₅₀=775 nM ).     

绿色基础设施在气候变化中的作用

气候变化正挑战着我们现在的城市建设方式以及规划和管理城市绿色空间的方式.在英格兰,大多数人生活在城镇,这些地区拥有大量的绿色空间.如果要保持我们城镇的蓬勃生机,城镇建设必须适应气候变化,而且应有助于减缓气候变化.这绝不是简单的设计和维护那些可适应变化的气候的公共绿地和绿色空间,而是改变城市区域的绿色基础设施,使绿色空间在保护整个城市区域免受气候变化危害的过程中扮演一个重要的新角色.     

Catalytic conversion of cellulose into ethylene glycol over supported carbide catalysts

In the current paper we present a combined catalytic and surface science studies to evaluate the utilization of carbide catalysts for the conversion of cellulose to polyols, especially to ethylene glycol (EG). Based on catalytic studies over a W₂C catalyst, the EG yield has been optimized by varying H₂ pressure, reaction temperature and time. The catalytic performance has been compared for several types of supported catalysts, including tungsten carbides, molybdenum carbides and platinum on different supports. Among all the catalysts, tungsten carbide supported on activated carbon, W₂C/AC, shows the highest EG yield, which is further enhanced to 61% with the promotion of Ni. The corresponding surface science studies indicate that the enhanced EG yield is at least partially due to a weaker bonding between EG and Ni-promoted tungsten carbide surface.     

Probing protein ligand interactions by automated hydrogen/deuterium exchange mass spectrometry

Amide hydrogen/deuterium exchange is a powerful biophysical technique for probing changes in protein dynamics induced by ligand interaction. The inherent low throughput of the technology has limited its impact on drug screening and lead optimization. Automation increases the throughput of H/D exchange to make it compatible with drug discovery efforts. Here we describe the first fully automated H/D exchange system that provides highly reproducible H/D exchange kinetics from 130 ms to 24 h. Throughput is maximized by parallel sample processing, and the system can run H/D exchange assays in triplicate without user intervention. We demonstrate the utility of this system to differentiate structural perturbations in the ligand-binding domain (LBD) of the nuclear receptor PPARgamma induced upon binding a full agonist and a partial agonist. PPARgamma is the target of glitazones, drugs used for treatment of insulin resistance associated with type II diabetes. Recently it has been shown that partial agonists of PPARgamma have insulin sensitization properties while lacking several adverse effects associated with full agonist drugs. To further examine the mechanism of partial agonist activation of PPARgamma, we extended our studies to the analysis of ligand interactions with the heterodimeric complex of PPARgamma/RXRalpha LBDs. To facilitate analysis of H/D exchange of large protein complexes, we performed the experiment with a 14.5-T Fourier transform ion cyclotron resonance mass spectrometer capable of measuring mass with accuracy in the ppb range.     

Biodegradation of synthetic base fluid surrogates in Gulf of Mexico sediments under simulated deep-sea conditions

In this study, an anaerobic marine biodegradability test was adapted to study the fate of synthetic base fluid (SBF) surrogates, ethyl oleate and tetradecene, by deep-sea microorganisms. Sediment samples from hundreds of meters deep in the Gulf of Mexico were incubated at low temperatures (4 degrees C) and high hydrostatic pressure in steel vessels. Stimulation of indigenous microbial communities to SBF biodegradation was evident in the fact that the rate of removal of ethyl oleate was greater in sediments that had some previous exposure to SBF (first-order decay coefficient kof -0.22 +/- 0.02 week(-1)) compared to unexposed control sediments (first-order decay coefficient k of -0.11 +/- 0.02 week(-1)). When sulfate-linked tetradecene degradation occurred within the test period, the activity could also be modeled as a first-order decay following an initial lag phase, with an average decay coefficient of k = -0.05 +/- 0.01 week(-1). This study also revealed that the degradation of SBF surrogates by microorganisms collected from deep-sea sediments was not significantly effected by the hydrostatic incubation pressure.