A new dimension in cyclic coinage metal pyrazolates: decoration with a second ring of coinage metals supported by inter-ring metallophilic interactions

When pyrazolate ligands with thioether chelate arms are used in cyclic coinage metal pyrazolates [Au(μ-pz)](n), the inner gold ring can be framed with an outer silver ring to give novel heterometallic double-crowned complexes [AuAg(μ-L(x))(BF(4))](4). They feature short intramolecular in-plane Ag-Au interactions, are stable as octanuclear species in solution, and show promising luminescence properties.     

Nuclear inelastic scattering and Mössbauer spectroscopy as local probes for ligand binding modes and electronic properties in proteins: vibrational behavior of a ferriheme center inside a β-barrel protein

In this work, we present a study of the influence of the protein matrix on its ability to tune the binding of small ligands such as NO, cyanide (CN(-)), and histamine to the ferric heme iron center in the NO-storage and -transport protein Nitrophorin 2 (NP2) from the salivary glands of the blood-sucking insect Rhodnius prolixus. Conventional M?ssbauer spectroscopy shows a diamagnetic ground state of the NP2-NO complex and Type I and II electronic ground states of the NP2-CN(-) and NP2-histamine complex, respectively. The change in the vibrational signature of the protein upon ligand binding has been monitored by Nuclear Inelastic Scattering (NIS), also called Nuclear Resonant Vibrational Spectroscopy (NRVS). The NIS data thus obtained have also been calculated by quantum mechanical (QM) density functional theory (DFT) coupled with molecular mechanics (MM) methods. The calculations presented here show that the heme ruffling in NP2 is a consequence of the interaction with the protein matrix. Structure optimizations of the heme and its ligands with DFT retain the characteristic saddling and ruffling only if the protein matrix is taken into account. Furthermore, simulations of the NIS data by QM/MM calculations suggest that the pH dependence of the binding of NO, but not of CN(-) and histamine, might be a consequence of the protonation state of the heme carboxyls.     

Asymmetric bioreduction of activated carbon–carbon double bonds using Shewanella yellow enzyme (SYE-4) as novel enoate reductase

Shewanella yellow enzyme (SYE-4), a novel recombinant enoate reductase, was screened against a variety of different substrates bearing an activated double bond, such as unsaturated cyclic ketones, diesters, and substituted imides. Dimethyl- and ethyl esters of 2-methylmaleic acid were selectively reduced to (R)-configured succinic acid derivatives and various N-substituted maleimides furnished the desired (R)-products in up to >99% enantiomeric excess. Naturally occurring (+)-carvone was selectively reduced to (?)-cis-dihydrocarvone and (?)-carvone was converted to the diastereomeric product, respectively. Overall SYE-4 proved to be a useful biocatalyst for the selective reduction of activated CC double bonds and complements the pool of synthetic valuable enoate reductases.     

The quest for ozone intensities in the 9–11 μm region: A retrospective

We review efforts to experimentally determine absolute line intensities for ozone transitions in the 9–11 μm spectral region over the last several decades. Much of this work has been driven by the requirements for remote sensing of terrestrial atmospheric ozone. While significant progress has been achieved, discrepancies persist among various infrared measurements, and the relation between infrared and ultraviolet standards is not clearly resolved.     

Atmospheric pressure plasma induced grafting of poly(ethylene glycol) onto silicone elastomers for controlling biological response

This study investigates the role that surface functionalisation of silicone elastomer (SE) by atmospheric pressure plasma induced graft immobilisation of poly(ethylene glycol) methyl ether methacrylate (PEGMA) plays in the attendant biological response. SE is used in modern ophthalmic medical devices and samples of the material were initially plasma treated using a dielectric barrier discharge reactor (DBD) to introduce reactive oxygen functionalities, prior to in situ grafting of two molecular weights of PEGMA (MW 1000 Da: PEGMA(1000), MW 2000 Da: PEGMA(2000)). The variously processed surfaces were characterised by water contact angle analysis, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry and atomic force microscopy. Lens epithelial cells were then cultured on the PEGMA grafted SE surfaces. It was found that cells on the pristine surface were not well spread and had shrunken morphology. On the DBD pre-treated surfaces, the cells were well spread. On the PEGMA(1000) surface, the cells displayed evidence of shrinkage and were on the verge of detaching. Remarkably, on the PEGMA(2000) surface, no cell adhesion was detection. Bacterial adhesion to the surfaces was studied using Staphylococcus aureus NTC8325. There was no difference in the number of bacteria adhering to any of the surfaces studied.     

Enhanced rigidity of recycled polypropylene from packaging waste by compounding with talc and high‐ crystallinity polypropylene

Polypropylene (PP) constituted 30% of the collected material in a Swedish collection system for rigid plastic packaging waste. The PP fraction was however a complex mixture of grades with widely different properties. In order to enhance the rigidity of the recycled PP, modified grades were prepared by compounding with talc and/or a virgin high‐crystallinity PP grade. Adding 20–40% of high‐crystallinity PP enhanced the stiffness and yield strength without impairing the impact resistance. A composite material consisting of 20% of this grade, 20% talc and 60% recycled PP gave mechanical properties similar to those of a commercial talc‐filled PP compound used for demanding engineering applications. The present study demonstrates that recycled PP derived from post‐consumer packaging waste can also be made useful for demanding engineering applications. Copyright © 2001 John Wiley & Sons, Ltd.     

Assay of Kanamycin A by HPLC with Direct UV Detection

The development of a simple reversed phase ion pair liquid chromatographic method for the assay of kanamycin A has been described. Because of the lack of a UV chromophore in the structure of kanamycin A, borate complexation was used to allow direct UV detection at 205 nm. Three columns were evaluated in this study: Zorbax Extend C18 (4.6 mm × 250 mm; 5 μm), XBridge C18 (4.6 mm × 250 mm; 5 μm) and apHera C18 (4.6 mm × 250 mm; 5 μm). The mobile phase was a mixture of 0.1 M disodium tetraborate (pH 9.0) and water (20:80, v/v) supplemented with 0.5 g L^?1 sodium octanesulphonate. Final chromatographic conditions were achieved on the XBridge column at 50 °C. The method was validated according to ICH guidelines and applied to a commercially available sample. It is much faster and more specific than the current microbiological assay prescribed in the European Pharmacopoeia. No expensive equipment is necessary to perform this assay making it a viable replacement.