Formation,preservation, and cleavage of the disulfide bond by vanadium

Reaction of the disulfide [HpicanS](2) (HpicanS is the carboxamide based on picolinate (pic) and o-mercaptoaniline (anS); the [] brackets are used to denote disulfides) with [VOCl(2)(thf)(2)] leads to reductive scission of the disulfide bond and formation of the mixed-valence (V(IV)/V(V)) complex anion [(OVpicanS)(2)mu-O](-) (1), with the dianionic ligand coordinating through the pyridine-N atom, the deprotonated amide-N atom, and thiophenolate-S atom. Reductive cleavage of the SbondS bond is also observed as [VCl(2)(tmeda)(2)] (tmeda=tetramethylethylenediamine) is treated with the disulfides [HsalanS](2) or [HvananS](2) (HsalanS and HvananS are the Schiff bases formed between o-mercaptoaniline and salicylaldehyde (Hsal) or vanillin (Hvan), respectively), yielding the V(III) complexes [VCl(tmeda)(salanS)] (2 a), or [VCl(tmeda)(vananS)] (2 b). The disulfide bond remains intact in the aerial reaction between [HsalanS](2) and [VCl(3)(thf)(3)] to yield the V(V) complex [VOCl[salanS](2)] (3), where (salanS)(2-) coordinates through the two phenolate and one of the imine functions. The S-S bond is also preserved as [VO(van)(2)] or [VO(nap)(2)] (Hnap=2-hydroxynaphthalene-1-carbaldehyde) is treated with bis(2-aminophenyl)disulfide, [anS](2), a reaction which is accompanied by condensation of the aldehyde and the diamine, and complexation of the resulting bis(Schiff bases) [HvananS](2) or [HnapanS](2) to form the complexes [VO[vananS](2)] (4 a) or [VO[napanS](2)] (4 b). In 4 a and 4 b, the phenolate and imine functions, and presumably also one of the disulfide-S atoms, coordinate to V(IV). 2-Mercaptophenyl-2'-pyridinecarboxamide (H(2)picanS) retains its identity in the presence of V(III); reaction between [VCl(3)(thf)(3)] and H(2)picanS yields [V[picanS](2)](-) (5). The dithiophenolate 2,6-bis(mercaptophenylthio)dimethylpyridine (6 a) is oxidized, mediated by VO(2+), to the bis(disulfide) octathiadiaza-cyclo-hexaeicosane 6 b. The relevance of these reactions for the speciation of vanadium under physiological conditions is addressed. [HNEt(3)]-1.0.5 NEt(3,) 3.3 CH(2)Cl(2), [HsalanS](2), [HNEt(3)]-5, and 6 b.4 THF have been characterized by X-ray diffraction analysis.     

SPIN LABELED CYSTEINES AS SENSORS FOR PROTEIN-LIPID INTERACTION AND CONFORMATION IN RHODOPSIN

In stoichiometric amounts, the spin label N-tempoyl-(p-chloromercuribenzamide) reacts rapidly with one cysteine residue in membrane-bound bovine rhodopsin. This residue is distinct from the two reactive cysteines previously used as attachment sites for spectroscopic labels, and is on the external surface of the protein near the cytoplasmic membrane/aqueous interface. The spin-labeled side chain has revealed a light-induced conformational change in membrane-bound rhodopsin that is apparently not associated with protein aggregation. The changes are reversible upon the addition of 11-cis retinal, and the magnitude of the change is dependent on the identity of the phospholipid in the surrounding bilayer. Alteration of lipid composition has a much larger effect on bleached rhodopsin than rhodopsin itself, indicating that the former is more readily deformable in response to changes in bilayer properties. This is consistent with the loss of 11-cis retinal binding energy in opsin compared to rhodopsin. These results provide direct structural evidence that the conformation of a membrane protein can be modulated by the lipid properties.     

Evaluation of Nanostructured coating layers formed on Ni balls during mechanical alloying of Cu powder

A novel coating method utilizing mechanical alloying was used to deposit a nickel-copper solid solution on the surface of nickel balls in a planetary ball mill. Mechanically milled copper powders were deposited by cold welding on the activated surface of the nickel balls. The impact of the nickel balls causes surface wear, leading to formation of mixed layered particles of copper-nickel and rewelding. In addition, diffusion takes place through the coating layer to form a Ni-Cu solid solution. The hardness of the coating reached a threefold increase (HV_0.01594) in comparison with the substrate hardness. Microstructural characterization of the coating surface performed using an optical microscope, SEM, and EPMA indicates that, with appropriate processing conditions, a thick, fully dense coating can be metallurgically bonded to the nickel balls. XRD results revealed the presence of a solid solution and nanocrystalline structure.     

The impact of in-line coagulant addition on fouling potential of secondary effluent at a pilot-scale immersed ultrafiltration plant

The impact of in-line coagulation pre-treatment of secondary effluent on the operation of an immersed hollow-fibre ultrafiltration membrane pilot was evaluated as part of a larger study on optimising phosphorus removal. The efficacy of alum and ferric chloride was investigated, with an emphasis on alum use. Both coagulants were found to shift the particle-size distribution of organic matter in the feed towards larger fractions, with a notable reduction in colloidal matter. This was reflected in a reduction of both average daily transmembrane pressure increases, as well as a reduction of transmembrane pressure increases within backpulse intervals. Fouling reduction was observed with both lower and higher membrane packing density modules (membrane surface areas of 55.7 and 62.7 m²/module). The results of one-way analysis of variance (ANOVA) testing indicate that for this pilot system, chemical pre-treatment and solids concentrations in the feed water played a statistically significant role in determining transmembrane pressure variations. Membrane packing density and membrane production method did not exhibit a statistically significant effect on transmembrane pressure under the conditions of this study.     

Functionalization of gold cysteamine self-assembled monolayer with ethylenediaminetetraacetic acid as a novel nanosensor

Electrochemical characterization of gold cysteamine self-assembled monolayer, in situ functionalized with ethylenediaminetetraacetic acid (Au-CA-EDTA SAM), is described by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and Osteryoung square wave voltammetry (OSWV). The results obtained by EIS and CV, in the presence of [Fe(CN)₆]^3−/4− redox probe, show that EDTA is successfully grafted to the surface of Au-CA electrode. Reproducible and reversible variation of the R_ct and ΔEp as a function of solution pH show that Au-CA-EDTA SAM is stable in a wide range of pH and potentials. Accumulation of the Pb²⁺ and Cu²⁺ ions on the Au-CA-EDTA SAM electrode is investigated using faradaic currents or impedimetric effects measured by OSWV and EIS, respectively. These results reveal the presence of active complexing functional groups of EDTA on the surface, and thus, the formation of Au-CA-EDTA SAM electrode. The new sensor responds to the Pb²⁺ and Cu²⁺ separately and simultaneously in a wide linear range of concentrations.     

Sprachverwirrung bei Gefahrgütern. Gefahrgut‐Informations‐ und ‐kommunikationssysteme

In the dangerous goods regulations there is no clear rule for the naming of dangerous goods which are not directly registered in the dangerous goods list. The use of different names for the same substances makes communication about these goods difficult. On the other hand, many chemical names include special characters (e.g. Greek letters, umlauts etc.) which are not easily transferable electronically. This results in a potential for substantial error in the case of an incident with dangerous goods. To solve this problem a database is recommended with uniform names which are easily transferable electronically.     

Mechanical and thermal investigation of thermoplastic nanocomposite films fabricated using micro- and nano-sized fillers from recycled cotton T-shirts

The thermal and mechanical performance of composites with nano-sized cotton fillers embedded in low-density polyethylene (LDPE) is investigated. Microfibrillated cotton was prepared by microgrinding mechanical treatment of pulverized cotton (pCot) derived from waste T-shirts, resulting in nano-sized fibrils of the cellulose that retain high crystallinity. Film composites of LDPE with pCot before and after microgrinding were fabricated through melt extrusion and the effect of filler size on mechanical, thermal and morphological properties of the composite was investigated. Compounding microfibrillated cotton with LDPE resulted in well-dispersed nanocomposites with no discoloration after 10 min of melt extrusion at 170 °C. At concentrations up to 10 % by weight, the composites showed increased modulus, increased tensile strength and a slight decrease in elongation to break. Further improvement in the dispersion and mechanical properties of the cotton-based fillers was realized by the use of LDPE powder instead of polymer pellets fed to the extruder. This research demonstrates the processing and applicability of the use of recycled cotton-based nano-sized fillers in melt-processing.     

Metallic spherical anechoic chamber for antenna pattern measurement

Anechoic chambers are used for indoor antenna measurements. The common method of constructing an anechoic chamber is to cover all inside walls by the electromagnetic absorbers. In this paper, a fully metallic spherical chamber structure is presented in which the propagation of the electromagnetic waves inside the chamber is controlled and they are guided to an absorber. In the proposed method, an appropriate quiet zone is obtained, and unlike ordinary anechoic chambers, the absorber usage amount is reduced greatly. The performance of the chamber is evaluated by simulation. The results show that the proposed method could provide a useful technique for the indoor antenna measurements.