Chemoenzymatic Asymmetric Synthesis of Pyridine-Based α-Fluorinated Secondary Alcohols

Fluoro-substituted and heteroaromatic compounds are valuable intermediates for a variety of applications in pharma- and agrochemistry and synthetic chemistry. This study investigates the chemoenzymatic preparation of chiral alcohols bearing a heteroaromatic ring with an increasing degree of fluorination in α-position. Starting from readily available picoline derivatives prochiral α-halogenated acyl moieties were introduced with excellent selectivity and 64–95 % yield. The formed carbonyl group was subsequently reduced to the corresponding alcohols using the alcohol dehydrogenase from Lactobacillus kefir, yielding an enantiomeric excess of 95–>99 % and up to 98 % yield.     

A magnetic resonance imaging study of planum temporale asymmetry in men with developmental dyslexia

The influence of ionic strength and composition on the binding and inhibition of human leukocyte elastase by glycosaminoglycans with variable degree and position of sulfation was investigated. The kinetic mechanism of inhibition had a hyperbolic, mixed-type character with a competitive component that was promoted by low ionic strength, reduced by phosphate ions, and which also depended on the substrate and glycosaminoglycan structure. Enzyme binding was a cooperative phenomenon that varied with ionic strength and composition. The inhibition patterns correlated with the cationic character of elastase and with the distribution of arginines on its molecular surface, most notably with residues located in the vicinity of the substrate binding region. The order of affinity for elastase binding was chondroitin 4-sulfate < chondroitin 6-sulfate < dermatan sulfate, iduronate-containing derivatives being superior with respect to the glucuronate-containing counterparts. Additional sulfation at both the 4- and 6- positions or at the N- and 4-positions of the N-acetylgalactosamine moiety decidedly improved the inhibitory efficiency. The results highlight a fundamental physiological role of enzyme-glycosaminoglycan interactions. In the azurophil granule of the human polymorphonuclear neutrophil, elastase and other enzymes are bound to a matrix of chondroitin 4-sulfate because this is the only glycosaminoglycan that simultaneously offers good binding for enzyme compartmentalization together with prompt release from the bound state at the onset of phagocytosis.     

Effects of alloy additions on the microstructures and tensile properties of cast Co-Cr-Mo alloy used for surgical implants

The composition of the Co-Cr-Mo alloy has been modified by additions of nickel and some trace elements aluminium, titanium and boron. In this paper, the first part of the present study, the effects of alloy additions on the microstructures and tensile properties of the as-cast Co-Cr-Mo alloy are discussed. The effects of alloy additions on the fatigue behaviour of the alloy will be discussed in the second part of the present study. It is found that alloy additions do not seem to result in changes in the nature of the casting structure. A directional, coarse dendritic cast structure is produced in the modified alloys as in the base alloY. However, the alloy additions affect the carbide precipitations and the formation of some fine details of the microstructure such as dislocations, stacking faults and twins produced during the solidification. A considerable improvement in the transient mechanical properties, especially in the tensile ductility, is achieved by modifying the base alloy with alloy additions.     

Higher Order Barycentric Coordinates

In recent years, a wide range of generalized barycentric coordinates has been suggested. However, all of them lack control over derivatives. We show how the notion of barycentric coordinates can be extended to specify derivatives at control points. This is also known as Hermite interpolation. We introduce a method to modify existing barycentric coordinates to higher order barycentric coordinates and demonstrate, using higher order mean value coordinates, that our method, although conceptually simple and easy to implement, can be used to give easy and intuitive control at interactive frame rates over local space deformations such as rotations.     

Nitric oxide reduction at noble metal electrodes: a voltammetric study in acid solution

Features of the electrochemical reduction of nitric oxide on platinum, palladium, rhodium and ruthenium in aqueous perchloric acid solutions (0.33–1.0 M) are compared. The results from voltammetric studies (ie linear potential sweep and rotating disc electrode) using the bulk metal electrodes are described and compared with residual current voltage plots in acid electrolyte alone. In general, three nitric oxide reduction peaks are observed on the metals. The most anodic peak, at ca E = 0.15 V vs sce is attributed to the one-electron reduction of nitric oxide to an adsorbed NOH intermediate on a bare metal surface (ie one free of oxides or adsorbed hydrogen). The other two peaks occur in potential regions where adsorbed hydrogen is present on the metal surface (ca E = 0.0 and −0.20 V, respectively). The co-adsorbed hydrogen complicates the analysis and precludes an unambiguous interpretation of these two peaks. However, they apparently reflect nitric oxide reduction to nitrogen, hydroxylamine and/or ammonia. In a cathodic scan on the rhodium electrode, a current plateau is seen instead of the first (most anodic) peak, a probable consequence of oxide film formation with subsequent chemical complications. On the ruthenium electrode the first two (most anodic) peaks are not observed probably due to a relatively stable oxide layer. Reaction selectivities at metal black gas diffusion cathodes operating in an electrogenerative (ie galvanic) mode with perchloric acid electrolyte are compared with the voltammetric results at the corresponding bulk electrodes. Dinitrogen formation is observed on the platinum and rhodium black electrodes as suggested from voltammetric results. A series-parallel reaction sequence is proposed to explain the results. Limitations of using simple voltammetric techniques for predicting behavior of large scale preparative electrochemical reactors are discussed.