Unsteady axisymmetric stagnation flow on a circular cylinder

Unsteady, axisymmetric stagnation flow about a circular cylinderis examined when the far-field flow is a periodic function oftime with a fixed time average and an oscillatory part of prescribedamplitude and frequency. Solutions are computed for arbitraryvalues of the Reynolds number, quantifying the effects of surfacecurvature, and a frequency parameter based on the period ofthe far-field flow. It is found that solutions remain regularand periodic provided that the far-field amplitude lies belowa critical value. Above this value, solutions terminate in afinite-time singularity. The blow-up time is delayed by increasingthe curvature of the surface. These results are corroboratedby asymptotic predictions valid in the limits of small and largeamplitude and frequency. For large Reynolds number, the problemreduces to the two-dimensional stagnation-point flow againsta plane wall studied by previous authors.     

Recent progress in insertion and cyclopropanation reactions of metal carbenoids from α-diazocarbonyl compounds

Research on Chemical Intermediates - Metal–carbenoids from α-diazocarbonyl compounds are well-known reactive intermediates with a long history of useful applications in synthetic organic...     

Polyethylene glycol matrix reduces the rates of photochemical and thermal release of nitric oxide from S-nitroso-N-acetylcysteine

S -nitrosothiols have many biological activities and may act as nitric oxide (NO) carriers and donors, prolonging NO half-life in vivo. In spite of their great potential as therapeutic agents, most S -nitrosothiols are too unstable to isolate. We have shown that the S -nitroso adduct of N -acetylcysteine (SNAC) can be synthesized directly in aqueous and polyethylene glycol (PEG) 400 matrix by using a reactive gaseous (NO/O₂) mixture. Spectral monitoring of the S–N bond cleavage showed that SNAC, synthesized by this method, is relatively stable in nonbuf-fered aqueous solution at 25°C in the dark and that its stability is greatly increased in PEG matrix, resulting in a 28-fold decrease in its initial rate of thermal decomposition. Irradiation with UV light (λ= 333 nm) accelerated the rate of decomposition of SNAC to NO in both matrices, indicating that SNAC may find use for the photogeneration of NO. The quantum yield for SNAC decomposition decreased from 0.65 ± 0.15 in aqueous solution to 0.047 ± 0.005 in PEG 400 matrix. This increased stability in PEG matrix was assigned to a cage effect promoted by the PEG microenvironment that increases the rate of geminated radical pair recombination in the homolytic S–N bond cleavage process. This effect allowed for the storage of SNAC in PEG at −20°C in the dark for more than 10 weeks with negligible decomposition. Such stabilization may represent a viable option for the synthesis, storage and handling of S -nitrosothiol solutions for biomedical applications.     

Phytochemical investigations of <Emphasis Type="Italic">Vernonia galamensis</Emphasis> seeds

Vernonia galamensis is a new potential industrial oil seed crop for semiarid areas with very high content of naturally epoxidized vernolic acid (80% of the oil). Chemical investigation of the seeds of Vernonia galamensis afforded two compounds, which are vernolic acid derivatives. Their structures were established by various spectroscopic techniques: IR, UV, NMR, and 2D NMR spectra (COSY, HSQC, and HMBC), and by comparison with literature data for the known compound methylvernolate. The cis-(12S,13R)-(3-methylpentyl) vernolate (1) and the cis-(12S,13R)-(2,3-propanediol) vernolate (2) were isolated and characterized.     

Hydrogen abstraction from H‐donor substrates by the 6‐CF3‐benzotriazol‐N‐oxyl radical (TFNO)

The aminoxyl radical 6‐trifluoromethyl‐benzotriazol‐N‐oxyl (TFNO) has been generated from the parent hydroxylamine 6‐CF₃‐1‐hydroxy‐benzotriazole (TFBT) by one‐electron oxidation with a Ce^IV salt and characterized by spectrophotometry and cyclic voltammetry (CV). Rate constants of H‐abstraction (k_H) by TFNO from a number of H‐donor benzylic substrates have been determined spectrophotometrically in MeCN solution at 25 °C. A radical H‐atom transfer (HAT) route of oxidation is substantiated for TFNO by several pieces of evidence. The kinetic data also testify the relevance of stereoelectronic effects upon the HAT reactivity of TFNO. Copyright © 2010 John Wiley & Sons, Ltd.     

A Modified Random Survival Forests Algorithm for High Dimensional Predictors and Self-Reported Outcomes

We present an ensemble tree-based algorithm for variable selection in high-dimensional datasets, in settings where a time-to-event outcome is observed with error. This work is motivated by self-reported outcomes collected in large-scale epidemiologic studies, such as the Women’s Health Initiative. The proposed methods equally apply to imperfect outcomes that arise in other settings such as data extracted from electronic medical records. To evaluate the performance of our proposed algorithm, we present results from simulation studies, considering both continuous and categorical covariates. We illustrate this approach to discover single nucleotide polymorphisms that are associated with incident Type 2 diabetes in the Women’s Health Initiative. A freely available R package icRSF has been developed to implement the proposed methods. Supplementary material for this article is available online.     

On the computation of material forces in continuum‐atomistic modelling

Material forces govern the behavior and evolution of defects in solids. In elastic materials these forces which are associated with the Eshelby stress tensor are used to describe fracture sensitivities and can be employed to compute the J‐integral [2]. Since crack propagation begins with a variety of fundamental processes which occur within highly localized ultra–fine volume of material that constitute the fracture process zone surrounding a crack tip [3], the question of appropriate growth criteria, i.e. how far and in which direction a crack will glide under a certain loading condition is implied by the material force. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Site-Selective Real-Time Observation of Bimolecular Electron Transfer in a Photocatalytic System Using L-Edge X-Ray Absorption Spectroscopy**

Time-resolved X-ray absorption spectroscopy has been utilized to monitor the bimolecular electron transfer in a photocatalytic water splitting system. This has been possible by uniting the local probe and element specific character of X-ray transitions with insights from high-level ab initio calculations. The specific target has been a heteroleptic [Ir^III(ppy)₂(bpy)]⁺ photosensitizer, in combination with triethylamine as a sacrificial reductant and as a water reduction catalyst. The relevant molecular transitions have been characterized via high-resolution Ir L-edge X-ray absorption spectroscopy on the picosecond time scale and restricted active space self-consistent field calculations. The presented methods and results will enhance our understanding of functionally relevant bimolecular electron transfer reactions and thus will pave the road to rational optimization of photocatalytic performance.     

Tris(2,2′-bipyridyl)ruthenium(II) electrochemiluminescent determination of ethyl formate

Analytical and Bioanalytical Chemistry - Ethyl formate is extensively used as food flavor, fungicide, and larvicide. It naturally exists in coffee, fruits, honey, brandy, and rum as well as dust...