Rate constant for the reaction of OH radicals with CH3C(O)Cl determined by direct kinetic method

Summary The fast flow technique with OH resonance fluorescence detection has been applied at T = 298 ± 2 K to study the kinetics of the overall reaction: H + CH₃C(O)Cl → products (1) A rate constant value of k₁ = (1.02 ± 0.12) x 10¹⁰ cm³ mol^-1 s^-1 has been determined which is the first direct kinetic parameter reported for reaction (1) in the literature (the error given refers to 2σ accuracy).     

Continuous transformation groups and series solution of initial value problems

This paper details an efficient method of deriving séries solutions of initial value problems traditionally encountered in non-linear mechanics. The developed technique, based on the theory of continuous transformation groups, can be used to solve autonomous as well as non-autonomous systems of ordinary differential equations. Solutions to selected problems are presented for illustration. In addition, the notion of invariants of a transformation group provides information on the nature of trajectories of an initial value problem.     

Kinetics and mechanism of the reactions of CH3CO and CH3C(O)CH2 radicals with O2. Low-pressure discharge flow experiments and quantum chemical computations

The reactions CH(3)CO + O(2)--> products (1), CH(3)CO + O(2)--> OH +other products (1b) and CH(3)C(O)CH(2) + O(2)--> products (2) have been studied in isothermal discharge flow reactors with laser induced fluorescence monitoring of OH and CH(3)C(O)CH(2) radicals. The experiments have been performed at overall pressures between 1.33 and 10.91 mbar of helium and 298 +/- 1 K reaction temperature. OH formation has been found to be the dominant reaction channel for CH(3)CO + O(2): the branching ratio, Gamma(1b) = k(1b)/k(1), is close to unity at around 1 mbar, but decreases rapidly with increasing pressure. The rate constant of the overall reaction, k(2), has been found to be pressure dependent: the fall-off behaviour has been analysed in comparison with reported data. Electronic structure calculations have confirmed that at room temperature the reaction of CH(3)C(O)CH(2) with O(2) is essentially a recombination-type process. At high temperatures, the further reactions of the acetonyl-peroxyl adduct may yield OH radicals, but the most probable channel seems to be the O(2)-catalysed keto-enol transformation of acetonyl. Implications of the results for atmospheric modelling studies have been discussed.     

Complexes of ferromagnetic fluids with photoditazin and their promising applications in photodynamic therapy

Nanosized complexes of ferroparticles with a sensitizer photoditazin (used in photodynamic therapy in oncology) have been synthesized and studied by small-angle neutron scattering. The structure of the complexes was determined, and the influence of the biocompatible polymer pluronic investigated. Clinical tests revealed increased efficiency of the complexes compared with the starting photoditazin. The complexes can be used as the first magnetically operated sensitizer for treatment of oncological diseases by photodynamic therapy.     

Investigation of the Reaction of Gold(III) with 2‐[2‐(4‐Dimethylamino‐Phenyl)‐Vinyl]‐1,3,3‐Trimethyl‐3H‐Indolium. Application for Determination of Gold

A new, simple, rapid, sensitive, efficient and low‐cost spectrophotometric procedure for the determination of gold was developed. The method is based on the reaction of [AuCl₄]^? with 2‐[2‐(4‐dimethylaminophenyl)‐vinyl]‐1,3,3‐trimethyl‐3H‐indolium reagent to form a colored ion associate extractable by various organic solvents. The molar absorptivity of the ion associates is in the range (5.7–9.2) × 10⁴ L mol^?1 cm^?1 depending on the extractant. Butyl acetate was chosen as the extractant. The optimum reaction conditions were established: pH 2–4, concentration of the dye reagent (0.8–1.5) × 10^?4 mol L^?1. The determination of gold is not hindered even by a 1000‐fold concentration of Ni and Co; a 500‐fold concentration of Pb and Zn; a 100‐fold concentration of Bi, Cu, Cd, Pt, Rh and Ru; or a 20‐fold concentration of Ag. The established method was applied to the determination of gold in model samples and enriched polymetallic ores.     

On the impact of anisotropic mesh adaptation on computational wind engineering

This paper addresses the critical issue of the accuracy of CFD predictions for wind engineering. Flows around the Silsoe Cube, a high‐rise building (the Jin Mao Tower), and a low‐rise large‐span building (the Pudong International Airport) are computed with the Navier–Stokes solver FENSAP and compared with measurements. Computations are carried out for two wind directions, by solving the steady‐state ensemble‐averaged Navier–Stokes equations with the Spalart–Allmaras one‐equation turbulence model. Pressure coefficients compare well with wind tunnel experiments and the accuracy of the flow solutions is further improved via an automatic mesh adaptation that dynamically places grid points where the flow physics require them, while keeping the number of unknowns and solution time substantially at the same level. Copyright © 2009 John Wiley & Sons, Ltd.     

Structure of the water salt solutions of DNA with sulfonated scandium diphthalocyanine

Interaction of sulfonated scandium diphthalocyanine ScPc₂(SO₃)₄(NH₄)₄ with DNA in water salt solutions was studied by small-angle neutron scattering, dynamic light scattering, and atomic force microscopy. The results provide evidence about packaging of DNA molecules and agree with previous viscosimetry and spectrophotometry data.     

Application of Inductively Coupled Plasma Spectrometric Techniques and Multivariate Statistical Analysis in the Hydrogeochemical Profiling of Caves—Case Study Cloșani,Romania

The aim of the study was to develop the hydrogeochemical profiling of caves based on the elemental composition of water and silty soil samples and a multivariate statistical analysis. Major and trace elements, including rare earths, were determined in the water and soil samples. The general characteristics of water, anions content, inorganic and organic carbon fractions and nitrogen species (NO₃⁻ and NH₄⁺) were also considered. The ANOVA—principal component analysis (PCA) and two-way joining analysis were applied on samples collected from Cloșani Cave, Romania. The ANOVA-PCA revealed that the hydrogeochemical characteristics of Ca²⁺-HCO₃⁻ water facies were described by five factors, the strongest being associated with water-carbonate rock interactions and the occurrence of Ca, Mg and HCO₃⁻ (43.4%). Although organic carbon fractions have a lower influence (20.1%) than inorganic ones on water characteristics, they are involved in the chemical processes of nitrogen and of the elements involved in redox processes (Fe, Mn, Cr and Sn). The seasonal variability of water characteristics, especially during the spring, was observed. The variability of silty soil samples was described by four principal components, the strongest influence being attributed to rare earth elements (52.2%). The ANOVA-PCA provided deeper information compared to Gibbs and Piper diagrams and the correlation analysis.     

Factors Influencing Prospective Teachers’ Recommendations to Students: Horizons,Hexagons, and Heed

This article examines pre-service secondary school teachers’ responses to a learning situation that presented a student's struggle with determining the area of an irregular hexagon. Responses were analyzed in terms of participants’ evoked concept images as related to their knowledge at the mathematical horizon, with attention paid toward the influence of one on the other. Specifically, our analysis attends to common features in participants’ understanding of the mathematical task, and explores the interplay between participants’ personal solving strategies and approaches and their identified preferences when advising a student. We conclude with implications for mathematics teacher education research and pedagogy.     

N-Glycosylation Profiling of Human Blood in Type 2 Diabetes by Capillary Electrophoresis: A Preliminary Study

Currently, diagnosing type 2 diabetes (T2D) is a great challenge. Thus, there is a need to find rapid, simple, and reliable analytical methods that can detect the disease at an early stage. The aim of this work was to shed light on the importance of sample collection options, sample preparation conditions, and the applied capillary electrophoresis bioanalytical technique, for a high-resolution determination of the N-glycan profile in human blood samples of patients with type 2 diabetes (T2D). To achieve the profile information of these complex oligosaccharides, linked by asparagine to hIgG in the blood, the glycoproteins of the samples needed to be cleaved, labelled, and purified with sufficient yield and selectivity. The resulting samples were analyzed by capillary electrophoresis, with laser-induced fluorescence detection. After separation parameter optimization, the capillary electrophoresis technique was implemented for efficient N-glycan profiling of whole blood samples from the diabetic patients. Our results revealed that there were subtle differences between the N-glycan profiles of the diabetic and control samples; in particular, two N-glycan structures were identified as potential glycobiomarkers that could reveal significant changes between the untreated/treated type 2 diabetic and control samples. By analyzing the resulting oligosaccharide profiles, clinically relevant information was obtained, revealing the differences between the untreated and HMG-CoA reductase-inhibitor-treated diabetic patients on changes in the N-glycan profile in the blood. In addition, the information from specific IgG N-glycosylation profiles in T2D could shed light on underlying inflammatory pathophysiological processes and lead to drug targets.