A new mechanism of acyl group transfer in the reaction catalyzed by D-glyceraldehyde-3-phosphate dehydrogenase

D-Glyceraldehyde-3-phosphate dehydrogenase (GAPDH, EC 1.2.1.12) catalyzes the oxidative phosphorylation of its substrate in a two-step reaction. Asa result of the first, oxidativestep, the covalent intermediate where in 3-phosphoglyceroyl moiety is bound to Cys149 of the active center is subjected to nucleophilic attack by inorganic phosphate, but remains resistant to hydrolytic decomposition. This ensures tight coupling of oxidation with phosphorylation in glycolysis. In this article, we present the experimental evidence for the conversion of GAPDH into a form capable of performing the reaction in the absence of inorganic phosphate. The structural basis for this conversion is the oxidation of a cysteine residue (probably Cys 153) into a sulfenic acid derivative under mild conditions to affect the integrity of the essential Cys 149. As a result, an intram olecular transfer of 3-phosphoglyceroyl group from the active center Cys 149 to Cys 153 becomes possible with subsequent hydrolysis of the sulfenyl carboxylate intermediate.     

Oxidative and photooxidative degradation of poly(acrylic acid)

The oxidative degradation of poly(acrylic acid) (PAA), a water soluble polymer, was studied at various temperatures with different concentrations of persulfates, potassium persulfate (KPS), ammonium persulfate (APS) and sodium persulfate (SPS). The photodegradation of PAA was also examined with APS as oxidizer. The degraded samples were analyzed for the time evolution of molecular weight distribution by gel permeation chromatography. A theoretical model based on the continuous distribution kinetics was developed that accounted for the polymer degradation and the dissociation of persulfate. The rate coefficients for the oxidative and photooxidative degradation of PAA were determined from the parametric fit of the model with experimental data. The rate of degradation increased with increasing amount of persulfate in both oxidative and photooxidative degradation. The rate of degradation also increased with increasing temperature in the case of oxidative degradation.     

Heterogeneous catalysis by new bead‐shaped polymer‐supported multisite phase transfer catalysts

Three different new insoluble bead‐shaped polymer‐supported multisite phase transfer catalysts containing two, four and six active sites have been prepared and characterized by FTIR, TGA, [chloride ion] and SEM analyses. The presence of number of active sites in each catalyst and their corresponding catalytic ability were studied by determining pseudo‐first order rate constants for C‐alkylation of phenylacetonitrile (PAN) and four different substituted PAN as the substrate using a low concentration of NaOH (25% w/w) at 50 °C. The observed rate constants were compared with rate constants of same reactions catalyzed by single‐site catalyst under identical reaction conditions. From comparative study, the efficiency of catalysts were found to be in the order six‐site>four‐site>two‐site>single‐site thus confirming number of active sites in each catalyst. Further, the detailed kinetic profile of C‐alkylation of PAN has been investigated using the superior six‐site catalyst by varying stirring speed, [substrate], [catalyst], [NaOH], and temperature. Based on the observed kinetic and activation parameters, an interfacial mechanism was proposed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 771–785, 2009     

Controlled Synthesis of CdClOH Sub-nanocones by Low-temperature Solution Process and Their Transformation into CdS Hollow Sub-nanocones

Novel CdClOH sub‐nanocone crystals were successfully synthesized on a large scale by a facile solution‐based method using polymers as crystal growth modifiers. The crystals showed cone‐like morphology. Some factors affecting the morphology and size of the product, such as reaction temperature, concentrations of polyacrylamide (PAM), and pH value of the solution, were systematically studied. Experiments implied that polymer PAM played a key role in the formation of CdClOH sub‐nanocones. A possible formation mechanism of CdClOH sub‐nanocones was suggested based on nucleation‐etching process‐recrystallization in a mild aqueous solution. Furthermore, the as‐prepared CdClOH sub‐nanocones could be further transformed into CdS hollow sub‐nanocones by an anion‐exchange reaction.     

Plasma-induced Degradation of Chlorobenzene in Aqueous Solution

Liquid-phase degradation of chlorobenzene (CB), induced by contact glow discharge electrolysis under various reaction conditions, such as, the initial solution pH, current intensity, volume of solution and iron salts was investigated. Experimental results indicated that, in the absence of catalysts, the depletion of CB followed first-order kinetics, where the observed value of the first-order rate constant ‘k’ is directly proportional to the applied current intensity and inversely proportional to the solution volume. Initial solution pH had little effect on the value of k. HPLC and IC analyses showed that the major intermediate products were chlorophenols, phenol, organic acids and chloride ions. During the treatment, a lot of hydrogen peroxide was formed. Role of Fenton’s reaction was examined. A reaction pathway is proposed based on the degradation kinetics and the distribution of intermediate products.     

Substituent Effects on Phosphate-Catalyzed Proton Exchange in Amides

The kinetics of phosphate-catalyzed proton exchange have been measured with NMR lineshape analysis for a series of amides, ureas, and carbamates. A hypothetical energy profile for transition structures of concerted phosphate catalysis ?_c and of stepwise phosphate catalysis ?₁, ?₂ is used for discussion of the substituent effects. The concerted mechanism of phosphate catalysis operates only for amides RCONHCH₃ for which the electron-donating ability of the substituent R is comparable with, or better than, that of the methyl group. We conclude that concerted phosphate catalysis is inoperative in proteins or polypeptides.     

Emitting layer analysis of blue thermally activated delayed fluorescence devices using capacitance–voltage method

In this paper, blue thermally activated delayed fluorescence (TADF) organic light-emitting diodes (OLEDs) have been elucidated, with a focus on the degradation characteristics of the emission layer (EML). The operational stability against electrical stress was investigated for two host materials and four doping concentrations, which were used as the EML. The operating stability of the devices was confirmed by comparing the peak capacitance before and after degradation. Devices using bis [2-(diphenyl-phosphino) phenyl] ether oxide (DPEPO) as a host exhibited poor degradation characteristics. However, high stability was confirmed when 3,3-di (9H-carba-zol-9-yl)-biphenyl (mCBP) was used. DPEPO host devices are most resistant against performance degradation when they are doped with 10 wt% 10,10'-(4,4′-sulfonylbis(4,1-phenylene))bis(9,9-dimethyl-9,10-dihydroacridine (DMAC-DPS). We successfully determined the electroluminescence characteristics of the device depending on the host material, as well as the doping concentration, using the capacitance–voltage method.     

Numerical simulation and experimental validation of multiphysics field coupling mechanisms for a high power ICP wind tunnel

We take the established inductively coupled plasma(ICP) wind tunnel as a research object to investigate the thermal protection system of re-entry vehicles. A 1.2-MW high power ICP wind tunnel is studied through numerical simulation and experimental validation. The distribution characteristics and interaction mechanism of the flow field and electromagnetic field of the ICP wind tunnel are investigated using the multi-field coupling method of flow, electromagnetic, chemical, and thermodynamic field. The accuracy of the numerical simulation is validated by comparing the experimental results with the simulation results. Thereafter, the wind tunnel pressure, air velocity, electron density, Joule heating rate, Lorentz force, and electric field intensity obtained using the simulation are analyzed and discussed. The results indicate that for the 1.2-MW ICP wind tunnel, the maximum values of temperature, pressure, electron number density, and other parameters are observed during coil heating. The influence of the radial Lorentz force on the momentum transfer is stronger than that of the axial Lorentz force. The electron number density at the central axis and the amplitude and position of the Joule heating rate are affected by the radial Lorentz force. Moreover, the plasma in the wind tunnel is constantly in the subsonic flow state, and a strong eddy flow is easily generated at the inlet of the wind tunnel.     

Insight into the chemomechanical coupling mechanism of kinesin molecular motors

Kinesin is a two-headed biological molecular motor that can walk processively on microtubule via consumption of ATP molecules. The central issue for the molecular motor is how the chemical energy released from ATP hydrolysis is converted to the kinetic energy of the mechanical motion, namely the mechanism of chemomechanical coupling. To address the issue, diverse experimental methods have been employed and a lot of models have been proposed. This review focuses on the proposed models as well as the qualitative and quantitative comparisons between the results derived from the models and those from the structural, biochemical and single-molecule experimental studies.     

大气压非平衡等离子体甲烷干法重整零维数值模拟

大气压非平衡等离子体由于其独特的非平衡特性,可为甲烷和二氧化碳稳定温室气体分子活化和重整提供非热平衡和活化环境.本文采用了零维等离子体化学反应动力学模型,考虑了详细的CH₄/CO₂等离子体化学反应集,重点研究了反应气体CH₄/CO₂摩尔分数(5%—95%)对大气压非平衡等离子体甲烷干法重整制合成气和重要含氧化合物的影响.首先,给出了进料气体不同体积比时电子密度和温度随时间的演化规律,结果表明初始甲烷摩尔分数的提高有利于获得较高的电子密度和电子温度.随后,讨论了主要自由基和离子数密度在不同的甲烷摩尔分数下随着时间的变化规律,并给出了反应气体的转化率、合成气体和重要含氧化合物的选择性.此外,还明确了合成气和含氧化合物主要生成和损耗的化学反应路径,发现甲基和羟基是合成含氧化合物的关键中间体.最后,归纳总结给出了主要等离子体粒子之间的总体等离子体化学反应流程图.