Structure and properties of the Nafion—polyaniline—palladium composite electrodes

Effect of conditions of deposition of palladium onto a composite polymeric film Nafion—polyaniline on the properties of the system thus obtained is studied. It is shown that the effect of the said conditions on the character of distribution of palladium in a polymer may be used when estimating electrocatalytic potentialities of such composites.Translated from Elektrokhimiya, Vol. 41, No. 2, 2005, pp. 213–218.Original Russian Text Copyright © 2005 by Andreev, Zolotarevskii.This revised version was published online in April 2005 with corrections to the article note and article title and cover date.     

Pulse radiolysis study of I− oxidation with radical anions Cl2 ⋅− in an aqueous solution

Radiation-chemical transformations of chloride solutions in the presence of iodide additives were studied by pulse radiolysis. Radical anion Cl₂ ^⋅− oxidize I⁻ ion, while in the secondary reactions Cl₂ reacts with I⁻ to form a mixed trihalide ion ICl₂ ⁻. A reaction model that satisfactorily describes the experimental data was proposed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1336–1340, June, 2005.     

Improvement of some pharmaceutical properties of nocloprost by β- and γ-Cyclodextrin Complexation

Inclusion complexation of nocloprost, a potent antiulcer prostaglandin derivative, with -, -, and -cyclodextrins (CyDs) in aqueous solutions has been studied by the solubility method and¹³C-NMR spectroscopy. The steric requirement of host-guest interaction was reflected in the magnitude of the stability constants and the thermodynamic parameters of the inclusion complexes. Solid complexes of nocloprost with - and -CyDs in a molar ratio of 1 : 2 were obtained on the basis of aBs-type phase solubility diagram. The X-ray diffraction data suggested that nocloprost is included in the cylindrical channel formed by coaxial alignment of -CyD molecules to give a channel type structure. Release and thermal behavior of the solid complexes was examined and compared with nocloprost itself. The results indicated that the -CyD complex may have great utility among the three CyDs, being a rapid dissolving form of nocloprost with improved thermal stability.     

Enzymatic degradation of highly phenolic lignin-based polymers (lignophenols)

Enzymatic degradation of two lignin-based polymers (lignophenols), lignocatechol and lignocresol, prepared by selectively grafting catechol and p-cresol to C_α positions of lignin, respectively, were carried out in aqueous organic solvents. Both lignophenols showed high reactivity in the peroxidase-catalyzed oxidation. Structural analyses by NMR spectroscopies revealed that the degraded lignophenols contained aliphatic chain content, which might be mainly formed in the reduction of the intermediate initially generated by the aromatic ring cleavage. Lower amount of aromatic units in the lignophenols after degraded by peroxidase also indicted the cleavage of aromatic rings. Due to the substitution of phenols at C_α positions of lignin, the degraded lignophenols did not have carbonyl structure, which was abundant in the biodegradation products of native lignin. The two lignophenols were also degraded by Rhus vernicifera laccase. But the degree of degradation was lower than that of the degradation by peroxidase, which might be due to the low activity of laccase on the lignin moieties in lignophenols.     

Gel permeation chromatographic characterization of sodium hyaluronate and its fractions prepared by ultrasonic degradation

Summary High-molecular-weight sodium hyaluronate isolated from rooster combs was degraded by ultrasonication. The molecular weight of hyaluronate and its polydispersity was determined by gel-permeation chromatography. During 75-min treatment the molecular weight value decreased from 1.39×10⁶ Da to 2.25×10⁵ Da while the polydispersity of the molecular weight increased from 1.29 to 2.36. The reciprocal value of the square of the hyaluronate's molecular weight was linearly proportional to the time of ultrasonication.     

Size exclusion chromatographic characterization of sodium hyaluronate fractions prepared by high energetic sonication

Summary A high molecular weight sodium hyaluronate isolated from rooster combs was degraded by ultrasonication. High-performance size exclusion chromatography allowed rapid and accurate determination of molecular weight parameters (M_z, M_w, M_n) and distributions. The time dependence of hyaluronan ultrasonication to the molecular characteristics of the polymer was investigated. A non-random nature of the degradation process was demonstrated and the reciprocal M_n value was found to be linearly proportional to the time of ultrasonication.     

芥子气模拟剂2-氯乙基乙基硫醚的光催化降解

利用连续流动微反、原位红外和GC/MS等手段考察了芥子气模拟剂2-氯乙基乙基硫醚（2-CEES）在P25 TiO2上的光催化降解反应,证实CO2和H2O是这个反应的最终产物.详细的跟踪分析表明,除了CO2和H2O外,在反应的气相混合物中可检测到C2H4、CH3CHO、CH4、CO、HCl和H2S；少量小分子的羧酸、醚和砜；微量C2H5SC2H5、C2H5S2C2H5、C2H5SC2H4Cl和CH2ClCH2Cl等中间产物;在反应后的催化剂表面可检测到C2H5S2C2H5、C2H5SC2H4OH、C4H9S2C2H5和C2H5S2C2H4OH、等物.根据这些结果提出了2-CEES光催化降解的反应机理,推断2-CEES的光催化降解涉及脱氯、C－S键断裂、有机硫化物光聚合和裂解等复杂过程最终转化为CO2和H2O.认为各种硫物种在表面的积聚引起了催化剂的缓慢失活.     

Effect of deacetylation rate on gelation kinetics of konjac glucomannan

Effect of deacetylation rate on the gelation behaviors on addition of sodium carbonate for native and acetylated konjac glucomannan (KGM) samples with a degree of acetylation (DA) range of 1.38-10.1 wt.% synthesized using acetic anhydride in the presence of pyridine as catalyst was studied by dynamic viscoelastic measurements. At a fixed alkaline concentration (C(Na)), both the critical gelation times (t(cr)) and the plateau values of storage moduli (G'(sat)) of the KGM gels increased with increasing DA. While at a fixed ratio of alkaline concentrations to values of DA (C(Na)/DA), the similar t(cr) and (G'(sat)) values independent of DA were observed. On the whole, increasing KGM concentration or temperature shortened the gelation time and enhanced the elastic modulus for KGM gel. The effect of deacetylation rate related to the C(Na)/DA on the gelation kinetics of the KGM samples were discussed.     

Thermal degradation of wood treated with guanidine compounds in air: Flammability study

Wood has been treated with guanidine phosphate, guanidine nitrate, guanidine carbonate and guanidine chloride to impart flame retardancy. The samples were subjected to differential thermal analysis (DTA) and thermogravimetry (TG) from ambient temperature to 800°C in air to study their thermal behaviors. From the resulting data, kinetic parameters for different stages of thermal degradation were obtained following the method of Broido. For the decomposition of wood and flame retardant wood, the activation energy was found to decrease from 116 to 54 kJ mol^–1; the char yield was found to increase from 5.6 to 34.9%, LOI from 18 to 41.5, which indicated that the flame retardancy of treated wood was improved. Effects of the different compounds on the degradation and flammability of wood have also been proposed.This revised version was published online in November 2005 with corrections to the Cover Date.     

应变速率和电位对应力腐蚀裂纹扩展的影响

以滑移-溶解-再钝化模型为基础,推导出应力腐蚀裂纹扩展速率与裂尖应变速率和电位之间的理论公式.计算表明,在裂纹扩展速率与裂尖应变速率的关系曲线中有两个特征区域.裂纹扩展速率在区域I随裂尖应变速率增加而增大,而在区域II不随裂尖应变速率的改变而变化.用慢应变速率拉伸技术（SSRT）测量了304L不锈钢的裂纹增长速率.当电位控制在区域II的阳极区时,理论计算的裂纹扩展速率与实验得到的结果比较吻合.