Oxidative radical generation via nitrogen dioxide dimer conversions induced by amide groups of macromolecules

The features of initiation of free radical reactions in polymers by dimers of nitrogen dioxide are considered. The conversion of planar dimers into nitrosyl nitrate in the presence of amide groups of macromolecules has been revealed. Nitrosyl nitrate initiates radical reactions in oxidative primary process of electron transfer with formation of intermediate radical cations and nitric oxide. As a result of subsequent reactions, nitrogen‐containing radicals are produced. The dimer conversion has been exhibited by estimation of the oxyaminoxyl radical yield in characteristic reaction of p‐benzoquinone with nitrogen dioxide on addition of aromatic polyamide and polyvinylpyrrolidone to reacting system. The isomerization of planar dimers is efficient in their complexes with amide groups, as confirmed by ab initio calculations. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Anodic oxidation of mecoprop herbicide at lead dioxide

The electrochemical oxidation of an aqueous solution containing mecoprop (2-(2-methyl-4-chlorophenoxy)propionic acid) has been studied at PbO₂ anodes by cyclic voltammetry and bulk electrolysis. The influence of current density, hydrodynamic conditions, temperature and pH on the degradation rate and current efficiency is reported. The results obtained show that the use of PbO₂ leads to total mineralization of mecoprop due to the production of oxidant hydroxyl radical electrogenerated from water discharge. The current efficiency for the electro-oxidation of mecoprop is enhanced by low current density, high recycle flow-rates and high temperature. In contrast, the pH effect was not significant. It has also been observed that mecoprop decay kinetics follows a pseudo-first-order reaction and the rate constant increases with rising current density.     

Ethynedithiol‐based polyeneoligosulfides as active cathode materials for lithium‐sulfur batteries

Ethynedithiol‐based polyeneoligosulfides have been synthesized in 96% yield by the reaction of sodium acetylides (HC?CNa, NaC?CSNa) and elemental sulfur through the Na? C_sp bond in liquid ammonia with the following spontaneous polymerization of ethynedithiols (HSC?CSH) formed by the hydrolysis. The polyeneoligosulfides synthesized are brown powders (up to 77% sulfur content, mp 128–184°C), partially soluble in organic solvents. They are high‐resistance semiconductors (10^?13 to 10^?14 S cm^?1), possess paramagnetic (10¹⁷ to 10¹⁸ spin g^?1) and redox properties. The oligosulfides obtained, being redox systems capable of reversible redox processes, provide high values of discharge capacity (345–720 mA h g^?1) of rechargeable lithium‐sulfur batteries. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

纳米掺钼二氧化钛光催化剂研究发展

介绍了纳米掺钼二氧化钛光催化剂的制备、特性及应用     

硫含量对钴钼型耐硫脱氧剂的脱氧活性影响

研究了工艺气中硫含量对钴钼型耐硫脱氧剂脱氧活性的影响。通过常压微反 -色谱装置测定脱氧剂的本征脱氧活性 ,加压原粒度反应器测定脱氧剂的表观脱氧活性 ,结合实际经验确定了耐硫脱氧剂所需的最低硫含量。还讨论了温度、压力、空速对耐硫脱氧剂脱氧活性的影响。结果表明 ,耐硫脱氧剂完全能满足耐硫变换工艺的要求 ,而且有耐硫变换的作用 ,并对耐硫变换催化剂起到保护作用     

塔河渣油高温催化临氢热转化技术研究

以塔河减压渣油（简称塔河减渣）为原料，在实验室小型试验装置和中型连续试验装置上，对在较高温度条件下催化临氢热转化加工塔河减渣的工艺操作条件及改质效果进行了系统研究。采用高分散的油溶性催化剂，在高压釜反应器中考察了反应温度、反应压力、催化剂添加量、溶剂油添加量、反应时间以及助剂添加量对塔河减渣催化临氢热转化反应的转化率和缩合率的影响，优化了操作参数。在优化的操作条件下，进行了塔河减渣催化临氢热转化中型试验，得到初馏点大于524 ℃组分的裂化率为85.2%，馏分油收率为80%，金属（Ni+V）和沥青质脱除率均大于90%。     

Morphological changes in poly(?-caprolactone) in dense carbon dioxide

Morphological changes that take place in poly(?-caprolactone) upon exposure to carbon dioxide at high pressures have been explored as a function of pressure and temperature. SEM and DSC results point to a competition between CO₂-modulated crystallization and pressure-induced phase separation which leads to unique morphologies. At 293 K, exposure to CO₂ at pressures up to 45 MPa leads to recrystallization resulting in higher level of crystallinity and higher melting temperatures. Highest crystallinity levels along with distinct crystal morphology were observed after exposure to CO₂ at 308 K and 21 MPa. At a higher pressure at this temperature (308 K/34 MPa) polymer undergoes melting, and foaming is achieved during depressurization prior to solidification. At 323 K, the polymer is found to display unique crystal morphology with concave crystal geometry as well as porous domains. The results are discussed in terms of the crystallization and phase separation paths that are followed during exposure to CO₂ and the depressurization stages.     

Study on Reduction of Sulfur Content in FCC Gasoline

Reduction of sulfur content in FCC gasoline was studied in a fixed fluid bed (FFB) unit by using metal-modified LV-23 FCC catalyst. The results showed that the sulfur content in FCC gasoline could be reduced with LV-23 catalyst modified with zinc, palladium, zinc-palladium, zinc-cobalt, and zinc-nickel. Among these metals or metal combinations, palladium-containing catalyst was the most effective. Desulfufization of the heavy fraction of FCC gasoline was more effective than full-range gasoline under the same conditions with palladium-containing catalysts. A high reaction temperature was favorable to desulfurization, but it would reduce the yield of liquid product. After desulfurization reaction, the olefm content of product gasoline decreased while the aromatic and iso-alkane contents increased. Removal of thiophene and benzothiophene is higher.     

Convective cooling of supercritical carbon dioxide inside tubes: heat transfer analysis through neural networks

In a previous work, convective heating of carbon dioxide was studied with neural networks (NN), obtaining a totally heuristical heat transfer equation from the direct regression of experimental data. In the present work, the analysis focuses on the cooling process, which has a technical relevance in various applications, as for example in transcritical refrigeration cycles. Heat transfer around the critical zone presents a marked enhancement, that follows the peaks in thermophysical properties like thermal conductivity and heat capacity. Similarly, other properties like density and enthalpy, present a strong variation in narrow temperature intervals around the critical point.This constitutes then a highly non-linear phenomenon, for which it is advisable to use a very flexible function approximator like the NNs. NN models were applied both in terms of dimensionless numbers and of physical quantities, obtaining the two corresponding NN architectures. The choice of the optimal number of neurons in the NN hidden layer is discussed. The NN models are then compared with a recent correlation from literature, for which the validation results present an AAD of 27% and a bias of −26% with an evident prediction shifting. On the other hand the NN models in terms of dimensionless numbers and of physical quantities have AAD and bias of 14% and −4%, and of 7% and −2%, respectively, showing a largely better performance.     

Effects of growth with ethanol on fermentation and membrane fluidity of Saccharomyces cerevisiae

Saccharomyces cerevisiae HSc was grown with ethanol at concentrations up to 10% (v/v). The immediate effects of additions of externally added ethanol on CO₂ production and O₂ consumption of washed organisms were studied by stopped-flow membrane inlet quadrupole mass spectrometry. Fermentative activities of organisms grown with ethanol (0–5% v/v) showed similar sensitivities to inhibition by ethanol, whereas those grown with 10% (v/v) ethanol had become protected and were markedly less sensitive. The fluidity of subcellular membrane fractions was measured by determination of the temperature dependence of the rotational order parameter of the spin label 5-doxyl stearic acid (free radical) by electron spin resonance. Mitochondria prepared from yeasts grown with 0, 7 and 9% (v/v) ethanol showed similar overall fluidity, although differences in temperature-dependent behaviour indicate altered lipid composition or lateral phase separations. On the other hand the microsomal fraction from organisms grown with 9% ethanol showed a remarkable increase in fluidity. These data suggest that the protective effects of growth with ethanol near the limit of tolerance on fermentative activities may arise from altered plasma membrane fluidity properties.