Classifying Structural Characteristics to Enhance Computation of Enthalpy of Formation of Halohydrocarbons

Density functional theory (DFT) calculations are made and least squares calibration performed for various halohydrocabons, which were 27 straight‐chain alkyl halides, 20 branch‐chain alkyl halides and 19 aromatic halides, to determine their enthalpies of formation (ΔH_f). The mean absolute error (M. |A.E.|) in ΔH_f across 66 molecular computations was only 7.8 kJ/mol (1.9 kcal/mol). Grouping the molecules by their structural characteristics improved M. |A.E.| of ΔH_f by 0.2–2.2 kJ/mol over that obtained using corresponding modified data for the same 66 unclassified molecules.     

Thermodynamic characteristics of solvation of individual ions in ethanol at −50 to 55°C

Experimentally determined are the enthalpies of solution of 12 electrolytes (LiBr, LiI, NaBr, NaI, NaBPh₄, Et₄NCl, Et₄NBr, Pr₄Br, Bu₄NBr, Am₄NBr, Ph₄PCl, Ph₄PBr) in ethanol at –50 to 55°C. _sH^o values obtained on the basis of four different extrapolation equations are analyzed. The effect of temperature changes on the thermodynamic parameters of solvation indindividual ions are calculated using thermodynamic data for the salt crystals (lattice) with the assumption that _solvC _p ^o (Ph₄P⁺)=_solvC _p ^o (Ph₄P^-).     

垃圾在流化床中焚烧NO排放特性研究

在Ф150 mm流化床上，研究了六类典型组分垃圾NO转化率与床温和过量空气系数(excess air简称EA)的关系。研究发现，纸渣与木块NO转化率最高，橡胶与塑料最低;织物、纸张、厨余、木块、塑料NO均具有中温生成特性，一般在800 ℃～850 ℃时即接近最大值，之后温度升高对NO的生成影响不大;橡胶与无烟煤由于含N化合物结构稳定，其NO转化率随床温升高而增大;由于挥发分析出的相互影响，较低的火焰温度，混合垃圾NO转化率一般低于单组分垃圾的线性叠加;少量水分不会对垃圾NO转化率造成很大影响，相反还会促进NO的转化，但过量水分会抑制NO的生成。     

Effect of enzyme concentration on the dynamic behavior of a membrane-bound enzyme system

The dynamic behavior of the reaction-diffusion system, composed of glucose oxidase (EC 1.1.3.4) immobilized at a uniform concentration in a membrane, used as a glucose electrode is represented by a diffusion equation with a nonlinear reaction-term in one-dimensional space. The mathematical model is analyzed by computer simulation, that is, numerical integration of the equation under various initial and boundary conditions, to examine the effect of enzyme concentration on the response characteristics (responsiveness and linearity in response) of the electrode. The analysis of the responses of the system to stepwise changes in the boundary value (glucose concentration in simple solution) infers that the enzyme concentration governs the patterns of the spatial distributions of the substrates (glucose and dissolved oxygen) in steady states and transient responses. It is also revealed that the response characteristics of the electrode are optimized with concentration of immobilized enzyme and that the system establishes the steady states at the same spatial distributions of the substrates, regardless of the boundary value. The diffusion of the substrates and the oxygen concentration also have significant effects on the response characteristics of the electrode.     

负载型CuO—ZnO／γ—Al2O3催化剂抗硫中毒性能的研究

采用XPS、TPR法证明浸渍法制备的CuO-ZnO/Al_2O_3催化剂中的CuO、ZnO和γ-Al_2O_3之间存在强相互作用,Cu量≤7.0wt%,Zn量≤11Wt%时,CuO和ZnO以单分子层分散在γ-Al_2O_3上.催化剂表面Cu和Zn实际含量的比值远小于配制时的比值(Cu/Zn=2),表明ZnO比CuO优先分布在表面.因ZnO比CuO更易和S作用生成ZnS,ZnO在表面的大量存在减少了Cu被S中毒的机率;另外CuO单层分散在Al_2O_3上,还原后生成的Cu~0,由于γ-Al_2O_3的拉电子作用使其处于缺电子状态(CU~(?+)),加上催化剂表面可能有部分CuO和Al_2O_3形成尖晶石,使一部分Cu以Cu~(n+)存在,Cu~((?)+)或Cu~(n+)对S的吸附弱.以上两个原因使负载型铜催化剂具有良好的抗硫中毒性能.     

Redox Transformation of Adducts from Cycloaddition of Diazoacetic Ester to β-Arylacryloyloxiranes

It was established that, in addition to ethyl 4-aryl-3-(2,3-epoxyalkanoyl)-4,5-dihydro-1H-pyrazole-5-carboxylates, the reaction of diazoacetic ester with β-arylacryloyloxiranes also gives ethyl 4-aryl-3(5)-(3-hydroxy-2-methylalkanoyl)-1H-pyrazole-5(3)-carboxylates. The latter are formed from the tautomeric ethyl 4-aryl-5-(2,3-epoxyalkanoyl)-4,5-dihydro-1H-pyrazole-3-carboxylates as a result of intramolecular oxidative-reductive disproportionation. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, 1150–1160, August, 2005.     

Synthesis of New Fluorinated Derivatives of Quinolinecarboxylic Acids

Ethyl esters of 1-(7-Z-1-ethyl-6-fluoro-4-oxo-1,4-dihydroquinoline-3-carbamoyl)-5-X-6,7,8-trifluoro-4-oxo-1,4-dihydroquinoline-3-carboxylic acids (X = H, F; Z = pyrrolidino-, piperidino-, hexamethylenimino-, morpholino-, thiomorpholino-) have been synthesized by the interaction of quinolone-3-carboxylic acid hydrazides with ethyl esters of 3-ethoxy-2-(polyfluorobenzoyl)acrylic acid . It was shown possible to cyclize intramolecularly the esters obtained with the formation of 1,3,4-oxadiazino[6,5,4-i,j]quinoline derivatives.     

含离子液体［bmim］Cl的反应介质中马肝醇脱氢酶的催化特性

 研究了马肝醇脱氢酶(HLADH)在含离子液体1-丁基-3-甲基咪唑氯酸盐(［bmim］Cl)的反应介质中的催化特性. 以乙醇为底物时,该酶在［bmim］Cl含量≤0.15 g/ml的体系中的活力高于在不含离子液体的体系中的活力; 离子液体浓度过高(＞0.15 g/ml)对酶活性有明显的抑制作用. 反应温度和pH对含离子液体的反应介质中酶活力的影响规律与不含离子液体时的规律相似. 与不含离子液体的反应介质相比, HLADH在含0.05 g/ml ［bmim］Cl的体系中催化乙醇氧化的活化能下降,酶反应的Vmax和Km均升高. 反应体系中低浓度(≤0.1 g/ml)的离子液体能提高酶的热稳定性,但高浓度(＞0.1 g/ml)的离子液体可降低酶的热稳定性. 紫外二阶导数光谱显示,在含不同浓度离子液体的反应介质中酶分子构象的变化有较大的差异.     

Operating characteristics and energy distribution in transferred plasma arc systems

A specially designed plasma chamber was constructed to study the operating characteristics of a dc plasma-transferred arc of argon, struck between a fluid convective cathode and a water-cooled anode. The arc voltage increased markedly with arc length and with an increase in the inlet velocity of the argon flow past the cathode tip, and much less with an increase in current. Radiation from the plasma column to the chamber walls and transfer of energy to the anode were the two principal modes of transfer of the arc energy. The former was dominant in the case of long arcs and at high inlet argon velocities. At the anode, the major contribution was from electron transfer, which occurred on a very small area of the anode (～5 mm in diameter). Convective heat transfer from the plasma was somewhat less. In all cases, the arc energy contributions to cathode cooling and to the exit gas enthalpy were small. From total heat flux and radiative heat transfer measurements, it was estimated that the plasma temperature just above the anode was in the range 10,000–12,000 K. Preliminary experiments with an anode consisting of molten copper showed that the arc root was no longer fixed but moved around continuously. The arc was othwewise quite stable, and its operating characteristics differed little from those reported for solid anodes, in spite of the greater extent of metal vaporization.     

内蒙古地区天然植物沙棘果中黄色素的提取工艺及性质研究

以内蒙古地区沙棘果实为原料，研究了提取黄色素的工艺条件，同时对该色素的性质进行了初步探讨。结果表明，以95％的乙醇溶液作浸提剂，提取的黄色素浓度最高，工艺流程简单易行，且无毒，无污染。对提取的黄色素进行的性质试验表明，沙棘黄色素对光、热具有较好的稳定性，适用于酸性或弱碱性的食品中，葡萄糖、氧化剂(H2O2)、还原剂(Na2SO3)等食品添加剂均无明显影响以上结果为这种优良天然色素的开发与应用提供了参考。