VNS反应合成LLM-116

以1,3-二硝基吡唑为原料,经热重排、氨气中和得到3,5-二硝基吡唑铵盐,然后酸化得到3,5-二硝基吡唑。以三甲基肼碘化物（TMHI）作为异常亲核取代氢（VNS）反应试剂,与3,5-二硝基吡唑在叔丁醇钾为催化剂,利用VNS反应合成4-氨基-3,5-二硝基吡唑（LLM-116）。采用红外分析、核磁共振、元素分析等仪器鉴定了其结构,讨论了VNS反应机理及影响因素。通过实验,得出最佳VNS反应试剂为TMHI,反应时间为4h,反应温度为25℃,收率达到60%。     

化学工业中反应-分离过程结合技术的研究进展

介绍了分离过程和反应过程相结合技术在化工生产中的研究及其应用、热点和难点问题的最新研究动态以及相应的研究成果，并对其发展前景进行了展望。     

二碘化钐在分子内环化反应中的应用

综述了二碘化钐在分子内环化反应中的应用。     

碱-碳酸盐反应热力学讨论

应用热力学方法探讨了温度对碱 碳酸盐反应的影响 ,反应温度升高时 ,反应的推动力减弱。对碱与碳酸盐发生反应生成沉淀时所需碱的浓度以及温度的影响进行了讨论。 2 98K ,pH≥ 10 .6时 ,碱 碳酸盐反应能发生 ,反应温度升高 ,碱 碳酸盐反应所需碱的浓度相应增大。对氢氧化锂与碳酸盐反应可能生成碳酸锂沉淀时溶液的碱的浓度作了计算 ,2 98K ,pH≥ 13.1时 ,氢氧化锂与碳酸盐反应除生成水镁石和方解石外还能生成碳酸锂沉淀 ,反应温度升高时 ,反应生成碳酸锂沉淀所需碱的浓度变化不大     

Drying with Chemical Reaction in Cocoa Beans

Desirable flavor qualities of cocoa are dependent on how the cocoa beans are fermented, dried, and roasted. During fermentation and drying, polyphenols such as leucocyanidin and apecatechin are oxidized by polyphenols oxidase to form o-quinone, which later react nonenzymatically with a hydroquinone in a condensation reaction to form browning products and moisture. The objective of this article is to model the cocoa beans drying together with the browning reaction. A Luikov drying model for the moisture and a simple Fick's law diffusion model combined with first-order reactions for both the enzymatic oxidation and nonenzymatic condensation reactions were constructed. Both models were used to identify moisture diffusivity coefficient and total polyphenols diffusivity in cocoa beans from experimental drying and polyphenols degradation data and published kinetic data of the reactions. The theoretical drying model fitted the experimental cocoa bean drying curves with low mean square of residuals. The polyphenols diffusion and reaction model also fitted the experimental polyphenols degradation curves with minimum mean residual squares. The rate of polyphenols degradation in the cocoa beans increases at higher temperature and higher relative humidity. This is because the increasing reaction rate of polyphenols oxidation reaction as well as higher moisture diffusion at higher relative humidity and temperature. The effective moisture diffusivity in cocoa beans is estimated to be between 8.194 × 10^-9 and 8.542 × 10^-9 m²·s^-1, which is of the same order of magnitude as published data. The effective total polyphenols diffusivity is estimated to be between 8.333 × 10^-12 to 1.000 × 10^-11 m²·s^-1 with minimum mean residual squares. It is three orders of magnitude less than the estimated moisture diffusivity because of the larger polyphenols molecules. The estimated polyphenols diffusivity is very close to those published in the literature for sorption and ultrafiltration processes.     

A novel methanol-tolerant Ir-Se chalcogenide electrocatalyst for oyxgen reduction

A novel methanol-tolerant oxygen-reduction catalyst, Iridium-selenium (Ir-Se) chalcogenide, was synthesized by chemical precipitation in an organic solvent. Auger electron spectroscopy (AES) analysis confirmed that the synthesized Ir-Se chalcogenide had a chemical formula of Ir₄Se. This chalcogenide showed strong catalytic activity towards the oxygen reduction reaction (ORR) and a high methanol tolerance. It was found that most of the oxygen could be directly reduced to water through a four-electron pathway with less than 10% hydrogen peroxide (H₂O₂) being produced during the ORR. The improvement in catalytic activity of the Ir-Se chalcogenide in comparison with that of pure Ir might be attributed to the effect of a bimetallic interaction.     

EC与~（99m）Tc－GH之间的配体交换反应动力学研究

实验表明，ＥＣ浓度与配体交换反应速度常数无关，体系的ｐＨ值对速度常数和９９ｍＴｃ－ＥＣ的标记率影响较大。测定并计算了不同ｐＨ值的交换反应速度常数。结果表明，为保证用配体交换法制备９９ｍｃ－ＥＣ时９９ｍｃ－ＥＣ的标记率大于９０％，体系的ｐＨ值必须≥８。     

Comparison of interfaces in Ti composites reinforced with uncoated and TiB2/C-coated SiC fibres

Interfaces play an important role in determining the mechanical properties of composite materials. The interfaces established between a titanium-alloy matrix (Ti-6Al-4V) and uncoated and TiB₂/C-coated SiC fibres are analysed by scanning electron microscopy, transmission electron microscopy and X-ray techniques. Emphasis is placed upon the interfacial morphology and microstructure, identification of reaction products, and the stability of the coating layer. Complex multi-reaction layers are observed frequently in the interfacial zones. Previous, often contradictory, reports about the interlayers are reviewed. Experimental observation demonstrates that the type and distribution of interlayers vary in a given system, due to prolonged treatment of the samples at temperature. The formation and distribution of the interlayers are discussed further, with respect to these and previous findings. Methods of reducing interfacial reactivity are discussed.     

高能球磨AL─Cu合金固态合成反应研究

采用扫描电镜、能谱分析、Ｘ射线衍射和示差扫描量热分析研究了具有较大负混合焓的Ａｌ＿ｘＣｕ＿（１－ｘ）对称扩散系合金的高能球磨固态合成反应。高能球磨时组元晶粒细化达纳米级，造成纳米晶界亚互溶，为室温固态合成反应创造了条件，球磨强度对反应进程影响显著，在ｘ＝０．３～０．７范围内仅形成一种金属间化合物。     

Zirconium-based intermetallics as heterogeneous catalysts for the fischer-tropsch reaction: I. Zr-Ni-Co catalysts

Alloys of the general formula Zr₅₀Ni_xCO_50-x, where 0 ≦x≧ 50, have been prepared and used in the temperature range 300–400°C, in the pressure range 1–9 barg in a microtubular reactor for the reaction of hydrogen with carbon monoxide to give hydrocarbons. The alloys or intermetallic materials were prepared by argon arc melting, powdered by hydrogen decrepitation and characterised by means of optical microscopy (metallography), scanning electron microscopy with surface analysis and magnetic susceptibility measurements. The selectivity towards higher hydrocarbons increased with (i) increase in the total pressure and (ii) decrease in hydrogen content of the feed gases. The kinetics were found to be of the form: where m = 1.0 ± 0.2 and n = 0. The apparent energy of activation (E_a) lay in the range of 80–130 kJ mole^?1 and there appeared to be a compensation effect between E_a and the pre-exponential factor A. The turnover numbers for the reaction exhibited an activity maximum for alloys of composition around Zr₅₀Ni₄₀Co₂₀ and Zr₅₀Ni₃₀Co₂₀. Magnetic susceptibility measurements indicated that alloys changed their nature from moderately paramagnetic to strongly paramagnetic or even ferromagnetic after use and this is attributed to the conversion of zirconium to zirconium oxide during reaction with the attendant production of free 3d-transition metals. Derived catalysts prepared by air treatment of the hydrogen-decrepitated intermetallics behaved almost identically to the latter materials and gave similar magnetic susceptibility values to used hydrided materials.