DEHYDROGENATION AND AROMATIZATION OF METHANE IN THE ABSENCE OF OXYGEN OVER DOPED Mo/HZSM-5 CATALYSTS

研究了在Ｍｏ／ＨＺＳＭ－５催化剂上添加助剂以及不同的反应预处理温度对甲烷无氧脱氢芳构化反应的影响。实验结果表明，由于第二组分的添加，Ｍｏ／ＨＺＳＭ－５催化剂的活性和选择性都得到了较大程度的改善。预处理温度是影响催化剂反应性能的关键因素。Ｍｏ－Ｒｕ／ＨＺＳＭ－５催化剂经过８７３Ｋ空气预处理后，甲烷在９７３Ｋ的转化率约为１０％，催化剂的稳定性也得到较大程度的提高。ＴＰＳＲ实验结果表明，Ｒｕ的加入降低了芳烃生成的温度。ＴＰＯ和ＤＴＡ实验结果表明，在Ｍｏ－Ｒｕ／ＨＺＳＭ－５催化剂上可生成较多的碳物种，结合反应结果，可以认为反应过程中生成的碳物种对甲烷的无氧脱氢芳构化反应是起积极作用的     

Preparation of a set of selectively protected disaccharides for modular synthesis of heparan sulfate fragments: toward the synthesis of several <Emphasis Type="Italic">O</Emphasis>-sulfonated [β-D-GlcUA-(1→4)-β-D-GlcNAc]OPr types

A concise method for a stereocontrolled synthesis of a set of selectively protected disaccharides is reported. Coupling of the donor 11 onto acceptors 23 and 24, promoted by trimethylsilyl triflate-N-iodosuccinimide (TMSOTf-NIS), generated the disaccharides 25 and 26. Under typical conditions, condensation of the fully protected donor 12 onto acceptors 23 and 24 produced the disaccharides 27 and 28. The building blocks 25–28 were prepared in moderate yields having exclusive β-stereoselectivity. A unique pattern of protecting groups distinguished clearly between positions to be sulfated and functional groups remaining as free hydroxyl groups. Acetyl and/or levulinoyl esters temporarily protected the positions to be sulfated, while benzyl ethers were used for permanent protection. The anomeric positions were protected as allyl ethers, whereas the 4′-positions were masked as p-methoxybenzyl (PMB) ethers. The orthogonality of the PMB and allyl groups can then be used for further elongation of the chain by recurrent deprotection and activation steps. The hydroxyl group, OH-6, of glucosamine moieties was protected as a TBDPS ether to avoid oxidation. A five-step deprotection/sulfonation sequence was applied to the disaccharide 27 to generate the corresponding sulfated [β-D-GlcUA-2-OSO₃Na-(1→4)-β-D-Glc pNAc]-(1→O-Pro) 34.     

煤自燃初期的反应机理研究

从实验得到的可能引起煤自燃的8个活性基团入手，提出了一系列简单煤分子模型，利用密度泛函DFT/6-31G对其完成了几何优化，计算了包括反应焓变、吉布斯自由能和活化能等，从热力学和动力学角度分析了计算结果。基于理论计算获得了煤活性基团的活泼性次序，得出了煤自燃初期的反应机理主要是氧分子先进攻煤分子中的活性基团，产生活泼性很高的中间体，然后中间体进一步反应得到水或二氧化碳及其他反应产物，计算结果与实验基本符合。     

Synthesis and Mesogenic Properties of Liquid Crystals Containing Terminal Cyclohexylmethanol,Cyclopentylmethanol, Cyclobutylmethanol and Cyclopropylmethanol Moiety

Four series of compounds 11?50 containing terminal alicyclic rings such as cyclohexylmethyl, cyclopentylmethyl, cyclobutylmethyl, and cyclopropylmethyl rings were synthesized and their liquid crystal behavior studied. The ring size and the length of flexible alkoxy chain influence the phase formation in different ways. While the smaller ring and the shorter alkoxy chain tend to favor the formation of the N phase, the larger ring and the longer alkoxy chain tend to favor the formation of the SmC phase. All the compounds except 11 and 21 exhibit SmA phases. The widest temperature range of the N, SmA, and SmC phases are found in the compounds 41 , 46 , and 20 , respectively, which are 75 °C for 41 , 115 °C for 46 , and 100 °C for 20 .     

A new method for inversion of hydroxyl group of carbocyclic nucleosides

The hydroxyl group of carbocyclic nucleosides was inversed when the compounds were treated with Me_3SiCl,KCN and a catalytic amount of NaI in DMF/CH_3CN.     

A new protecting group for the exocyclic amino groups of nucleosides

A new protecting group has been developed for the exocyclic amino groups of nucleosides that occur in DNA. 3-Phenyl-[{N-(2-trimethylsilyl-ethoxycarbonyl)-2-amino}]-propanoic acid used as the protective agent.     

Effect of the rhenium additive to VOx/TiO2 and MoOx/TiO2 catalysts on their properties in oxidative dehydrogenation of propane

VO_x/TiO₂ and MoO_x/TiO₂ catalysts with the addition of Re (Re/V or Mo = 0.5) were synthetized and tested in oxidative dehydrogenation of propane and in reduction by propane. XPS measurements showed depletion of the surface in Re. The Re additive does not affect the total conversion of propane, but increases the selectivity to propene. The effect is more pronounced for the MoO_x/TiO₂ catalyst. The increase in the selectivity to propene is accompanied with the increase in the reducibility of the catalysts.     

气相[（SiO2）nX]^—团簇产生机理

利用ＸｅＣｌ准分子激光烧蚀多种硅氧多孔结构材料，在负离子通道测得丰富的「（ＳｉＯ２）ｎＸ」＾－负离子团簇，并讨论了多孔网结构和表面活性基团的分布对激光能量的吸收，传输及团簇产生的重要作用。     

Thermal degradation of copolymers of styrene with dicarboxylic acids - II: Copolymers obtained by radical copolymerisation of styrene with maleic acid or fumaric acid

Thermal degradation processes in copolymers of styrene with two stereoisomers of 1,2-ethylenedicarboxylic acids (i.e. maleic acid (the cis-isomer) and fumaric acid (the trans-isomer)) have been studied by mass spectrometry, FTIR and TG measurements. The influence of the chemical composition on thermal degradation of copolymers with acid by non-isothermal thermogravimetric analysis (TG) was also studied. The stereo-configuration of carboxyl groups in copolymers was analysed by potentiometric titration. It was found that copolymers degrade in two main complex stages. The initial step in the decomposition involves the formation of cyclic five-membered anhydrides. The presence of trans configuration of carboxyl groups hinders the formation of cyclic anhydrides and shifts the decomposition to higher temperatures, making decarboxylation competitive. At higher temperatures anhydride decomposition takes place and finally the degradation of main chains occurs.     

Convenient and High-Yielding Preparations of Mono(5-carboxy-2-ethylpentyl) Phthalate and its Ring-Deuterated Isomer – The “Third” Major Metabolite of Bis(2-ethylhexyl) Phthalate

Summary. The synthesis of an oxidative major metabolite of bis(2-ethylhexyl) phthalate is described. The target molecule and its ring-deuterated isomer were obtained via acylation of the appropriate -hydroxy benzyl ester or the corresponding carboxylate with phthalic anhydride or phthalic anhydride-d₄. All transformation steps proceed with high yields.