在带有尾气回流的固定床合成装置中水煤气合成醇的研究

研究了在C-02型催化剂上尾气回流和改变原料气组成对合成醇的影响.尾气回流有利于醇的生成,在50%左右的转化深度下,折算醇收率从无回流时的46.0克/米~3转化(CO+H_2)提高到回流比等于10时的110克/米~3转化(CO+H_2);含氧化合物中醇占99%以上,其中水相醇达90%以上.降低原料气中CO_2的浓度对反应未产生显著影响,而降低原料气中H_2/CO比则使醇收率大大下降.     

Cyano- and Nitro-containing Compounds from the Roots of Semiaquilegia adoxoides

Four cyano-containing compounds, (1E,4α,5β,6α)-4,5,6-trihydroxy-2-cyclohexen-l-ylideneacetonitrile (1), lithospermoside (2), 4-hydroxy-2-β-D-glucopyranosyl oxyphenylacetonitrile (3) and 4-[β-D-apiofuranosyl-(1→6)-O-β-D-glucopyranosyl oxy]phenylacetonitrile (4), and a nitro-containing one, 4-[β-D-xylopyranosyl-(1→6)-O-β-D-glucopyranosyloxy]-1-(2-nitroethyl)benzene (5), as well as eleven other types of compounds, were isolated from the roots of Semiaquilegia adoxoides. Their structures were elucidated mainly by spectroscopic methods. Among them, 1 and 4 are new isolated compounds. The cyano- and nitro-containing compounds are very rare in plants and their isolation from one traditional Chinese medicine is really interesting.     

钇磷钨三元杂多配合物的合成及其稀土多元渗与导电性的研究

合成了未见报道的标题配合物。通过化学分析、ICP和TG曲线确定了其化学式为K_8H_3[Y(PW_(11)O_(39))_2]·25H_2O;利用IR、UV、XRD、~(183)W-NMR、循环伏安等手段对其结构进行了表征,结果表明杂多阴离子为β_2型Keggin结构。采用稀土多元渗的方法对配合物进行了气相热扩渗,经ICP和XPS测试表明:微量的稀土元素La和Ce可以渗入到配合物的体相,并与组份元素存在键合作用。扩渗后化合物的化学式为K_8H_6YLa_(0.11)Ce_(0.18)P_2W_4~ⅤW_(18)~ⅥO_(78)·15H_2O,其晶体属单斜晶系,晶胞参数:a=6.3775nm,b=3.6771nm,c=3.7727nm,β=90.192°,V=88.47326nm~3;导电性的测试结果表明:室温时,扩渗后试样的电导率提高了约10~3倍,且热稳定范围变宽,523K时的电导率为1.33×10~(-2)S·cm~(-1),有望成为实用化的导电材料;~1H MAS NMR测试结果表明其存在三种质子,其导电机理可能是质子导电。     

稀土元素对铬酵母中铬含量影响的研究

研究了稀土化合物在铬酵母制备过程中对总铬和有机铬含量的影响作用。镧、铈、镨、钕等轻稀土化合物均能明显提高铬酵母中总铬和有机铬的含量 ,其中镧化合物对铬酵母中总铬和有机铬含量的提高作用最显著 ,总铬含量可达到 70 8.33μg·g- 1 ,有机铬含量可达到 6 39.0μg·g- 1 ,是未加稀土铬酵母样品的近 3倍 ;添加钕化合物的铬酵母中有机铬占总铬的比例最高 ,可达到 97.5 %。通过紫外光谱分析 ,发现有机铬在 2 6 0nm处有特征吸收峰 ,通过红外光谱分析 ,发现有机铬在 478cm- 1 处有特征吸收峰 ,而加稀土化合物的铬酵母样品在此两处的吸收峰值均高于未加稀土的铬酵母样品     

伊文思蓝作荧光探针研究牛血清白蛋白与红霉素之间的竞争反应

用伊文思蓝(EB,Evans blue)作荧光探针研究了红霉素(erythromycin,EM)对牛血清白蛋白(BSA,bo-vine serum albumin)的竞争反应。根据Stern-Volmer方程研究了荧光猝灭的类型及机理,伊文思蓝与牛血清白蛋白作用,使牛血清白蛋白荧光发生静态猝灭,即伊文思蓝和牛血清白蛋白形成了一种稳定的复合物。伊文思蓝与牛血清白蛋白的结合常数KBSA-EB=1.122×106L/mol,结合点数n=0.9935。当加入红霉素后,牛血清白蛋白的相对荧光强度恢复,表明红霉素与牛血清白蛋白发生了竞争反应,探讨了相关机理,得到了伊文思蓝与红霉素的结合常数KEB-EM=1.950×104L/mol。     

Keggin结构过渡金属杂多阴离子中配位水与奎宁的取代反应

The substitution reaction of quinine by the 18 types of heteropoly complexes, for these formed compounds are Keggin structure and the molecular formulas are [XM₁₁O₃₉M′(OH)₂]^6-(X=Si,Ge,P;M=Mo or W;M′=Co,Ni,Cu), was studied by the means of phase transfer. The results of characterization that were accomplished by UV and ESR indicated that the quinine does form the chemical bond with the hetropoly ligands. Spectral experiment demonstrated that the structure held the same when the heteropoly complex contained Cu²⁺ was reacted with qui-nine, while the heteropoly complex contained Ni²⁺ resulted in the changing of the structure. Such a result of op-tical rotatory opticity testified that quinine reacting with heteropoly acid contained transitional metals could form a kind of new complexes which were optical rotation.     

超临界二氧化碳参与的两相体系及其在有机合成反应中的应用

均相催化剂具有催化活性高、选择性好等优点, 但是产物难于纯化、催化剂不易回收等问题一直制约它的应用. 两相体系为这些问题的解决提供了一条新途径. 超临界二氧化碳参与的两相体系是使用超临界二氧化碳作流动相, 其它一些对环境友好的反应介质, 如: 水、离子液体、聚乙二醇等, 用于固定催化剂, 进行金属络合物催化的有机合成反应. 其显著特点是将反应与分离两步操作并于一个过程中完成, 即所谓“均相反应、非均相分离”过程, 实现均相催化过程的连续化. 综述了近几年来超临界二氧化碳促进的两相体系的研究进展, 并介绍其在有机合成反应中的应用.     

取代苯基—异喹啉基甲醇的还原和氧化反应

中药青风藤中的微量生物碱——青藤定（Ｓｉｎｏｍｅｎｄｉｎｅ）具有阿朴啡类结构［１］。在合成青藤定的过程中，需将２，３二甲氧基６溴苯基１’（５’甲氧基异喹林）甲醇（ｌａ）关环制备化合物（２）。当用光化学方法［２，３］进行中压汞灯照射下的反应时，没有得到预期产物（２）。反应后除回收原料外分离到一个Ｒｆ值较大的化合物（３）。ＩＲ谱鉴定表明化合物（３）的结构中无羟基峰。进一步的鉴定证明该化合物是原料（ｌａ）中羟基被氢原子置换的产物。结构为１（２’，３’二甲氧基６’溴苯甲基）５…     

Approximate Homotopy Direct Reduction Method: Infinite Series Reductions to Perturbed mKdV Equations

An approximate homotopy direct reduction method is proposed and applied to two perturbed modified Korteweg- de Vries （mKdV） equations with fourth-order dispersion and second-order dissipation. The similarity reduction equations are derived to arbitrary orders. The method is valid not only for single soliton solutions but also for the Painlevd Ⅱ waves and periodic waves expressed by Jacobi elliptic functions for both fourth-order dispersion and second-order dissipation. The method is also valid for strong perturbations.