添加微量铝对TS-2合成及苯酚羟基化的影响

以硅溶胶为硅源合成分子筛TS 2时 ,在溶胶制备过程中添加微量的铝 ,可以降低模板剂氢氧化四丁基铵 (TBAOH)的用量 ,当TBAOH/SiO2 降低到 0 .1以下时 ,仍然合成了性能优良的TS 2 ,而且用于苯酚过氧化氢羟基化反应过程中催化活性也大大提高。所得催化剂用XRD ,IR ,ICP进行了表征     

CYP154C5 Regioselectivity in Steroid Hydroxylation Explored by Substrate Modifications and Protein Engineering**

CYP154C5 from Nocardia farcinica is a P450 monooxygenase able to hydroxylate a range of steroids with high regio- and stereoselectivity at the 16α-position. Using protein engineering and substrate modifications based on the crystal structure of CYP154C5, an altered regioselectivity of the enzyme in steroid hydroxylation had been achieved. Thus, conversion of progesterone by mutant CYP154C5 F92A resulted in formation of the corresponding 21-hydroxylated product 11-deoxycorticosterone in addition to 16α-hydroxylation. Using MD simulation, this altered regioselectivity appeared to result from an alternative binding mode of the steroid in the active site of mutant F92A. MD simulation further suggested that the entrance of water to the active site caused higher uncoupling in this mutant. Moreover, exclusive 15α-hydroxylation was observed for wild-type CYP154C5 in the conversion of 5α-androstan-3-one, lacking an oxy-functional group at C17. Overall, our data give valuable insight into the structure–function relationship of this cytochrome P450 monooxygenase for steroid hydroxylation.     

甲基对苯二酚的合成进展

综述了甲基对苯二酚的各种制备方法,并比较了各自的优缺点.着眼于反应条件温和,环境友好的发展方向及选择高效的催化剂,指出双氧水直接羟基化邻甲酚制备甲基对苯二酚是最具有潜力的工艺方法.     

Liquid-Phase Catalytic Hydroxylation of Phenol Using Cu(II), Ni(II) and Zn(II) Complexes of Amidate Ligand Encapsulated in Zeolite-Y as Catalysts

Copper(II), nickel(II) and zinc(II) complexes of amidate ligand 1,2-bis(2-hydroxybenzamido)ethane(H₂hybe) encapsulated in the super cages of zeolite-Y have been prepared and characterized by spectroscopic studies and thermal as well as X-ray diffraction (XRD) patterns. These complexes catalyze the liquid-phase hydroxylation of phenol with H₂O₂ to catechol as a major product and hydroquinone as a minor product. Considering the concentration of substrate and oxidant, amount of catalyst, temperature of the reaction and volume of solvent, a best-suited reaction condition has been optimized to get maximum hydroxylation. Under the optimized reaction conditions, [Cu(hybe)]-Y has shown the highest conversion of 40% after 6h, which is followed by [Ni(hybe)]-Y with 37% conversion and [Zn(hybe)]-Y has shown the poorest performance with 33% conversion. All these catalysts are more selective towards catechol formation (90%), irrespective of their catalytic performance.     

Selective oxidation reactions over titanium and vanadium metallosilicate molecular sieves

Selective oxidation reactions like the oxyfunctionalization of alkanes, hydroxylation of aromatics and sulfoxidation of thioethers have been carried out with dilute hydrogen peroxide over titanium and vanadium metallosilicate molecular sieves with MEL topology, viz., TS-2 and VS-2. Though both the catalysts possess similar activities, substantial differences in the product distribution are observed. The oxyfunctionalization of the primary carbon atoms of the alkanes and the oxidation of the methyl substituents of the aromatic hydrocarbons distinguish VS-2 from TS-2. Both the catalysts are found to be equally active in the hydroxylation of phenol, though they possess different activities in different solvents. In general, the oxidations are deeper over VS-2 than on TS-2.     

乳化剂对坎利酮增溶及生物转化的影响

探索不同乳化剂sp60、sp80、tw60、tw80及其复合乳化剂对坎利酮羟基化的影响。结果表明乳化剂对坎利酮有增溶作用,且tw80、复合乳化剂tw80—sp60对坎利酮微生物转化有促进作用。其中单组分乳化剂tw80的最佳质量分数为0．18％,转化率为90．32％;复合乳化剂tw80-sp60,最佳质量分数为0．09％,转化率为92．22％。     

苯酚直接羟化制备苯二酚催化剂的活性计算

苯酚直接羟化制备苯二酚为液-固相的强放热快反应，催化剂的活性衰减很快，催化剂失活对催化过程的工艺流程、设备及操作条件的选择起着决定性的作用，本文利用催化剂的活性关联式计算了不同流程和操作条件下反应器中催化剂的平均活性，结果表明：宜采用三釜阶式串联反应流程，催化剂回用比例为0．8，过氧化氢加人总量应与平均活性相对应，调节回用比例可控制产物分布，延长催化剂开始失活时间有利于减少生产成本。     

对叔丁基邻苯二酚合成工艺及催化剂研究进展

对国内外对叔丁基邻苯二酚的合成工艺及其最新的研究进展进行了介绍。论述了对叔丁基苯酚羟基化法、邻苯二酚与叔丁醇烷基化法和邻苯二酚与异丁烯烷基化法生产对叔丁基邻苯二酚的合成路线的催化剂。其中对叔丁基苯酚羟基化法是绿色化学工艺,是今后研究的重点。     

氮化硼包覆碳化硅纤维表面CVD法生长碳纳米管研究

目的 通过调节化学气相沉积（CVD）的工艺参数,实现碳纳米管（CNTs）在氮化硼（BN）包覆的碳化硅纤维（SiCf）表面的可控生长。方法 通过控制单一变量,采用扫描电子显微镜、热重分析、X射线光电子能谱等表征手段,系统地研究了CVD工艺参数和BN表面改性对CNTs形貌、长度、含量的影响。结果 通过改变CVD工艺参数,实现了对CNTs形貌、长度、含量的调节与控制,获得了CNTs和BN协同改性的SiC纤维（SiC@BN-CNTs）。其中,SiC@BN-OH在反应温度为700 ℃、反应时间为20 min等参数下具有最大的CNTs产率（质量分数为10.6%）,且形貌良好、含量较高。结论 浸渍催化剂和缩短碳源与载体的距离对生长CNTs有积极影响,增加了CNTs的长度和生长密度;通过调节反应温度和时间能够实现对CNTs长度、含量的精确控制,从而获得高质量、高结晶度的CNTs;在反应器中,气体和催化剂的含量相互影响,在制备过程中需要考虑气体和催化剂的比例,按比例同时增加气体和催化剂的流入速率能够获得更好的结果。BN表面羟基化改性处理增强了BN对催化剂的吸附,促进了催化剂颗粒的分散,提高了CNTs的产率。