金属改性的介孔硅材料FSM-16催化苯酚与H_2O_2合成苯二酚

研究了金属改性的介孔硅材料FSM-16在该反应中的催化性能。其中Fe和Cu改性的FSM-16表现出比较好的性能。在Fe-FSM-16的作用下,苯酚的转化率达到27.8%,对苯二酚和邻苯二酚选择性达到96.4%(邻/对=1.8)。FT-IR和XRD表征证明铜离子进入了FSM-16的骨架,并形成了Si—O—Cu键。     

One-step Continuous Phenol Synthesis Technology via Selective Hydroxylation of Benzene over Ultrafine TS-1 in a Submerged Ceramic Membrane Reactor☆

A new route towards phenol production by one-step selective hydroxylation of benzene with hydrogen peroxide over ultrafine titanium silicalites-1 (TS-1) in a submerged ceramic membrane reactor was deve...     

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     

The 2-oxoglutarate-dependent oxygenase JMJD6 catalyses oxidation of lysine residues to give 5S-hydroxylysine residues

Amino acid analyses reveal that JMJD6-catalysed hydroxylation of RNA-splicing regulatory protein fragments occurs to give hydroxylysine products with 5S stereochemistry. This contrasts with collagen lysyl hydroxylases, which give 5R-hydroxylated products. The work suggests that more than one subfamily of lysyl hydroxylases has evolved and illustrates the importance of stereochemical assignments in proteomic analyses.     

11α hydroxylation of 16α, 17‐epoxyprogesterone in biphasic ionic liquid/water system by Aspergillus ochraceus

BACKGROUND: The improved efficiency of steroid biotransformation using the biphasic system is generally attributed to the positive effect on the solubility of substrate in aqueous media. A promising alternative for the application of organic solvents in biphasic systems is the use of ionic liquids (ILs). This study aims to investigate the applicability of the biphasic ILs/water system for 11α hydroxylation of 16α, 17‐epoxyprogesterone (HEP) by Aspergillus ochraceus. RESULTS: Of the seven ILs tested, [C₃mim][PF₆] exhibited the best biocompatibility, with markedly improved biotransformation efficiency. In the [C₃mim][PF₆]‐based biphasic system, substrate conversion reached 90% under the condition in which buffer pH, volume ratio of buffer to ILs, cell concentration, and substrate concentration were 4.8, 10/1, 165 g L^?1 and 20 g L^?1, respectively. This is more efficient than that of the monophasic aqueous system. The effects of the cations and anions of these ILs on the 11α hydroxylation of 16α, 17‐epoxyprogesterone (HEP) by A. ochraceus is also discussed. CONCLUSION: The above results showed that IL/water biphasic system improved the efficiency of 11α hydroxylation of 16α, 17‐epoxyprogesterone (HEP) by A. ochraceus, thus suggesting the potential industrial application of ILs‐based biphasic systems for steroid biotransformation. © 2012 Society of Chemical Industry     

Mammalian Cytochrome P450-Dependent Metabolism of Polychlorinated Dibenzo-p-dioxins and Coplanar Polychlorinated Biphenyls

Polychlorinated dibenzo-p-dioxins (PCDDs) and coplanar polychlorinated biphenyls (PCBs) contribute to dioxin toxicity in humans and wildlife after bioaccumulation through the food chain from the environment. The authors examined human and rat cytochrome P450 (CYP)-dependent metabolism of PCDDs and PCBs. A number of human CYP isoforms belonging to the CYP1 and CYP2 families showed remarkable activities toward low-chlorinated PCDDs. In particular, human CYP1A1, CYP1A2, and CYP1B1 showed high activities toward monoCDDs, diCDDs, and triCDDs but no detectable activity toward 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-tetraCDD). Large amino acids located at putative substrate-recognition sites and the F-G loop in rat CYP1A1 contributed to the successful metabolism of 2,3,7,8-tetraCDD. Rat, but not human, CYP1A1 metabolized 3,3'',4,4'',5-pentachlorobiphenyl (CB126) to two hydroxylated metabolites. These metabolites are probably less toxic than is CB126, due to their higher solubility. Homology models of human and rat CYP1A1s and CB126 docking studies indicated that two amino acid differences in the CB126-binding cavity were important for CB126 metabolism. In this review, the importance of CYPs in the metabolism of dioxins and PCBs in mammals and the species-based differences between humans and rats are described. In addition, the authors reveal the molecular mechanism behind the binding modes of dioxins and PCBs in the heme pocket of CYPs.     

铁酸镁催化剂催化苯酚羟化作用的研究

采用共沉淀法合成了一种新的用于苯酚羟基化反应的催化剂铁酸镁( Mg Fe2 O4 ) ,用 XRD、IR进行了表征。考察了溶剂、氧化剂对苯酚羟基化反应的影响。研究结果表明 ,以水为溶剂、过氧化氢为氧化剂 ,铁酸镁催化剂催化苯酚羟基化反应有较高的催化活性 ,并初步提出了反应机理。     

硅烷偶联剂改性玻璃纤维增强硅气凝胶的研究

为了达到增强硅气凝胶力学性能的目的,采用硅烷偶联剂KH550与KH560二步改性接枝玻璃纤维,进而制备纤维增强硅气凝胶。利用扫描电子显微镜、红外光谱仪、比表面及孔径分布仪、热重-差热分析仪、导热系数仪、电子动静态疲劳试验机等对其表征。实验结果表明：硅烷偶联剂改性玻璃纤维与硅气凝胶复合后网络结构更加均匀、骨架强度更加稳定、孔径多在30 nm以下、具有良好的热稳定性;同时,改性玻璃纤维的最佳添加量为20%（质量分数）,此时其密度为0.167 g/cm³,导热系数为0.018 5 W/（m·K）,接触角为127°,抗弯强度为1.042 MPa,抗压强度为0.669 MPa,达到预期实验目的。     

类水滑石CuNiAl的制备、表征及其催化性能的研究

采用水热法和尿素水解法首次合成了三元类水滑石CuNiAl(Cu+Ni/Al=3,Cu/Ni=5.0,3.0,1.0,0.33),将合成的类水滑石用于苯羟基化反应。采用X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、扫描电镜(SEM)和透射电镜(TEM)等手段对类水滑石进行表征,以CuNiAl31作为催化剂,考察了反应时间、反应温度、溶剂及溶剂用量、催化剂用量、n(benzene)/n(H_2O_2)对苯羟化反应的影响。结果表明:与CuNiAl11、CuNiAl21、CuNiAl13催化剂相比,CuNiAl31具有较高的反应活性,反应的最佳条件为:反应时间6h、反应温度65℃、15 ml吡啶作为溶剂、10mg催化剂、n(benzene)/n(H_2O_2)=3.0时,苯的转化率为7%,苯酚的选择性几乎为100%。     

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。