Epoxide‐Hydrolase‐Initiated Hydrolysis/Rearrangement Cascade of a Methylene‐Interrupted Bis‐Epoxide Yields Chiral THF Moieties without Involvement of a “Cyclase”

Cyclase‐free at last : A methylene‐interrupted meso‐bis‐epoxide was stereoselectively converted into dihydroxy‐tetrahydrofuran derivatives with excellent de and ee values through an enzyme‐triggered nucleophilic hydrolysis/cyclisation cascade. Molecular modelling showed that the point of enzyme attack was determined by the stereospecificity of the epoxide hydrolase, whereas the stereochemical course of the cyclisation step was solely governed by Baldwin's rules and did not invoke the involvement of a “cyclase”.

     

Modification of Substrate Specificity Resulting in an Epoxide Hydrolase with Shifted Enantiopreference for (2,3‐Epoxypropyl)benzene

Random mutagenesis targeted at hotspots of noncatalytic active‐site residues of potato epoxide hydrolase StEH1 combined with an enzyme‐activity screen allowed the isolation of enzyme variants displaying altered enantiopreference in the catalyzed hydrolysis of (2,3‐epoxypropyl)benzene. The wild‐type enzyme favored the S enantiomer with a ratio of 2.5:1, whereas the variant displaying the most radical functional changes showed a 15:1 preference for the R enantiomer. This mutant had accumulated four substitutions distributed over two out of four mutated hotspots: W106L, L109Y, V141K, and I151V. The underlying causes of the enantioselectivity were a decreased catalytic efficiency in the catalyzed hydrolysis of the S enantiomer combined with retained activity with the R enantiomer. The results demonstrate the feasibility of molding the stereoselectivity of this biocatalytically relevant enzyme.     

Relative Importance of Soluble and Microsomal Epoxide Hydrolases for the Hydrolysis of Epoxy-Fatty Acids in Human Tissues

Epoxy-fatty acids (EpFAs) are endogenous lipid mediators that have a large breadth of biological activities, including the regulation of blood pressure, inflammation, angiogenesis, and pain perception. For the past 20 years, soluble epoxide hydrolase (sEH) has been recognized as the primary enzyme for degrading EpFAs in vivo. The sEH converts EpFAs to the generally less biologically active 1,2-diols, which are quickly eliminated from the body. Thus, inhibitors of sEH are being developed as potential drug therapeutics for various diseases including neuropathic pain. Recent findings suggest that other epoxide hydrolases (EHs) such as microsomal epoxide hydrolase (mEH) and epoxide hydrolase-3 (EH3) can contribute significantly to the in vivo metabolism of EpFAs. In this study, we used two complementary approaches to probe the relative importance of sEH, mEH, and EH3 in 15 human tissue extracts: hydrolysis of 14,15-EET and 13,14-EDP using selective inhibitors and protein quantification. The sEH hydrolyzed the majority of EpFAs in all of the tissues investigated, mEH hydrolyzed a significant portion of EpFAs in several tissues, whereas no significant role in EpFAs metabolism was observed for EH3. Our findings indicate that residual mEH activity could limit the therapeutic efficacy of sEH inhibition in certain organs.     

碳亲核试剂与氮杂环丙烷开环反应的研究进展

氮杂环丙烷化合物是有机合成中重要的杂环化合物之一,其开环反应越来越受到有机化学家的关注.本文综述了近年来各类碳亲核试剂与氮杂环丙烷开环反应的研究进展,大多具有反应条件温和、易控制、区域选择性好、收率高等优点.     

Improved Stabilization of Genetically Modified Penicillin G Acylase in the Presence of Organic Cosolvents by Co‐ Immobilization of the Enzyme with Polyethyleneimine

Penicillin G acylase (PGA) is an enzyme that hardly interacts with polycationic polymers (e.g., polyethyleneimine, PEI) and thus the enzyme cannot be stabilized against the action of organic solvents by its co‐immobilization with the polymer in the same support, neither covalently attached to the support nor adsorbed on the already immobilized enzyme. However, a new mutant PGA bearing eight additional Glu residues homogenously distributed throughout the enzyme surface may interact with the polymer. The co‐immobilization of the enzyme and PEI on glyoxyl‐agarose allows one to fully take advantage of the stabilization produced by the multipoint covalent attachment and by the protective hydrophilic micro‐environment generated by the polycationic polymer, enabling a significant stabilization of the immobilized PGA in the presence of organic solvents.     

新型光电催化反应器对甲基橙的脱色降解研究

以热氧化法制备的TiO2/Ti薄膜电极为阳极、石墨电极为阴极和饱和甘汞电极为参比电极,设计一种新型的光电化学催化反应器。研究了三种不同催化体系对甲基橙的降解率,同时研究了初始pH、反应时间对脱色率的影响,结果显示,光电化学催化体系对甲基橙的降解效果优于另外两种催化体系。当溶液初始pH=3.0,其他条件不变的情况下,双槽反应器阴阳两极槽甲基橙溶液的脱色率分别达到82.35%和91.30%,单槽反应器脱色率为85.00%。单双槽反应器均达到了＂双极双效＂的目的。     

Geranylation of Cyclic Dipeptides by the Dimethylallyl Transferase AnaPT Resulting in a Shift of Prenylation Position on the Indole Ring

The dimethylallyl transferase AnaPT from Neosartorya fischeri is involved in the biosynthesis of acetylaszonalenin and catalyses the regioselective and stereospecific C3α‐prenylation of (R)‐benzodiazepinedione in the presence of dimethylallyl diphosphate. This enzyme also converts several tryptophan‐containing cyclic dipeptides to C3α‐prenylated indolines. In this study, we demonstrate the geranylation of (R)‐benzodiazepinedione and five other cyclic dipeptides by AnaPT in the presence of geranyl diphosphate (GPP). Interestingly, structure elucidation by NMR and MS analyses revealed that, with GPP, the geranyl moiety is attached to C‐6 or C‐7 rather than C‐3 of the indole ring of the enzyme products. For (R)‐benzodiazepinedione, one dominant C6‐geranylated derivative was obtained, whereas the other five substrates yielded both C6‐ and C7‐geranylated products. Neither acceptance of GPP by a dimethylallyl transferase from the dimethylallyltryptophan synthase superfamily, nor the alkylation shift from C‐3 to the benzene ring of the indole nucleus has been reported previously.     

Fenton氧化法处理难降解有机废水研究进展

系统地分析了Fenton氧化法处理难降解有机废水时,pH、H2O2投加量、初始Fe2＋浓度、反应温度和反应时间等对处理效果的影响,并指出处理废水时应注意的相关细节。     

有机精细化工中间体的发展现状及仿生催化氧化在中间体合成中的研究进展

综述了近年来我国有机精细化工中间体研究开发以及生产的现状,分析了我国有机精细化工中间体在研究开发、生产及应用方面所面临的问题及今后发展的机遇。同时介绍了笔者在仿生催化氧化合成有机精细化工中间体方面的研究进展,展望了仿生催化氧化技术在有机精细化工中间合成体领域的应用前景。     

固体酸对苯与烯烃烷基化反应的催化活性研究

对改性粘土类、固体超强酸ＺｒＯ２－ＳＯ４２－／ＳｉＯ２及改性Ｙ型分子筛三大类固体酸催化剂进行了比表面、孔径分布测定及正丁胺－ＴＰＤ表征，评价了它们对苯与烯烃烷基化反应的催化性能，并对催化活性的改性Ｙ型分子筛Ｓｒｌａｙ催化剂进行了失活与再生实验。     

Studies on the substitution of inorganic fertilizers with organic manure and their effect on soil fertility in rice—wheat rotation

Field studies on the substitution of N and P fertilizers with farm yard manure (FYM) and their effect on the fertility status of a loamy sand soil in rice—wheat rotation are reported. The treatments consisted of application of 12 t FYM ha^–1 in combination with graded levels of N and P. Application of fertilizer N, FYM and their different combinations increased the rice yield significantly. There was no significant response to P application. The magnitude of response to the application of 12 t FYM and its combined use with each of 40 kg and 80 kg N ha^–1 was 0.7, 2.2 and 3.9 t ha^–1 respectively. Application of 120 kg N ha^–1 alone increased the yield by 3.9 t ha^–1, and was comparable to rice yield obtained with 80 kg N and 12 t FYM ha^–1. This indicated that 12 t FYM ha^–1 could be substituted for 40 kg N as inorganic fertilizer in rice. In addition FYM gave residual effects equivalent to 30 kg N and 13.1 kg P ha^–1 in the succeeding wheat. The effect of single or combined use of inorganic fertilizers and FYM was significantly reflected in the build up of available N, P, K and organic carbon contents of the soil. The relationship for predicting rice yield and nutrients uptake were also computed and are discussed.     

Perturbed Angular Correlation Characterization of Indium Species on In/H-ZSM5 in the Presence of Water and Catalytic Deactivation Studies During the SCR of NO x with Methane

An In(4 wt%)-impregnated H-ZSM5 catalyst was characterized under wet and dry conditions by time-differential perturbed angular correlation (PAC) and by temperature-programmed reduction (TPR). Different indium species were quantified, correlating their structure with the catalyst deactivation due to the presence of water during the NO selective catalytic reduction (SCR) with methane. The fresh sample contains 60% of indium oxide and 40% of (InO)⁺ species at exchange sites, the latter being the active species for the reaction under study. Under wet atmosphere, hyperfine interactions determined by PAC indicate the formation of two types of In hydroxide species and the decrease of both (InO)⁺ and In₂O₃. TPR and PAC characterizations also show that deactivation is due to the decrease of (InO)⁺ at exchange sites to form, after water is removed, different non-active In oxide species.