Mechanism of OH formation from ozonolysis of isoprene: a quantum-chemical study

The formation and unimolecular reactions of primary ozonides and carbonyl oxides arising from the O(3)-initiated reactions of isoprene have been investigated using density functional theory and ab initio molecular orbital calculations. The activation energies of O(3) cycloaddition to the two double bonds of isoprene are found to be comparable (3.3-3.4 kcal mol(-1)), implying that the initial two O(3) addition pathways are nearly equally accessible. The reaction energies of O(3) addition to isoprene are between -47 and -48 kcal mol(-1). Cleavage of primary ozonides to form carbonyl oxides occurs with a barrier of 11-16 kcal mol(-1) above the ground state of the primary ozonide, and the decomposition energies range from -5 to -13 kcal mol(-1). OH formation is shown to occur primarily via decomposition of the carbonyl oxides with the syn-positioned methyl (alkyl) group, which is more favorable than isomerization to form dioxirane (by 1.1-3.3 kcal mol(-1)). Using the transition-state theory and master equation formalism, we determine an OH yield of 0.25 from prompt and thermal decomposition of the carbonyl oxides.     

亚临床肝性脑病患者的血清锌,铜含量的测定及临床意义

检测了３０例慢性活动性肝炎患者、３０例肝硬化患者、３０例亚临床肝性脑病患者血清中的铜、锌含量，并与正常对照组进行比较分析，探讨了微量元素铜、锌的血清含量改变及其影响因素，分析其临床意义。结果表明体内的铜锌含量与肝脏功能有密切的关系。在慢性活动性肝炎时，虽然肝脏功能有一定的损害，但由于肝脏的代偿能力强，铜，锌含量仍可保持在正常水平，而在肝硬化、亚临床肝性脑病时，铜锌明显降低，而铜锌含量的降低又导致机     

Kinetic isotope effects implicate the iron-oxene as the sole oxidant in P450-catalyzed N-dealkylation

Multiple oxidants have been implicated as playing a role in cytochrome P450-mediated oxidations. Herein, we report results on N-dealkylation, one of the most facile reactions mediated by P450 enzymes. We have employed the N-oxides of a series of para-substituted 13C2H2-labeled N,N-dimethylanilines to function as both substrates and surrogate oxygen atom donors for P450cam and P4502E1. Kinetic isotope effect profiles obtained using the N-oxide system were found to closely match the profiles produced using the complete NAD(P)H/NAD(P)-P450 reductase/O2 system. The results are consistent with oxidation occurring solely through an iron-oxene species.     

超分子结构二氟尼柳插层镁铝水滑石的合成与表征

采用离子交换和共沉淀两种不同方法将二氟尼柳插入镁铝水滑石层间，得到一种新型的有机-无机层状复合材料。通过X射线粉末衍射、红外光谱、元素分析和热重-差热等手段对材料进行了表征。结果表明，离子交换法和共沉淀法成功地将二氟尼柳插入水滑石，得到的材料层状结构完整、晶相单一，且层间距均大于二氟尼柳分子尺寸，扩大为1.81～2.14 nm；二氟尼柳插入后，复合水滑石材料的热稳定性大幅度提高。客体二氟尼柳与主体层板之间存在超分子作用力，二氟尼柳分子的羧基与水滑石层板之间相互作用，以双层倾斜交替地排列于层板之间。此外，根据其超分子作用力建立了二氟尼柳插层镁铝水滑石的超分子结构模型。     

Effect of pressure on the proton transfer rate from a photoacid to a solvent. 4. Photoacids in methanol

The pressure dependence of the excited-state proton dissociation rate constant of four photoacids, 2-naphthol-6,8-disulfonate (2N68DS), 10-hydroxycamptothecin (10-CPT), 5-cyano-2-naphthol (5CN2), and 5,8-dicyano-2-naphthol (DCN2), are studied in methanol. The results are compared with the results of the pressure dependence study we recently conducted for several photoacids in water, ethanol, and propanol. The pressure dependence is explained using an approximate stepwise two-coordinate proton transfer model. The increase in rate, as a function of pressure, manifests a strong dependence of proton tunneling on the distance which decreases with an increase of pressure between the two oxygen atoms involved in the process. The decrease in the proton transfer rate with increasing pressure reflects the dependence of the reaction on the solvent relaxation rate. We found that, for the relatively weak photoacids 2N68DS, 10-CPT, and 5CN2, the proton transfer rate constant increases by a factor of about 5-8 at a pressure of about 1.5 GPa. For a strong photoacid like DCN2, the rate increase was only by a factor of 2.     

Double cyclisation of phenylglycine-o-carboxylic acids—I: New stable mesoionic oxazolones

Remarkably stable mesoionic oxazolones possessing an oxazolo[3,2-a]quinolinium structure (5a–b),8,16, 17) were obtained by the double cyclisation of phenylglycine-o-carboxylic acids (3a–c) in refluxing acetic anhydride or in benzoic anhydride at 140°, The 0-Ac group was eliminated to give the corresponding lactones (6a–b) or replaced by O-Ts (7). IR stretching vibrations of the endo-carbonyl were in the range 1710–1768 cm^?1, while v_1-CH exhibited unusually high values (3159–3194 cm^-1). 1-Acyl derivatives could be obtained only with TFAA (23–24), although easy deuteration of the same position took place in the presence of traces of trifluoroacetic acid. Hydrolysis of 5b led to the α-quinolone-N-acetic acid 27a. In the case of 5a, hydrolysis was accompanied by self-acylation of the nucleophilic site at C-4 with formation of a dimeric acid 28a. The presence of an additional Me group in phenylalanine-o-carboxylic acid (36) activates the corresponding mesoionic oxazolone 37 so that 1-acylation becomes possible with formation of the fused oxazole 38 by the Dakin-West reaction. Temperature dependent magnetic non-equivalence of methylene protons has been observed in acids 3b-d and f and also in the 7-membered anhydride 48b.     

PMR-Spektren einiger Alkoxy-9-chlor-6-nitroacridine

The spectra of some 9-chloro-6-nitroacridines with methoxy substituents in position 1,4; 2,4; 3,4; 2,3; and ethoxy substituents in positions 1, 2, 3, were recorded. The influence of electron releasing alkoxy groups and electron withdrawing nitro groups on chemical shifts of protons in the 9-chloroacridinic cycle was discussed and PMR parameters were determined, comparatively with those of acridine and 9-chloroacridine. Good agreement between calculated and experimental values is observed. The spectrum of 9-chloro-1,2,3-triethoxyacridine shows for the four protons of the ringC. (H-5, H-6, H-7, H-8) anAMNX coupling pattern whose parameters were determined.     

玉米芯水溶性多糖的分离纯化和抗凝血活性研究

从玉米芯中提取到水提水溶性粗多糖,通过乙醇分级、冻融、凝胶过滤层析,生物测定导向等手段,分离到一种能延长体外凝血时间,而且具有外源抗凝血功能的多糖CCⅢ.CCⅢ对活化部分凝血酶原时间(APTT)无显著影响,但可显著延长体外抗凝血时间(PT).将CCⅢ纯化,经糖组成分析、甲基化、高碘酸氧化、Smith降解和GC-MS分析,确定该多糖结构为:β-(1→4)Glc,(1→3)Xyl构成主链,Glc在6-O处有分枝.平均每10个糖残基有1个分枝,支链由β-(1→3)Xyl,(1→3)Glc构成.     

High-throughput screening of enzyme libraries: thiolactonases evolved by fluorescence-activated sorting of single cells in emulsion compartments

Single bacterial cells, each expressing a different library variant, were compartmentalized in aqueous droplets of water-in-oil (w/o) emulsions, thus maintaining a linkage between a plasmid-borne gene, the encoded enzyme variant, and the fluorescent product this enzyme may generate. Conversion into a double, water-in-oil-in-water (w/o/w) emulsion enabled the sorting of these compartments by FACS, as well as the isolation of living bacteria cells and their enzyme-coding genes. We demonstrate the directed evolution of new enzyme variants by screening >10(7) serum paraoxonase (PON1) mutants, to yield 100-fold improvements in thiolactonase activity. In vitro compartmentalization (IVC) of single cells, each carrying >10(4) enzyme molecules, in a volume of <10 femtoliter (fl), enabled detection and selection despite the fast, spontaneous hydrolysis of the substrate, the very low initial thiolactonase activity of PON1, and the use of difusable fluorescent products.     

一种新的磷酸根离子敏感电极研究

一种新的磷酸根离子敏感电极研究肖丹，俞汝勤，李军，袁孔铨（湖南大学化学化工系，长沙，４１００８２）关键词磷酸根，离子选择电极，磷酸二氢根磷酸根离子浓度的测定在化学化工、环境保护、生命科学和临床医学等领域有着重要的意义。对磷酸根离子敏感电极的研究和探索...