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91.
Jian-Kun Yang Bin Zhang Tong Gao Meng-Yue Yang Guo-Zheng Zhao Hua-Jie Zhu 《Natural product research》2018,32(19):2366-2369
A pair of enantiomeric 4-oxabicyclic[4.3.0]lactam derivatives, (+)- and (?)-penicilactam A (1), and one new polyketide derivative penicitrinone F (2) were isolated from the marine-derived fungus Penicillium griseofulvum GT-10. Their structures and absolute configurations were elucidated through extensive spectroscopic analyses combined with the calculated ECD spectra. Penicitrinone F (2) had moderate inhibitory activity towards Bacillus subtilis with a MIC value of 6.3 μM. 相似文献
92.
93.
Shram SI Lazurkina TYu Myasoyedov NF Varfolomeyev SD 《Applied biochemistry and biotechnology》1999,82(1):37-56
Synthesis of prostanoids is accompanied by various processes reducing the product yield. These processes are also known to
affect syntheses of thromboxane (TX) and 12(S)-hydroxy-5(Z),8(Z),10(E),14(Z)-eicosatetraenoic acid (12-HETE). Partially purified preparations of TX synthase and prostaglandin
(PG) synthase were used to optimize TX synthesis with respect to concentrations of the enzymes and eicosapolyenoic acid (EPA).
Conditions for the maximum product yield and the minimum consumption of enzymes were determined. Consumption of the TX synthase
was large owing to its inactivation during the reaction and the nonenzymatic destruction of the intermediate product PG-endoperoxide.
Separate addition of PG and TX synthases increased the product yield by preventing EPA sorption on ballast proteins. Microsomal
12-lipoxygenase (12-LO) was also shown to be inactivated during the reaction, and this process was the major limitation of
12-HETE synthesis. Lipoxygenase reaction in the presence of some reducing agents led to a considerable increase of the 12-HETE
yield, supposedly by preventing further oxidation of the 12-LO reaction product 12-hydroperoxy derivative of eicosatetraenoic
acid. The possibility of using human blood platelet microsomes for preparation of some derivatives of EPAs is discussed. 相似文献
94.
In the present paper we report a quantum chemical (PM3) investigation of reagents, transition structures, intermediates and final products of the nucleophilic addition of hydroxylamine to uracil (U) and 5-fluorouracil (FU). This reaction serves as a model for the more complex enzymatic methylation of 2′-deoxyuridine-5′-monophosphate (dUMP) and 5-fluoro-2′-deoxyuridine-5′-monophosphate (FdUMP) by thymidylate synthase. From the analysis of the frontier orbitals of the isolated and complexed species, as well as from the calculation of activation barriers, we propose that nucleophilic attack usually proceeds after formation of an initial complex between U (or FU) and one neutral and one protonated molecule of hydroxylamine. Our results give some insight into the mechanism of these reactions and account for the higher rate of addition of hydroxylamine to FU, compared to U. The main connection between the chemical simulation and the biological scheme is that in both reactions hydrogen bonding residues are found to be necessary to assist catalysis. 相似文献
95.
Free energy perturbation calculations have been applied to evaluate the relative free energies of binding of 2'-deoxyuridine-5'-monophosphate (dUMP) and its 2- and/or 4-thio and/or 5-fluoro analogues to the wild-type E. coli thymidylate synthase (ecTS). The results accurately reproduce experimentally measured differences in the free energy of binding of dUMP versus 5-fluoro-dUMP to thymidylate synthase. They indicate that preferred binding of dUMP compared to 5-fluoro-dUMP in the binary complex is equally related to (i) more favorable electrostatic interactions of the dUMP molecule in the enzyme active site, and (ii) its less favorable solvation in the aqueous solution. The relative free energies of binding in the binary complex show moderate and qualitatively indistinguishable discrimination among the studied fluorinated and non-fluorinated 2- and/or 4-thio analogues of dUMP. The binding free energies of monothio analogues of dUMP and 5-fluoro-dUMP correspond quite well with experimentally measured activities of these nucleotides in the thymidylate synthase reaction. On the other hand, the binding free energies of both dithio analogues, 2,4-dithio-dUMP and 2,4-dithio-FdUMP, show lack of such correlation. The latter suggests that very low activities of the dithio analogues of dUMP and 5-fluoro-dUMP may relate more to the covalent reaction of these nucleotides within the ternary complex with TS and 5,10-methylenetetrahydrofolate, than to their pre-covalent binding. We speculate that a lack of substrate activity of 2,4-dithio-dUMP is related to the high aromaticity of its pyrimidine ring that prevents the Michael addition of the active site cysteine thiol to the pyrimidine C6 atom. A stronger affinity of the fluorinated analogues of dUMP to thymidylate synthase, compared to the non-fluorinated congeners, results from the fluorine substituent producing a local strain in the C6 region in the pyrimidine ring, thus sensitizing C6 to the Michael addition of the cysteine thiol. 相似文献
96.
Octaketide synthase, a novel plant-specific type III polyketide synthase from Aloe arborescens, efficiently accepted (2RS)-methylmalonyl-CoA as a sole substrate to produce 6-ethyl-4-hydroxy-3,5-dimethyl-2-pyrone. On the other hand, a tetraketide-producing chalcone synthase from Scutellaria baicalensis and a diketide-producing benzalacetone synthase from Rheum palmatum also yielded the unnatural methylated C9 triketide pyrone as a single product by sequential decarboxylative condensations of three molecules of (2RS)-methylmalonyl-CoA. 相似文献
97.
为探讨表没食子儿茶素没食子酸酯(EGCG)对白介素-4(IL-4)刺激的巨噬细胞精氨酸酶1(Arg-1)和诱导型一氧化氮合成酶(iNOS)表达的影响.将6~8周龄Balb/c小鼠经无血清DMEM培养基刺激后,收集腹腔巨噬细胞用于体外培养.体外培养的巨噬细胞经20ng/mL IL-4和不同浓度EGCG处理后,用实时荧光定量PCR(RTqPCR)和酶联免疫吸附试验(ELISA)方法检测Arg-1和iNOS的mRNA表达水平和含量.结果显示IL-4和EGCG单独处理均可显著刺激Arg-1的表达和抑制iNOS的表达,而EGCG(12.5~50μM)增强IL-4刺激的Arg-1表达和IL-4对iNOS表达的抑制作用,且存在剂量依赖效应.上述结果提示EGCG以剂量依赖方式促进IL-4刺激的Arg-1表达、抑制iNOS的表达. 相似文献
98.
将人的诱导型一氧化氮合成酶(hiNOS)启动子构建在带荧光素酶基因的载体pGL3-basic上, 构建成用荧光素酶为系统的启动子, 以研究载体p8.3iNOS. 结果显示, 肾母细胞肿瘤抑制因子(WT1)能够有效地抑制hiNOS启动子的转录; 且WT1的4个选择性剪接本的抑制效果有所不同, 其中WT1(-/-)在两种肝癌细胞(HepG2和Hep3B)中对hiNOS的表达均具有最强的抑制作用, 并且抑制效果具有剂量依赖性, 用Western blot检测结果进一步证实HepG2细胞中WT1(-/-)过量表达能下调hiNOS表达. 以上结果说明WT1在肝癌细胞中对人的hiNOS具有转录调节作用. 相似文献
99.
SU Yan-bin LI Zheng-qiang SU Yan-wen ZHANG Fen-rong 《高等学校化学研究》2008,24(1):65-68
To study the effects of Siqi decoction on rats with Myocardial Ischemia, the model of Myocardium Ischemia was made for the Wistar rats cured with posterior pituitary injection through vein in tail. Siqi decoction, Diaoxinxuekang(DK) and Fufangdanshenpian(FD), the latter two drugs of which were effective TCM drugs of anti-Myocardial Ischemia at present, were administrated to the rats with Myocardium Ischemia for 5 days to compare the effect of anti-Myocardium Ischemia as reference drugs by measuring the changes of NO concentration and activity of NOS in the rat blood serum with Myocardial Ischemia. There was a remarkable increase in the NO concentration and activity of NOS in serum in Siqi decoction groups compared with those in control group(p〈0.05). The results of the prevention group in experiment of Siqi decoction are better than those of the cure group. Siqi decoction was really fit for Myocardium Ischemia via increasing NO concentration by stimulating the activity of NOS in serum. The effect of Siqi decoction against Myocardium Ischemia in preventive group is better than the curative that of Siqi decoction in the curative group. 相似文献
100.
Peter Zipper Manfred Kriechbaum Rudolf Wilfing Helmut Durchschlag 《Monatshefte für Chemie / Chemical Monthly》1986,117(5):557-572
The X-ray induced aggregation of the sulfhydryl enzyme malate synthase in aqueous solution was monitoredin situ by time-resolved small-angle X-ray scattering. Experiments were performed in the absence/presence of various additives: formate, superoxide dismutase, catalase, NaCl, acetyl-CoA, glyoxylate, malate, pyruvate, -ketobutyrate, oxaloacetate, glycollate, lactate. The scattering curves were measured as a function of the time of irradiation and were analysed in terms of radii of gyration, degrees of aggregation, distance distribution functions, and parameters derived therefrom. Irradiation in the absence of additives resulted in a strong aggregation of enzyme particles. Each of the additives impeded aggregation, however to a different extent. The OH scavenger formate reduced aggregation efficiently; less pronounced effects were registered for superoxide dismutase and/or catalase (the scavengers for
and H2O2), and for NaCl. Very pronounced diminutions of the aggregation phenomena were provided by substrates or analogues; the efficiency of these substances as radioprotectors may be explained by their action as both scavengers and specific ligands. Based on these results some implications for the performance of conventional small-angle X-ray scattering experiments on biopolymers are derived.
Der Einfluß von Zusätzen auf die röntgeninduzierte Aggregation der Malatsynthase. Registrierung des Aggregationsvorganges in situ mittels zeitaufgelöster Röntgenkleinwinkelstreuung
Zusammenfassung Die röntgeninduzierte Aggregation des Sulfhydrylenzyms Malatsynthase in wäßriger Lösung wurdein situ mittels zeitaufgelöster Röntgenkleinwinkelstreuung messend verfolgt. Streuexperimente wurden in An- bzw. Abwesenheit verschiedener Zusätze durchgeführt: Formiat, Superoxiddismutase, Catalase, NaCl, Acetyl-CoA, Glyoxylat, Malat, Pyruvat, -Ketobutyrat, Oxalacetat, Glycolat, Lactat. Die Streukurven wurden als Funktion der Bestrahlungsdauer registriert. Die Auswertung lieferte Streumassenradien, Aggregationsgrade, Abstandsverteilungsfunktionen, und daraus abgeleitete Parameter. Die Bestrahlung in Abwesenheit von Zusätzen verursachte eine starke Aggregation der Enzymteilchen. Jeder der Zusätze verminderte die Aggregation, wenn auch in unterschiedlichem Ausmaß. Der OH Fänger Formiat verringerte die Aggregation wirksam; weniger stark ausgeprägte Effekte ergaben sich für die bzw. H2O2 Fänger Superoxiddismutase bzw. Catalase und für NaCl. Substrate und Substratanaloge reduzierten das Ausmaß der Aggregation besonders wirkungsvoll; der Schutzeffekt dieser Substanzen kann durch ihre zweifache Wirkung als Fänger bzw. spezifische Liganden erklärt werden. Ausgehend von diesen Ergebnissen werden einige Schlußfolgerungen für die Durchführung üblicher Röntgenkleinwinkelexperimente an Biopolymeren abgeleitet.相似文献