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21.
采用UωB97X-D/6-311+G**方法, 研究了气相、 甲苯和水中OH自由基(·OH)引发CH3SSCH3自由基阳离子(CH3SSC +, DMDS?+)裂解的反应机理, 并讨论了溶剂效应对反应的影响. 结果表明, ·OH和DMDS·+首先形成自由基耦合产物CH3S(OH)SCH3+(R1)和氢提取产物复合物[CH2=SSCH3+H2O]+(R2); 随后R1裂解直接发生 S—S键断裂协同质子转移, 而R2裂解依次发生构象变化、 C=S键亲碳加成和S—S键断裂协同质子转移. 去质子化的裂解产物为CH3SOH, CH2=S和HSCH2OH. 甲苯略微降低了裂解反应速控步骤的自由能垒. 水溶剂有利于R1裂解, 但不利于R2裂解, 尤其是单个水分子参与反应. 在气相、 甲苯和水中, 以·OH和DMDS·+为初始反应物, 虽然速控步骤的自由能垒为167.6~202.8 kJ/mol, 但裂解反应均是放热反应(?154.3~?31.4 kJ/mol). 相似文献
22.
《Arabian Journal of Chemistry》2022,15(4):103707
Alsophila spinulosa is a tree-like fern, and many evidences suggested that plant polyphenols had the potential therapeutic for Alzheimer s disease (AD). Herein, polyphenols (ASP) was isolated from A. spinulosa leaves and its major constituent were isoorientin and vitexin. ASP displayed excellent antioxidant activity and obvious anti-lipid peroxidation capacity in vitro. ASP improved the survival rate of C. elegans under high temperature by enhancing the antioxidant enzymes activities and decreasing the lipid peroxidation level. Moreover, ASP alleviated β-amyloid (Aβ) induced paralysis and reduced Aβ deposition, decreased reactive oxygen species (ROS) accumulation and improved the level of skn-1 mRNA. In addition, ASP decreased the levels of pdk-1 and akt-1 mRNA in P13K/AKT signaling pathway. In conclusion, ASP may be a potential ingredient for the alleviation of AD. 相似文献
23.
《Arabian Journal of Chemistry》2022,15(9):104037
This study aimed to investigate the beneficial role of Millettia ferruginea extract (MF) in preventing cisplatin (Cisp) induced nephrotoxicity in rats. A total of 55 metabolites were identified using LC-MS analysis. The in vivo results indicated that MF pretreatment for 4 weeks (20 mg/kg b.w.) remarkably attenuated the altered renal biomarkers by decreasing the levels of plasma creatinine, urea, and uric acid when compared to the Cisp-group. The nephroprotective capacity of MF was further strengthened by histopathological observations, where Cisp + MF treated rats showed lower number of inflammatory cells and tubular degenerative changes than the Cisp-group. The harmful effects of cisplatin on renal oxidative stress indicators (MDA, SOD, CAT, and GPx), were restored by the treatment of MF. In addition, the reduction of inflammatory markers (IL-6 and TNF-α), associated with alleviating DNA fragmentation, highlighted the preventive effect of MF in kidney tissue. Additionally, MF components presented lower binding energies when docked into the active site of TNF-α and IL-6. The present findings concluded that M. ferruginea extract exhibited nephroprotective potential, which may be attributed to its antioxidant and anti-inflammatory properties. Further work is recommended to confirm the current results, explore the involved mechanism of action, and determine the therapeutic doses and time. 相似文献
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SynthesesandStudiesofPEG┐b┐PNIPABlockPolymersCAOWei-xiao**andZHANGTao(ColegeofChemistryandMolecularEnginering,PekingUniversit... 相似文献
26.
芦荟大黄素的电化学研究 总被引:8,自引:1,他引:8
用单扫示波极谱法研究了芦荟大黄素的电化学行为。在5%Na2CO3+5%NaOH(9+1)底液中,芦荟大黄素于-0.84V(P1)和-0.97V(P2)处产生两个示波极谱峰,利用P1可测定芦荟大黄素,线性范围为 0.11-24mg/L和3.0-28.6mg/L,检测限为0.06mg/L。将该法应用于中药大黄中的芦荟大黄素的测定,结果满意。另外,讨论了芦荟大黄素清除由邻苯三酚自氧化产生的超氧自由基(O2)的作用。 相似文献
27.
Lactate derivatives are important synthetic precursors to a variety of pharmaceutical products. Previously reported methods to prepare lactates require multiple steps or have limited scopes. Herein, we report a Ni-catalyzed reductive addition of a variety of alkyl iodides to α-oxyacrylates to afford substituted lactates. Exploring the scope of radical acceptors reveals that electron-deficient alkenes, ranging from cyclohexenone to para-caboxystyrene, undergo efficient coupling with alkyl iodides. This method represents an alternative strategy access lactate derivatives. 相似文献
28.
A Mn(III)-promoted radical oxidative ipso-annulation reaction of biaryl ynones with sodium sulfinates to construct various substituted spiro[5.5]trienones has been explored in this study. This protocol is characterized by mild reaction conditions, good substrates functional group compatibility, cheap and easily prepared Mn(OAc)3·2H2O, and it demonstrates a simple operation. 相似文献
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30.
Pedro J.?Silva Pedro A.?Fernandes Maria J.?RamosEmail author 《Theoretical chemistry accounts》2003,110(5):345-351
Prostaglandin H synthase catalyzes the oxygenation of arachidonic acid into the cyclic endoperoxide, prostaglandin G2 (PGG2), and the subsequent reduction of PGG2 to the corresponding alcohol, prostaglandin H2 (PGH2), the precursor of all prostaglandins and thromboxanes. Both radical abstraction by a neighboring tyrosyl radical and combined radical/carbocationic models have been proposed to explain the cyclooxygenase part of this reaction. We have used density functional theory calculations to study the mechanism of the formation of the cyclooxygenated product PGG2. We found an activation free energy for the initial hydrogen abstraction by the tyrosine radical of 15.6 kcal/mol, and of 14.5 kcal/mol for peroxo bridge formation, in remarkable agreement with the experimental value of 15.0 kcal/mol. Subsequent steps of the radical-based mechanism were found to happen with smaller barriers. A combined radical/carbocation mechanism proceeding through a sigmatropic hydrogen shift was ruled out, owing to its much larger activation free energy of 36.5 kcal/mol. Supplementary material is available in the online version of this article at http://dx.doi.org/10.1007/s00214-003-0476-9. Electronic Supplementary MaterialSupplementary material is available in the online version of this article at
Electronic Supplementary Material: Supplementary material is available in the online version of this article at 相似文献