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光和热驱动金催化邻炔基酚与芳基重氮盐的反应:两种机制相似性和差异性的理论研究
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作者 金蕊 郭昕怡 +3 位作者 彭灵雅 刘向洋 方维海 崔刚龙 《Chinese Journal of Chemical Physics》 SCIE EI CAS CSCD 2024年第1期87-99,I0036-I0092,I0118,共71页
实验上发现,邻炔基酚与芳基重氮盐在热催化和光催化条件下反应可生成不同的产物,然而反应机理尚不清晰.本文采用MSCASPT2和密度泛函理论方法研究了热和光驱动反应的催化机理.结果表明,热催化和光催化反应的初始历程相同,都是在HCO3-协... 实验上发现,邻炔基酚与芳基重氮盐在热催化和光催化条件下反应可生成不同的产物,然而反应机理尚不清晰.本文采用MSCASPT2和密度泛函理论方法研究了热和光驱动反应的催化机理.结果表明,热催化和光催化反应的初始历程相同,都是在HCO3-协助下由Au(Ⅰ)催化剂和邻炔基酚反应得到乙烯基Au(Ⅰ)中间体.在此过程中,Au(l)催化剂与邻炔基酚反应克服14.8 kcal/mol的能垒生成结构扭曲的配合物,此时邻炔基酚的C≡C三键被活化.随后,乙烯基Au(Ⅰ)中间体和芳基重氮盐形成复合物,热催化和光催化反应开始分叉.在黑暗条件下,反应克服15.7 kcal/mol的能垒后生成最终的热催化产物,此时芳基重氮盐的末端N原子直接与乙烯基Au(Ⅰ)中间体的C原子成键.在光照条件下,复合物首先弛豫到激发单重态,经9.8×10^(9)s^(-1)的高效系间窜跃过程衰变到T_(1)态.在T_(1)态,克服7.8 kcal/mol的能垒完成脱氮反应,产生与乙烯基Au(Ⅰ)中间体的Au原子具有相互作用的芳基自由基,随后发生系间窜跃过程到达基态.在基态形成最终的光催化产物.本研究为理解Au(Ⅰ)催化剂与芳基重氮盐的热催化和光催化反应提供了重要的机理见解,发现了无辐射跃迁在光催化反应中的关键作用. 展开更多
关键词 光氧化还原催化 过渡金属配合物 密度泛函理论 反应机理 Au(Ⅰ)催化剂 光物理 芳基重氮盐 邻炔基酚
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Fas-670 A/G polymorphism predicts prognosis of hepatocellular carcinoma after curative resection in Chinese Han population
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作者 xin-yi guo Yi-Lin Xia +4 位作者 Zhi-Yang Li Ran Li Yang Fan Wen-Mo Yao Fei Liu 《Hepatobiliary & Pancreatic Diseases International》 SCIE CAS CSCD 2022年第1期33-40,共8页
Background:Apoptosis,also called programmed cell death,is a genetically controlled process against hyperproliferation and malignancy.The Fas-Fas ligand(FasL)system is considered a major pathway for apoptosis in cells ... Background:Apoptosis,also called programmed cell death,is a genetically controlled process against hyperproliferation and malignancy.The Fas-Fas ligand(FasL)system is considered a major pathway for apoptosis in cells and tissues.Thus,this study aimed to investigate whether single nucleotide polymor-phisms(SNPs)in Fas and FasL gene may have effects on the recurrence and survival of patients with hepatocellular carcinoma(HCC)after curative hepatectomy.Methods:We investigated the relationship between Fas rs1800682,rs2234767 and FasL rs763110 poly-morphisms and recurrence-free survival(RFS)as well as overall survival(OS)in 117 Chinese Han patients with HCC who underwent hepatectomy.Results:In Kaplan-Meier survival analysis,only Fas rs1800682(-670 A/G)was associated with RFS and OS.Compared with AA genotype,the AG/GG genotype was significantly associated with better RFS(P=0.008)and OS(P=0.020).Moreover,multivariate Cox regression analysis showed that Fas rs1800682 remained as a significant independent predictor of RFS for HCC patients with hepatectomy[AG/GG vs.AA:adjusted hazard ratio=0.464,95%confidence interval:0.275-0.782,P=0.004],but was not an independent predictor of OS(P=0.395).Conclusions:This study demonstrated that Fas-670 G allele may play a protective role in the recurrence and survival of HCC patients with hepatectomy.Furthermore,Fas rs1800682 polymorphism might be a promising biomarker for HCC patients after hepatectomy. 展开更多
关键词 Hepatocellular carcinoma Single nucleotide polymorphism Cell apoptosis PROGNOSIS RESECTION
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