应用量子化学计算研究As_(4)S_(4)与H^(+)、OH^(-)相互作用的复合物  

Complexes of As_(4)S_(4) interacting with H^(+) and OH^(-) by computational quantum chemistry

作　　者：王楚茵 陈杨[1] 王泓力 赵希彤 张谦[1] 金宏威[2] 关君[1] WANG Chu-yin;CHEN Yang;WANG Hong-li;ZHAO Xi-tong;ZHANG Qian;JIN Hong-wei;GUAN Jun(School of Chinese Materia Medica,Beijing University of Chinese Medicine,Beijing 102488;State Key Laboratory of Natural and Biomimetic Drugs,Peking University Health Science Center,Beijing 100191)

机构地区：[1]北京中医药大学中药学院,北京102488 [2]北京大学医学部天然药物及仿生药物国家重点实验室,北京100191

出　　处：《中南药学》2024年第5期1109-1118,共10页Central South Pharmacy

基　　金：国家自然科学基金面上项目(No.82074001);国家自然科学基金青年科学基金项目(No.81403069);北京市“双一流”-支持高水平中医药重点学科23年经费-中药分析学(No.CGSQ-2023-746)。

摘　　要：目的 应用量子化学计算方法研究As_(4)S_(4)与H^(+)、OH^(-)相互作用的复合物,探讨雄黄在酸性、碱性介质中可能存在的砷形态。方法 首先采用GaussianView软件设计As_(4)S_(4)异构体与H^(+)、OH^(-)相互作用形成的复合物;接着采用Gaussian 09软件,在HF/STO-3G、B3LYP/6-31G^(*)、B3LYP/6-311+G^(*)理论水平下,对可能形成的[As_(4)S_(4)-H]^(+)复合物进行几何优化和热力学计算;对可能形成的[As_(4)S_(4)-OH]^(-)复合物,则在HF/STO-3G、B3LYP/6-31+G^(*)、B3LYP/6-311+G^(*)理论水平上进行几何优化和热力学计算。然后分别在B3LYP/6-31G^(*)和B3LYP/6-31+G^(*)水平下对[As_(4)S_(4)-H]^(+)和[As_(4)S_(4)-OH]^(-)复合物进行自然键轨道分析。结果 雄黄的两种稳定的As_(4)S_(4)异构体与H^(+)、OH^(-)均可以形成1∶1比例的复合物,所形成的21种复合物均具有热力学稳定性。前线轨道能级和键级分析表明,[As_(4)S_(4)-H]+和[As_(4)S_(4)-OH]^(-)复合物的热力学稳定性较差。结论 雄黄在酸性介质和碱性介质中所形成的复合物可以作为短寿命的分子离子存在,这些分子离子可能是雄黄在酸性、碱性介质中的活性中间体。Objective To determine the possible arsenic species of realgar in acidic and alkaline media,by studying the complexes of As_(4)S_(4) interacting with H+and OH-with computational quantum chemistry method.Methods Firstly,the GaussianView software was used to design the possible complexes formed by interaction between As_(4)S_(4) isomers with H+and OH^(-);subsequently,Gaussian 09 software was used to perform geometric optimization and thermodynamic calculations on the possible formation of[As_(4)S_(4)-H]^(+) complexes at the HF/STO-3G,B3LYP/6-31G^(*)and B3LYP/6-311+G^(*)theory levels;for the possible formation of[As_(4)S_(4)-OH]-complexes,geometric optimization and thermodynamic calculations were conducted at the HF/STO-3G,B3LYP/6-31+G^(*),and B3LYP/6-311+G^(*)theory levels.Then,natural bond orbital analysis was performed on[As_(4)S_(4)-H]^(+) and[As_(4)S_(4)-OH]^(-)complexes at the B3LYP/6-31G^(*)and B3LYP/6-31+G^(*)levels.Results Two isomers of As_(4)S_(4) could both form complexes with H^(+)and OH^(-)ions at a 1∶1 ratio,and 21 complexes found were thermodynamically stable.The frontier orbital energy level and bond level analysis showed that the stability of[As_(4)S_(4)-H]^(+)and[As_(4)S_(4)-OH]^(-)complexes were relatively poor.Conclusion The complexes generated by realgar in acidic and alkaline media may exist as short-lived species,which may be the reactive intermediates in acidic and alkaline media.

关 键 词：As_(4)S_(4) 复合物 砷形态 量子化学计算 

分 类 号：TS201.2[轻工技术与工程—食品科学]