二甲基硅氧烷环体和线性体的电喷雾离子化效率研究  

Investigation on the ESI Efficiency of the Cyclic and the Linear Dimethylsilicanes

作　　者：张华蓉[1] 陈奕伊 聂长虹 蒋可志[1] ZHANG Huarong;CHEN Yiyi;NIE Changhong;JIANG Kezhi(Key Laboratory of Organosilicon Chemistry and Material Technology,Hangzhou Normal University,Hangzhou 311121,China;Hoshine Silicon Limited Corporation,Jiaxing 314201,China)

机构地区：[1]杭州师范大学有机硅化学及材料技术教育部重点实验室,浙江杭州311121 [2]合盛硅业股份有限公司,浙江嘉兴314201

出　　处：《杭州师范大学学报（自然科学版）》2019年第5期470-475,共6页Journal of Hangzhou Normal University(Natural Science Edition)

基　　金：浙江省氟硅精细化学品与材料制造协同中心开放基金项目(FSi2018A020;FSi2018A021)

摘　　要：采用高分辨电喷雾质谱和量化计算研究了二甲基硅氧烷环体、线性体的ESI电离效率.实验发现,线性体比相应的环体更容易在ESI-MS中检测到;而环体中六甲基环三硅氧烷(D3)和八甲基环四硅氧烷(D4)在ESI-MS中几乎没有检测到.量化计算结果表明,线性体具有柔性结构,使得其[M+H]^+结构中存在分子内氢键,其[M+Na]^+结构中多个位点氧原子与Na^+相作用,从而增加缔合物的稳定性.环体D3和D4具有刚性结构,其质子亲和能和Na^+亲和能都比较小;十甲基环五硅氧烷(D5)和十二甲基环六硅氧烷(D6)结构具有一定柔软性,在准分子离子中存在氢键或与Na^+多位点作用.计算结果比较合理地解释了ESI-MS实验结果.In this work,the ESI efficiency of the cyclic and the linear dimethylsilicanes was investigated by ESI-MS and quantum calculation.The experimental results indicated that linear dimethylsilicane was more feasible to be ionized than the corresponding cyclic one in ESI-MS analysis,D3 and D4 were not be detected.The calculated results indicated that there was an intramolecular hydrogen bond in[M+H]^+of linear dimethylsilicanes and multi-site interaction with Na^+in their Na^+-adducts due to their flexible structure,and the corresponding quasi-molecular ions had a relative stable structure.However,the proton affinity and the Na+-bonding energy of D3 or D4 were very low due to their rigid structure,while D5 and D6 had a flexible structure and there was an intramolecular hydrogen bond and multi-site interaction with Na+in their quasi-molecular ions.The ESI-MS results could be reasonably explained by the quantum calculation.

关 键 词：二甲基硅氧烷线性体 二甲基硅氧烷环体 电喷雾电离质谱 量化计算 

分 类 号：O657.63[理学—分析化学]