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甲醇解形成的羟基封端聚二甲基硅氧烷的负离子模式电喷雾串联质谱分析

Negative Ion Mode Electrospray Tandem Mass Spectrometry of Hydroxy-Terminated Polydimethylsiloxanes Formed upon Methanolysis.

作者信息

Fouquet Thierry, Charles Laurence, Sato Hiroaki

机构信息

National Institute of Advanced Industrial Science and Technology (AIST), Research Institute for Sustainable Chemistry.

Aix Marseille University, CNRS, ICR, Institut de Chimie Radicalaire.

出版信息

Mass Spectrom (Tokyo). 2017;6(1):A0057. doi: 10.5702/massspectrometry.A0057. Epub 2017 Jun 15.

DOI:10.5702/massspectrometry.A0057
PMID:28630810
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5469726/
Abstract

Ethoxy-, methoxy- and hydroxy-terminated polydimethylsiloxanes (PDMS) are formed as the result of the methanolysis of diethoxy-ended PDMS during its infusion in electrospray ionization. The negative ion mode permits only hydroxy-ended products to be detected, and isomeric interference is avoided in single stage and tandem mass spectrometry. The routes for the fragmentation of (ethyl, hydroxy)-, (methyl, hydroxy)- and (hydro, hydroxy)-ended PDMS upon collision activated dissociation (CAD) were explored in the negative ion mode using either formate or acetate anion adduction. Symmetrical (hydro, hydroxy)-ended PDMS decomposed to product ions carrying one of the hydroxy terminations through the abstraction of an acidic hydrogen and depolymerization (expulsion of cyclic neutral species) regardless of the adducted anion. Asymmetric (ethyl, hydroxy)-ended (resp. (methyl, hydroxy)-ended) PDMS yielded both ethoxy-ended (resp. methoxy-ended) fragment ions through the abstraction of the only acidic hydrogens and linear product ions carrying both terminations still interacted with the anion. The production of information-rich ethoxy-ended (resp. methoxy-ended) fragment ions was limited by formate but favored when acetate (higher proton affinity) was used in a CAD fingerprint complementary to the positive ion mode.

摘要

乙氧基、甲氧基和羟基封端的聚二甲基硅氧烷（PDMS）是二乙氧基封端的PDMS在电喷雾电离注入过程中发生甲醇解的产物。负离子模式仅能检测到羟基封端的产物，并且在单级和串联质谱中可避免异构体干扰。在负离子模式下，使用甲酸根或乙酸根阴离子加合物，研究了（乙基，羟基）-、（甲基，羟基）-和（氢，羟基）-封端的PDMS在碰撞诱导解离（CAD）时的碎裂途径。对称的（氢，羟基）-封端的PDMS通过夺取酸性氢和解聚（环状中性物种的排出）分解为带有一个羟基端基的产物离子，而与加合阴离子无关。不对称的（乙基，羟基）-封端的（相应地，（甲基，羟基）-封端的）PDMS通过夺取唯一的酸性氢产生乙氧基封端的（相应地，甲氧基封端的）碎片离子，并且带有两个端基的线性产物离子仍与阴离子相互作用。富含信息的乙氧基封端的（相应地，甲氧基封端的）碎片离子的产生受到甲酸根的限制，但当使用乙酸根（更高的质子亲和力）时在与正离子模式互补的CAD指纹图谱中更有利。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/804a/5469726/3137059485f9/massspectrometry-6-1-A0057-scheme03.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/804a/5469726/3b0840ec0f2e/massspectrometry-6-1-A0057-scheme01.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/804a/5469726/d9ea030b14a3/massspectrometry-6-1-A0057-figure01.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/804a/5469726/c3a52ac64752/massspectrometry-6-1-A0057-figure02.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/804a/5469726/0f79fe35f7c9/massspectrometry-6-1-A0057-scheme02.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/804a/5469726/80ff5c1b550c/massspectrometry-6-1-A0057-figure03.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/804a/5469726/3137059485f9/massspectrometry-6-1-A0057-scheme03.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/804a/5469726/3b0840ec0f2e/massspectrometry-6-1-A0057-scheme01.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/804a/5469726/d9ea030b14a3/massspectrometry-6-1-A0057-figure01.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/804a/5469726/c3a52ac64752/massspectrometry-6-1-A0057-figure02.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/804a/5469726/0f79fe35f7c9/massspectrometry-6-1-A0057-scheme02.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/804a/5469726/80ff5c1b550c/massspectrometry-6-1-A0057-figure03.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/804a/5469726/3137059485f9/massspectrometry-6-1-A0057-scheme03.jpg

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本文引用的文献

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