Cargando…
Negative Ion Mode Electrospray Tandem Mass Spectrometry of Hydroxy-Terminated Polydimethylsiloxanes Formed upon in situ Methanolysis
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...
Autores principales: | , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Mass Spectrometry Society of Japan
2017
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5469726/ https://www.ncbi.nlm.nih.gov/pubmed/28630810 http://dx.doi.org/10.5702/massspectrometry.A0057 |
_version_ | 1783243627335516160 |
---|---|
author | Fouquet, Thierry Charles, Laurence Sato, Hiroaki |
author_facet | Fouquet, Thierry Charles, Laurence Sato, Hiroaki |
author_sort | Fouquet, Thierry |
collection | PubMed |
description | 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. |
format | Online Article Text |
id | pubmed-5469726 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2017 |
publisher | The Mass Spectrometry Society of Japan |
record_format | MEDLINE/PubMed |
spelling | pubmed-54697262017-06-19 Negative Ion Mode Electrospray Tandem Mass Spectrometry of Hydroxy-Terminated Polydimethylsiloxanes Formed upon in situ Methanolysis Fouquet, Thierry Charles, Laurence Sato, Hiroaki Mass Spectrom (Tokyo) Original Article 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. The Mass Spectrometry Society of Japan 2017 2017-06-15 /pmc/articles/PMC5469726/ /pubmed/28630810 http://dx.doi.org/10.5702/massspectrometry.A0057 Text en Copyright © 2017 Thierry Fouquet, Laurence Charles, and Hiroaki Sato. http://creativecommons.org/licenses/by-nc/3.0/ This is an open access article distributed under the terms of Creative Commons Attribution License, which permits use, distribution, and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes. For permission to reuse copyrighted content from this publication, please go to www.copyright.com (http://www.copyright.com) , or contact Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923 |
spellingShingle | Original Article Fouquet, Thierry Charles, Laurence Sato, Hiroaki Negative Ion Mode Electrospray Tandem Mass Spectrometry of Hydroxy-Terminated Polydimethylsiloxanes Formed upon in situ Methanolysis |
title | Negative Ion Mode Electrospray Tandem Mass Spectrometry of Hydroxy-Terminated Polydimethylsiloxanes Formed upon in situ Methanolysis |
title_full | Negative Ion Mode Electrospray Tandem Mass Spectrometry of Hydroxy-Terminated Polydimethylsiloxanes Formed upon in situ Methanolysis |
title_fullStr | Negative Ion Mode Electrospray Tandem Mass Spectrometry of Hydroxy-Terminated Polydimethylsiloxanes Formed upon in situ Methanolysis |
title_full_unstemmed | Negative Ion Mode Electrospray Tandem Mass Spectrometry of Hydroxy-Terminated Polydimethylsiloxanes Formed upon in situ Methanolysis |
title_short | Negative Ion Mode Electrospray Tandem Mass Spectrometry of Hydroxy-Terminated Polydimethylsiloxanes Formed upon in situ Methanolysis |
title_sort | negative ion mode electrospray tandem mass spectrometry of hydroxy-terminated polydimethylsiloxanes formed upon in situ methanolysis |
topic | Original Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5469726/ https://www.ncbi.nlm.nih.gov/pubmed/28630810 http://dx.doi.org/10.5702/massspectrometry.A0057 |
work_keys_str_mv | AT fouquetthierry negativeionmodeelectrospraytandemmassspectrometryofhydroxyterminatedpolydimethylsiloxanesformeduponinsitumethanolysis AT charleslaurence negativeionmodeelectrospraytandemmassspectrometryofhydroxyterminatedpolydimethylsiloxanesformeduponinsitumethanolysis AT satohiroaki negativeionmodeelectrospraytandemmassspectrometryofhydroxyterminatedpolydimethylsiloxanesformeduponinsitumethanolysis |