Electron ionization mass spectrometric fragmentation and detection of autoxidation products of 2,6,10,14‐tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5‐ene in Arctic sediments
Rationale Some highly branched isoprenoid (HBI) alkenes are commonly used as proxies for palaeoceanographic reconstructions. However, there is a need to identify compounds that are sufficiently stable and abundant to be used as tracers of HBI oxidation in sediments. 2,6,10,14‐Tetramethyl‐7‐(3‐methyl...
Published in: | Rapid Communications in Mass Spectrometry |
---|---|
Main Authors: | , , |
Format: | Article in Journal/Newspaper |
Language: | English |
Published: |
Wiley
2020
|
Subjects: | |
Online Access: | http://dx.doi.org/10.1002/rcm.8816 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Frcm.8816 https://onlinelibrary.wiley.com/doi/pdf/10.1002/rcm.8816 https://onlinelibrary.wiley.com/doi/full-xml/10.1002/rcm.8816 |
id |
crwiley:10.1002/rcm.8816 |
---|---|
record_format |
openpolar |
spelling |
crwiley:10.1002/rcm.8816 2024-03-31T07:50:48+00:00 Electron ionization mass spectrometric fragmentation and detection of autoxidation products of 2,6,10,14‐tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5‐ene in Arctic sediments Rontani, Jean‐François Smik, Lukas Belt, Simon T. 2020 http://dx.doi.org/10.1002/rcm.8816 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Frcm.8816 https://onlinelibrary.wiley.com/doi/pdf/10.1002/rcm.8816 https://onlinelibrary.wiley.com/doi/full-xml/10.1002/rcm.8816 en eng Wiley http://onlinelibrary.wiley.com/termsAndConditions#vor Rapid Communications in Mass Spectrometry volume 34, issue 15 ISSN 0951-4198 1097-0231 Organic Chemistry Spectroscopy Analytical Chemistry journal-article 2020 crwiley https://doi.org/10.1002/rcm.8816 2024-03-04T13:01:07Z Rationale Some highly branched isoprenoid (HBI) alkenes are commonly used as proxies for palaeoceanographic reconstructions. However, there is a need to identify compounds that are sufficiently stable and abundant to be used as tracers of HBI oxidation in sediments. 2,6,10,14‐Tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5( Z/E )‐en‐4‐ols resulting from 2,6,10,14‐tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5‐ene appear to be useful for this purpose. Methods Comparison of electron ionization (EI) mass spectra and retention times with those of standards allowed formal identification of autoxidation products of 2,6,10,14‐tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5‐ene. EI‐MS fragmentations of TMS ethers of the main oxidation products (2,6,10,14‐tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5( Z/E )‐en‐4‐ols) were deduced by gas chromatography/electron ionization mass spectrometry (GC/EI‐MS), low‐energy collision‐induced dissociation tandem mass spectrometry (CID‐MS/MS) and accurate mass measurements. These compounds were then quantified in Arctic sediment samples in MS/MS multiple reaction monitoring (MRM) mode using transitions based on the main fragmentation pathways elucidated. Results 2,6,10,14‐Tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5( Z/E )‐en‐4‐ols were identified after autoxidation of the HBI alkene 2,6,10,14‐tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5‐ene. Low‐energy CID‐MS/MS analyses and accurate mass measurements allowed the EI‐MS fragmentation pathways of their trimethylsilyl (TMS) derivatives to be elucidated. Some specific fragment ions and chromatographic retention times were also useful for further characterization. As an application of some of the described fragmentations, TMS derivatives of these metabolites were characterized and quantified in MRM mode in Arctic sediments. Conclusions Due to their production in high proportions during autoxidation of their parent HBI diene, their apparent stability in sediments, and their specific EIMS fragmentations, ( Z and E ... Article in Journal/Newspaper Arctic Wiley Online Library Arctic Rapid Communications in Mass Spectrometry 34 15 |
institution |
Open Polar |
collection |
Wiley Online Library |
op_collection_id |
crwiley |
language |
English |
topic |
Organic Chemistry Spectroscopy Analytical Chemistry |
spellingShingle |
Organic Chemistry Spectroscopy Analytical Chemistry Rontani, Jean‐François Smik, Lukas Belt, Simon T. Electron ionization mass spectrometric fragmentation and detection of autoxidation products of 2,6,10,14‐tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5‐ene in Arctic sediments |
topic_facet |
Organic Chemistry Spectroscopy Analytical Chemistry |
description |
Rationale Some highly branched isoprenoid (HBI) alkenes are commonly used as proxies for palaeoceanographic reconstructions. However, there is a need to identify compounds that are sufficiently stable and abundant to be used as tracers of HBI oxidation in sediments. 2,6,10,14‐Tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5( Z/E )‐en‐4‐ols resulting from 2,6,10,14‐tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5‐ene appear to be useful for this purpose. Methods Comparison of electron ionization (EI) mass spectra and retention times with those of standards allowed formal identification of autoxidation products of 2,6,10,14‐tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5‐ene. EI‐MS fragmentations of TMS ethers of the main oxidation products (2,6,10,14‐tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5( Z/E )‐en‐4‐ols) were deduced by gas chromatography/electron ionization mass spectrometry (GC/EI‐MS), low‐energy collision‐induced dissociation tandem mass spectrometry (CID‐MS/MS) and accurate mass measurements. These compounds were then quantified in Arctic sediment samples in MS/MS multiple reaction monitoring (MRM) mode using transitions based on the main fragmentation pathways elucidated. Results 2,6,10,14‐Tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5( Z/E )‐en‐4‐ols were identified after autoxidation of the HBI alkene 2,6,10,14‐tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5‐ene. Low‐energy CID‐MS/MS analyses and accurate mass measurements allowed the EI‐MS fragmentation pathways of their trimethylsilyl (TMS) derivatives to be elucidated. Some specific fragment ions and chromatographic retention times were also useful for further characterization. As an application of some of the described fragmentations, TMS derivatives of these metabolites were characterized and quantified in MRM mode in Arctic sediments. Conclusions Due to their production in high proportions during autoxidation of their parent HBI diene, their apparent stability in sediments, and their specific EIMS fragmentations, ( Z and E ... |
format |
Article in Journal/Newspaper |
author |
Rontani, Jean‐François Smik, Lukas Belt, Simon T. |
author_facet |
Rontani, Jean‐François Smik, Lukas Belt, Simon T. |
author_sort |
Rontani, Jean‐François |
title |
Electron ionization mass spectrometric fragmentation and detection of autoxidation products of 2,6,10,14‐tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5‐ene in Arctic sediments |
title_short |
Electron ionization mass spectrometric fragmentation and detection of autoxidation products of 2,6,10,14‐tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5‐ene in Arctic sediments |
title_full |
Electron ionization mass spectrometric fragmentation and detection of autoxidation products of 2,6,10,14‐tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5‐ene in Arctic sediments |
title_fullStr |
Electron ionization mass spectrometric fragmentation and detection of autoxidation products of 2,6,10,14‐tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5‐ene in Arctic sediments |
title_full_unstemmed |
Electron ionization mass spectrometric fragmentation and detection of autoxidation products of 2,6,10,14‐tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5‐ene in Arctic sediments |
title_sort |
electron ionization mass spectrometric fragmentation and detection of autoxidation products of 2,6,10,14‐tetramethyl‐7‐(3‐methylpent‐4‐enyl)‐pentadec‐5‐ene in arctic sediments |
publisher |
Wiley |
publishDate |
2020 |
url |
http://dx.doi.org/10.1002/rcm.8816 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Frcm.8816 https://onlinelibrary.wiley.com/doi/pdf/10.1002/rcm.8816 https://onlinelibrary.wiley.com/doi/full-xml/10.1002/rcm.8816 |
geographic |
Arctic |
geographic_facet |
Arctic |
genre |
Arctic |
genre_facet |
Arctic |
op_source |
Rapid Communications in Mass Spectrometry volume 34, issue 15 ISSN 0951-4198 1097-0231 |
op_rights |
http://onlinelibrary.wiley.com/termsAndConditions#vor |
op_doi |
https://doi.org/10.1002/rcm.8816 |
container_title |
Rapid Communications in Mass Spectrometry |
container_volume |
34 |
container_issue |
15 |
_version_ |
1795029284034707456 |