(-)ESI/CAD MS n Procedure for Sequencing Lignin Oligomers Based on a Study of Synthetic Model Compounds with β-O-4 and 5-5 Linkages

Huaming Sheng, Weijuan Tang, Jinshan Gao, James S. Riedeman, Guannan Li, Tiffany M. Jarrell, Matthew R. Hurt, Linan Yang, Priya Murria, Xin Ma, John J. Nash, Hilkka I. Kenttämaa

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Abstract

Seven synthesized G-lignin oligomer model compounds (ranging in size from dimers to an octamer) with 5-5 and/or β-O-4 linkages, and three synthesized S-lignin model compounds (a dimer, trimer, and tetramer) with β-O-4 linkages, were evaporated and deprotonated using negative-ion mode ESI in a linear quadrupole ion trap/Fourier transform ion cyclotron resonance mass spectrometer. The collision-activated dissociation (CAD) fragmentation patterns (obtained in MS 2 and MS 3 experiments, respectively) for the negative ions were studied to develop a procedure for sequencing unknown lignin oligomers. On the basis of the observed fragmentation patterns, the measured elemental compositions of the most abundant fragment ions, and quantum chemical calculations, the most important reaction pathways and likely mechanisms were delineated. Many of these reactions occur via charge-remote fragmentation mechanisms. Deprotonated compounds with only β-O-4 linkages, or both 5-5 and β-O-4 linkages, showed major 1,2-eliminations of neutral compounds containing one, two, or three aromatic rings. The most likely mechanisms for these reactions are charge-remote Maccoll and retro-ene eliminations resulting in the cleavage of a β-O-4 linkage. Facile losses of H 2 O and CH 2 O were also observed for all deprotonated model compounds, which involve a previously published charge-driven mechanism. Characteristic "ion groups" and "key ions" were identified that, when combined with their CAD products (MS 3 experiments), can be used to sequence unknown oligomers.

Original languageEnglish
Pages (from-to)13089-13096
Number of pages8
JournalAnalytical Chemistry
Volume89
Issue number24
DOIs
StatePublished - 19 Dec 2017

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Lignin
Oligomers
Ions
Dimers
Negative ions
Cyclotron resonance
Mass spectrometers
Fourier transforms
Experiments
Chemical analysis

Cite this

Sheng, Huaming ; Tang, Weijuan ; Gao, Jinshan ; Riedeman, James S. ; Li, Guannan ; Jarrell, Tiffany M. ; Hurt, Matthew R. ; Yang, Linan ; Murria, Priya ; Ma, Xin ; Nash, John J. ; Kenttämaa, Hilkka I. / (-)ESI/CAD MS n Procedure for Sequencing Lignin Oligomers Based on a Study of Synthetic Model Compounds with β-O-4 and 5-5 Linkages In: Analytical Chemistry. 2017 ; Vol. 89, No. 24. pp. 13089-13096.
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abstract = "Seven synthesized G-lignin oligomer model compounds (ranging in size from dimers to an octamer) with 5-5 and/or β-O-4 linkages, and three synthesized S-lignin model compounds (a dimer, trimer, and tetramer) with β-O-4 linkages, were evaporated and deprotonated using negative-ion mode ESI in a linear quadrupole ion trap/Fourier transform ion cyclotron resonance mass spectrometer. The collision-activated dissociation (CAD) fragmentation patterns (obtained in MS 2 and MS 3 experiments, respectively) for the negative ions were studied to develop a procedure for sequencing unknown lignin oligomers. On the basis of the observed fragmentation patterns, the measured elemental compositions of the most abundant fragment ions, and quantum chemical calculations, the most important reaction pathways and likely mechanisms were delineated. Many of these reactions occur via charge-remote fragmentation mechanisms. Deprotonated compounds with only β-O-4 linkages, or both 5-5 and β-O-4 linkages, showed major 1,2-eliminations of neutral compounds containing one, two, or three aromatic rings. The most likely mechanisms for these reactions are charge-remote Maccoll and retro-ene eliminations resulting in the cleavage of a β-O-4 linkage. Facile losses of H 2 O and CH 2 O were also observed for all deprotonated model compounds, which involve a previously published charge-driven mechanism. Characteristic {"}ion groups{"} and {"}key ions{"} were identified that, when combined with their CAD products (MS 3 experiments), can be used to sequence unknown oligomers.",
author = "Huaming Sheng and Weijuan Tang and Jinshan Gao and Riedeman, {James S.} and Guannan Li and Jarrell, {Tiffany M.} and Hurt, {Matthew R.} and Linan Yang and Priya Murria and Xin Ma and Nash, {John J.} and Kentt{\"a}maa, {Hilkka I.}",
year = "2017",
month = "12",
day = "19",
doi = "10.1021/acs.analchem.7b01911",
language = "English",
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Sheng, H, Tang, W, Gao, J, Riedeman, JS, Li, G, Jarrell, TM, Hurt, MR, Yang, L, Murria, P, Ma, X, Nash, JJ & Kenttämaa, HI 2017, ' (-)ESI/CAD MS n Procedure for Sequencing Lignin Oligomers Based on a Study of Synthetic Model Compounds with β-O-4 and 5-5 Linkages ', Analytical Chemistry, vol. 89, no. 24, pp. 13089-13096. https://doi.org/10.1021/acs.analchem.7b01911

(-)ESI/CAD MS n Procedure for Sequencing Lignin Oligomers Based on a Study of Synthetic Model Compounds with β-O-4 and 5-5 Linkages . / Sheng, Huaming; Tang, Weijuan; Gao, Jinshan; Riedeman, James S.; Li, Guannan; Jarrell, Tiffany M.; Hurt, Matthew R.; Yang, Linan; Murria, Priya; Ma, Xin; Nash, John J.; Kenttämaa, Hilkka I.

In: Analytical Chemistry, Vol. 89, No. 24, 19.12.2017, p. 13089-13096.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - (-)ESI/CAD MS n Procedure for Sequencing Lignin Oligomers Based on a Study of Synthetic Model Compounds with β-O-4 and 5-5 Linkages

AU - Sheng, Huaming

AU - Tang, Weijuan

AU - Gao, Jinshan

AU - Riedeman, James S.

AU - Li, Guannan

AU - Jarrell, Tiffany M.

AU - Hurt, Matthew R.

AU - Yang, Linan

AU - Murria, Priya

AU - Ma, Xin

AU - Nash, John J.

AU - Kenttämaa, Hilkka I.

PY - 2017/12/19

Y1 - 2017/12/19

N2 - Seven synthesized G-lignin oligomer model compounds (ranging in size from dimers to an octamer) with 5-5 and/or β-O-4 linkages, and three synthesized S-lignin model compounds (a dimer, trimer, and tetramer) with β-O-4 linkages, were evaporated and deprotonated using negative-ion mode ESI in a linear quadrupole ion trap/Fourier transform ion cyclotron resonance mass spectrometer. The collision-activated dissociation (CAD) fragmentation patterns (obtained in MS 2 and MS 3 experiments, respectively) for the negative ions were studied to develop a procedure for sequencing unknown lignin oligomers. On the basis of the observed fragmentation patterns, the measured elemental compositions of the most abundant fragment ions, and quantum chemical calculations, the most important reaction pathways and likely mechanisms were delineated. Many of these reactions occur via charge-remote fragmentation mechanisms. Deprotonated compounds with only β-O-4 linkages, or both 5-5 and β-O-4 linkages, showed major 1,2-eliminations of neutral compounds containing one, two, or three aromatic rings. The most likely mechanisms for these reactions are charge-remote Maccoll and retro-ene eliminations resulting in the cleavage of a β-O-4 linkage. Facile losses of H 2 O and CH 2 O were also observed for all deprotonated model compounds, which involve a previously published charge-driven mechanism. Characteristic "ion groups" and "key ions" were identified that, when combined with their CAD products (MS 3 experiments), can be used to sequence unknown oligomers.

AB - Seven synthesized G-lignin oligomer model compounds (ranging in size from dimers to an octamer) with 5-5 and/or β-O-4 linkages, and three synthesized S-lignin model compounds (a dimer, trimer, and tetramer) with β-O-4 linkages, were evaporated and deprotonated using negative-ion mode ESI in a linear quadrupole ion trap/Fourier transform ion cyclotron resonance mass spectrometer. The collision-activated dissociation (CAD) fragmentation patterns (obtained in MS 2 and MS 3 experiments, respectively) for the negative ions were studied to develop a procedure for sequencing unknown lignin oligomers. On the basis of the observed fragmentation patterns, the measured elemental compositions of the most abundant fragment ions, and quantum chemical calculations, the most important reaction pathways and likely mechanisms were delineated. Many of these reactions occur via charge-remote fragmentation mechanisms. Deprotonated compounds with only β-O-4 linkages, or both 5-5 and β-O-4 linkages, showed major 1,2-eliminations of neutral compounds containing one, two, or three aromatic rings. The most likely mechanisms for these reactions are charge-remote Maccoll and retro-ene eliminations resulting in the cleavage of a β-O-4 linkage. Facile losses of H 2 O and CH 2 O were also observed for all deprotonated model compounds, which involve a previously published charge-driven mechanism. Characteristic "ion groups" and "key ions" were identified that, when combined with their CAD products (MS 3 experiments), can be used to sequence unknown oligomers.

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U2 - 10.1021/acs.analchem.7b01911

DO - 10.1021/acs.analchem.7b01911

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