In:
Rapid Communications in Mass Spectrometry, Wiley, Vol. 27, No. 17 ( 2013-09-15), p. 1913-1918
Abstract:
Isosorbide is a promising biomass‐derived molecule that can be used as a replacement for fossil resource‐derived diol monomers used in polyester synthesis. Due to its increased use in sustainable development, it is useful to understand the tandem mass spectrometric (MS/MS) fragmentation pathways of the isosorbide‐based copolymer as an aid to interpreting the MS/MS spectra of other isosorbide‐containing copolymers. METHODS Collision‐activated dissociation (CAD) experiments were performed on the sodiated/protonated molecules, [(AB) n A+Na(or H)] + , n = 2–5, of isosorbide (A)–1,4‐cyclohexanedicarboxylic acid (B) oligomers formed by ion‐trap electrospray ionization (ESI). RESULTS Product ions arose from cleavage of the bonds between isosorbide and 1,4‐cyclohexanedicarboxylic acid. In the MS/MS spectra, f n '' product ions were most abundant, followed by e n ions. McLafferty rearrangement appeared to provide the most facile pathway to yield the abundant f n '' and e n ions. In addition, a n , b n '', f n '' u n '', and e n + ions were observed. Inductive cleavage and β‐elimination were suggested to be the pathways involved in generating e n + ‐ and e n / b n ''‐type ions, respectively. CONCLUSIONS Based on the obtained CAD spectra, the alternating sequences of two copolymer building blocks, A and B, were unambiguously determined. The fragmentation pathways leading to the observed product ion types were also established. Copyright © 2013 John Wiley & Sons, Ltd.
Type of Medium:
Online Resource
ISSN:
0951-4198
,
1097-0231
Language:
English
Publisher:
Wiley
Publication Date:
2013
detail.hit.zdb_id:
2002158-6
detail.hit.zdb_id:
58731-X
SSG:
11
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