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ATRP poly(acrylate) star formation: a comparative study between MALDI and ESI mass spectrometry

(2009) POLYMER. 50(9). p.1986-2000
Author
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Abstract
Optimised matrix-assisted laser desorption/ionisation (MALDI) and electrospray ionisation (ESI) mass spectrometry (MIS) methodologies were systematically compared in terms of their relative abilities to identify distinct chemical species present in samples associated with a polymer mechanistic study. In order to perform the investigation, formation processes involved in atom transfer radical polymerisation (ATRP) mediated methyl acrylate (MA) star polymerisations were studied. In addition to the 4-armed ATRP initiator employed in the polymerisations, initiator side-products were found to generate oligomeric chains. At a relatively high monomer to polymer conversion, terminal Br loss was observed in these oligomers; this Br loss was hypothesised to occur via degradative transfer reactions involving the radicals (CH3)(2)(C) over dotOH, (C) over dotH(3) and (C) over dotH(2)COCH(3), which were derived from the acetone used as a solvent in the polymerisations, as well as hydrogen radicals donated by the ligand N,N',N',N '',N ''-pentamethyldiethylenetriamine (PMDETA). In performing these studies, ESI was found to identify a greater number of distinct chemical species in the samples under investigation when compared to the employed MALDI technique, suggesting that the utilisation of ESI must be strongly considered in polymer mechanistic investigations if the maximum number of end-group functionalities within a given polymer sample are to be identified.
Keywords
SIZE-EXCLUSION CHROMATOGRAPHY, SYNTHETIC-POLYMERS, ELECTROSPRAY SAMPLE DEPOSITION, LASER-DESORPTION IONIZATION, Star polymers, KeyWords Plus: TRANSFER RADICAL POLYMERIZATION, Author Keywords: Mass spectrometry, Atom transfer radical polymerisation (ATRP), REACTION PATHWAYS, FAST-EVAPORATION, METHYL ACRYLATE, TOF-MS, ACETONE

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Citation

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MLA
Hart-Smith, Gene et al. “ATRP Poly(acrylate) Star Formation: a Comparative Study Between MALDI and ESI Mass Spectrometry.” POLYMER 50.9 (2009): 1986–2000. Print.
APA
Hart-Smith, G., Lammens, M., Du Prez, F., Guilhaus, M., & Barner-Kowollik, C. (2009). ATRP poly(acrylate) star formation: a comparative study between MALDI and ESI mass spectrometry. POLYMER, 50(9), 1986–2000.
Chicago author-date
Hart-Smith, Gene, Mieke Lammens, Filip Du Prez, Michael Guilhaus, and Christopher Barner-Kowollik. 2009. “ATRP Poly(acrylate) Star Formation: a Comparative Study Between MALDI and ESI Mass Spectrometry.” Polymer 50 (9): 1986–2000.
Chicago author-date (all authors)
Hart-Smith, Gene, Mieke Lammens, Filip Du Prez, Michael Guilhaus, and Christopher Barner-Kowollik. 2009. “ATRP Poly(acrylate) Star Formation: a Comparative Study Between MALDI and ESI Mass Spectrometry.” Polymer 50 (9): 1986–2000.
Vancouver
1.
Hart-Smith G, Lammens M, Du Prez F, Guilhaus M, Barner-Kowollik C. ATRP poly(acrylate) star formation: a comparative study between MALDI and ESI mass spectrometry. POLYMER. THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND: ELSEVIER SCI LTD; 2009;50(9):1986–2000.
IEEE
[1]
G. Hart-Smith, M. Lammens, F. Du Prez, M. Guilhaus, and C. Barner-Kowollik, “ATRP poly(acrylate) star formation: a comparative study between MALDI and ESI mass spectrometry,” POLYMER, vol. 50, no. 9, pp. 1986–2000, 2009.
@article{708663,
  abstract     = {Optimised matrix-assisted laser desorption/ionisation (MALDI) and electrospray ionisation (ESI) mass spectrometry (MIS) methodologies were systematically compared in terms of their relative abilities to identify distinct chemical species present in samples associated with a polymer mechanistic study. In order to perform the investigation, formation processes involved in atom transfer radical polymerisation (ATRP) mediated methyl acrylate (MA) star polymerisations were studied. In addition to the 4-armed ATRP initiator employed in the polymerisations, initiator side-products were found to generate oligomeric chains. At a relatively high monomer to polymer conversion, terminal Br loss was observed in these oligomers; this Br loss was hypothesised to occur via degradative transfer reactions involving the radicals (CH3)(2)(C) over dotOH, (C) over dotH(3) and (C) over dotH(2)COCH(3), which were derived from the acetone used as a solvent in the polymerisations, as well as hydrogen radicals donated by the ligand N,N',N',N '',N ''-pentamethyldiethylenetriamine (PMDETA). In performing these studies, ESI was found to identify a greater number of distinct chemical species in the samples under investigation when compared to the employed MALDI technique, suggesting that the utilisation of ESI must be strongly considered in polymer mechanistic investigations if the maximum number of end-group functionalities within a given polymer sample are to be identified.},
  author       = {Hart-Smith, Gene and Lammens, Mieke and Du Prez, Filip and Guilhaus, Michael and Barner-Kowollik, Christopher},
  issn         = {0032-3861},
  journal      = {POLYMER},
  keywords     = {SIZE-EXCLUSION CHROMATOGRAPHY,SYNTHETIC-POLYMERS,ELECTROSPRAY SAMPLE DEPOSITION,LASER-DESORPTION IONIZATION,Star polymers,KeyWords Plus: TRANSFER RADICAL POLYMERIZATION,Author Keywords: Mass spectrometry,Atom transfer radical polymerisation (ATRP),REACTION PATHWAYS,FAST-EVAPORATION,METHYL ACRYLATE,TOF-MS,ACETONE},
  language     = {eng},
  number       = {9},
  pages        = {1986--2000},
  publisher    = {ELSEVIER SCI LTD},
  title        = {ATRP poly(acrylate) star formation: a comparative study between MALDI and ESI mass spectrometry},
  url          = {http://dx.doi.org/10.1016/j.polymer.2009.03.009},
  volume       = {50},
  year         = {2009},
}

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