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

Gene Hart-Smith, Mieke Lammens, Filip E. Du Prez*, Michael Guilhaus, Christopher Barner-Kowollik

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

26 Citations (Scopus)


Optimised matrix-assisted laser desorption/ionisation (MALDI) and electrospray ionisation (ESI) mass spectrometry (MS) 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)2ĊOH, ĊH3 and ĊH2COCH3 , 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.

Original languageEnglish
Pages (from-to)1986-2000
Number of pages15
Issue number9
Publication statusPublished - 24 Apr 2009
Externally publishedYes


  • mass spectrometry
  • atom transfer radical polymerisation (ATRP)
  • star polymers


Dive into the research topics of 'ATRP poly(acrylate) star formation: a comparative study between MALDI and ESI mass spectrometry'. Together they form a unique fingerprint.

Cite this