Atmospheric Pressure Photoionization Mass Spectrometry of Polyisobutylene Derivatives

S. Kéki, János Török, Lajos Nagy, M. Zsuga

Research output: Contribution to journalArticle

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Abstract

Atmospheric pressure photoionization mass spectrometric (APPI-MS) study on three types of polyisobutylene derivatives is reported. Two of the polyisobutylenes investigated were polyisobutylene with dihydroxy and diolefinic end-groups derived from aromatic moieties [dicumyl chloride, 1,4-bis(2-chloro-2-propyl)benzene], and the third contained no aromatic moieties with a monohydroxy end-group. All three polyisobutylene derivatives (PIBs) had an average molecular weight (Mn) of ∼2000 g/mol, with a polydispersity lower than 1.2. In the positive ion APPI mode, protonated PIB molecules were formed, but the molecular weights obtained were considerably lower than those expected, indicating fragmentation of the PIB chains. In the negative APPI mode, using solvents such as tetrahydrofuran and toluene as dopants, no signal was obtained. However, in chlorinated solvents, such as CCl4, CHCl3, and CH2Cl2, in the presence of toluene dopant, PIB adducts with chloride ions were formed with relatively high signal intensity. In the case of CH2Cl2, no dopant (toluene) was necessary to generate chlorinated adduct ions, albeit increasing the toluene concentration in the flow increased the PIB signal intensity. The effect of the toluene concentration on PIB signal intensity was studied and models that include (1) photoionization of toluene, (2) formation of chloride ions from the chlorinated solvents by dissociative electron capture, (3) formation of chlorinated adduct ions and charge recombination reactions between the toluene radical cation, (4) chloride ions, and (5) chlorinated adduct ions are proposed based on the experimental results.

Original languageEnglish
Pages (from-to)656-665
Number of pages10
JournalJournal of the American Society for Mass Spectrometry
Volume19
Issue number5
DOIs
Publication statusPublished - May 2008

Fingerprint

Photoionization
Atmospheric Pressure
Toluene
Atmospheric pressure
Mass spectrometry
Mass Spectrometry
Ions
Derivatives
Chlorides
Doping (additives)
Molecular Weight
Molecular weight
Polydispersity
polyisobutylene
Benzene
Genetic Recombination
Cations
Positive ions
Electrons
Molecules

ASJC Scopus subject areas

  • Structural Biology
  • Spectroscopy

Cite this

Atmospheric Pressure Photoionization Mass Spectrometry of Polyisobutylene Derivatives. / Kéki, S.; Török, János; Nagy, Lajos; Zsuga, M.

In: Journal of the American Society for Mass Spectrometry, Vol. 19, No. 5, 05.2008, p. 656-665.

Research output: Contribution to journalArticle

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