Multiple charging of poly(propylene glycol) by binary mixtures of cations in electrospray

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Single, double and triple charging of poly(propylene glycol) (PPG) (M n = 1900 g/mol) in the presence of binary mixtures of cations (Li+, Na+, K+, Cs+, and NH 4+) under electrospray ionization (ESI) conditions were investigated. For these studies, sodium ion was selected as the reference cation, and the resulting ion-intensities were evaluated as a function of the [Na+]/[C+] ratio (where C+ is the other cation, i.e., Li+, K+, Cs+ and NH4 +). A linear relationship was found between INa+/I C+ and [Na+]/[C+] (INa+ and I C+ stand for the intensity of the singly charged PPG molecules cationized with Na+ and C+ ions, respectively). The slope of the INa+/IC+ - [Na+]/[C+] plot (α) indicates the binding selectivity of Na+ ions to PPG chains with respect to cation C+. In the case of the doubly charged PPG chains, the INaNa2+/INaC2+ and INaC2+/I CC2+ versus [Na+]/[C+] ratio also yield straight lines with slopes of approximately α/2 and 2α, respectively (INaNa2+, INaC2+ and ICC2+ are the intensity of the doubly charged PPG chains cationized with two Na+ ions, Na+ and C+ ions, and two C+ ions, respectively). Similarly, linear dependences with the [Na+]/[C +] ratio for the corresponding intensity ratios of the triply charged PPG were found. Based on the value of α, the selectivity of the cations was found to increase in the order of Li+ < Cs+ ≈ Na+ < K+ ≈ NH4+. The observed relative ion intensities are interpreted on the basis of the solution state equilibrium between PPG and the cations. In addition, the investigations showed that the abundances of the doubly and triply charged PPG-containing mixed cations can be optimized in a simple way using the value of α.

Original languageEnglish
Pages (from-to)152-157
Number of pages6
JournalJournal of the American Society for Mass Spectrometry
Issue number2
Publication statusPublished - Feb 1 2005


ASJC Scopus subject areas

  • Structural Biology
  • Spectroscopy

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