Negative Ion MALDI Mass Spectrometry of Polyoxometalates (POMs): Mechanism of Singly Charged Anion Formation and Chemical Properties Evaluation

  • Jean E. Boulicault
  • Sandra Alves
  • Richard B. Cole
Research Article

DOI: 10.1007/s13361-016-1400-6

Cite this article as:
Boulicault, J.E., Alves, S. & Cole, R.B. J. Am. Soc. Mass Spectrom. (2016) 27: 1301. doi:10.1007/s13361-016-1400-6
  • 265 Downloads

Abstract

MALDI-MS has been developed for the negative ion mode analysis of polyoxometalates (POMs). Matrix optimization was performed using a variety of matrix compounds. A first group of matrixes offers MALDI mass spectra containing abundant intact singly charged anionic adduct ions, as well as abundant in-source fragmentations at elevated laser powers. A relative ranking of the ability to induce POM fragmentation is found to be: DAN > CHCA > CNA > DIT> HABA > DCTB > IAA. Matrixes of a second group provide poorer quality MALDI mass spectra without observable fragments. Sample preparation, including the testing of salt additives, was performed to optimize signals for a model POM, POMc12, the core structure of which bears four negative charges. The matrix 9-cyanoanthracene (CNA) provided the best signals corresponding to singly charged intact POMc12 anions. Decompositions of these intact anionic species were examined in detail, and it was concluded that hydrogen radical-induced mechanisms were not prevalent, but rather that the observed prompt fragments originate from transferred energy derived from initial electronic excitation of the CNA matrix. Moreover, in obtained MALDI mass spectra, clear evidence of electron transfer to analyte POM species was found: a manifestation of the POMs ability to readily capture electrons. The affinity of polyanionic POMc12 toward a variety of cations was evaluated and the following affinity ranking was established: Fe3+ > Al3+ > Li+ > Ga3+ > Co2+ > Cr3+ > Cu2+ > [Mn2+, Mg2+] > [Na+, K+]. Thus, from the available cationic species, specific adducts are preferentially formed, and evidence is given that these higher affinity POM complexes are formed in the gas phase during the early stages of plume expansion.

Graphical Abstract

Keywords

Negative Ion MALDI Polyoxometalates (POMs) In-source decay MALDI mechanisms Cationic adduct Fragmentation 

Supplementary material

13361_2016_1400_MOESM1_ESM.doc (363 kb)
ESM 1(DOC 363 kb)

Copyright information

© American Society for Mass Spectrometry 2016

Authors and Affiliations

  • Jean E. Boulicault
    • 1
  • Sandra Alves
    • 1
  • Richard B. Cole
    • 1
  1. 1.Sorbonne Universités, UPMC Univ Paris 06, CNRS, Institut Parisien de Chimie Moléculaire (IPCM)Paris Cedex 05France