Electron transfer reactivity in matrix-assisted laser desorption/ionization (MALDI): ionization energy, electron affinity and performance of the DCTB matrix within the thermochemical framework

Yury V Vasil'ev; Olga G Khvostenko; Alexey V Streletskii; Olga V Boltalina; Sotirios G Kotsiris; Thomas Drewello

doi:10.1021/jp060568f

Electron transfer reactivity in matrix-assisted laser desorption/ionization (MALDI): ionization energy, electron affinity and performance of the DCTB matrix within the thermochemical framework

J Phys Chem A. 2006 May 11;110(18):5967-72. doi: 10.1021/jp060568f.

Authors

Yury V Vasil'ev¹, Olga G Khvostenko, Alexey V Streletskii, Olga V Boltalina, Sotirios G Kotsiris, Thomas Drewello

Affiliation

¹ Department of Chemistry, University of Warwick, Coventry, CV4 7AL, England, UK.

PMID: 16671662
DOI: 10.1021/jp060568f

Abstract

DCTB [(H(3)C)(3)C-p-Ph-CH=C(CH(3))-trans-CH=C(CN)(2)] has recently advanced to the most promising matrix material for matrix-assisted laser desorption/ionization (MALDI) within material sciences. However, data that would allow the evaluation of the electron-transfer reactivity within a thermochemical framework are sparse. The present study reports the first-time determination of the ionization energy (IE) of DCTB applying photoelectron (PE) spectroscopy. The experimental IE (8.54 +/- 0.05 eV) is in excellent agreement with the theoretical value of 8.47 eV, obtained by AM1 calculations. The same level of theory determines the electron affinity (EA) as 2.31 eV. Model analytes of known thermochemistry (phenanthrene [C(14)H(10)], anthracene [C(14)H(10)] and fluorofullerene [C(60)F(46/48)]) are used to bracket the electron-transfer reactivity within DCTB-MALDI. The formation of molecular ions of these analytes either is expected or is beyond the thermochemical accessibility of the DCTB matrix.