Chinese Journal of Chromatography ›› 2014, Vol. 32 ›› Issue (4): 395-401.DOI: 10.3724/SP.J.1123.2013.11001

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Preliminary exploration of energy transfer about sample ionization process in electrospray ionization source

ZHANG Weibing1,2, GAO Fangyuan1, GUAN Yafeng2, ZHANG Yukui2   

  1. 1. East China University of Science and Technology, Shanghai 200237, China;
    2. Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
  • Received:2013-11-04 Revised:2014-01-16 Online:2014-04-08 Published:2014-03-28

Abstract:

Electrospray ionization source (ESI) can be used not only for the detection of small molecules, but also for large molecules such as proteins and peptides. This article proposes energy transfer theory based on the lowest energy principle by systematically analyzing ionization processes. The transference of the analyte from liquid phase to gas phase can be influenced by multiple forces during the ionization and vaporization processes, such as electrostatics force and van der Waals' force. The ionization of samples is the result of the interactions among multiple forces. During different stages of the ionization process, different forces lead to different effects. There are competition between evaporation and formation of multi-charge ions for charges. For molecules with different structures, Gibbs free energy between two phases from the changes of molecule shape or conformation may lead to ion evaporation, multiply charged macromolecule and chain ejection, etc. The energy transfer theory can simplify the three existing theories, as well as explain the solvent effect and electrolyte ion effect during ionization process. The proposed theory provides foundation to optimize the detection condition for different samples and to understand the real process of ionization.

Key words: charges transfer energy, electrospray ionization source (ESI), principle of lowest energy, sample ionization

CLC Number: