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Physicochemical Property Correlations with Ionization Efficiency in Capillary Vibrating Sharp-Edge Spray Ionization

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Capillary vibrating sharp-edge spray ionization (cVSSI) shows different chemical property influences on ion intensity compared to electrospray ionization (ESI). Field-enabled cVSSI highlights partition coefficient (log P), while field-free cVSSI emphasizes basicity (pKb) and proton affinity (PA).

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Area of Science:

  • Analytical Chemistry
  • Mass Spectrometry
  • Separation Science

Background:

  • Electrospray ionization (ESI) is a widely used technique for mass spectrometry (MS) analysis.
  • Understanding the factors influencing ionization efficiency is crucial for quantitative MS analysis.
  • Capillary vibrating sharp-edge spray ionization (cVSSI) is a newer ionization technique with potential advantages.

Purpose of the Study:

  • To investigate the relative contributions of molecular chemical properties to ionization efficiency in cVSSI.
  • To compare ionization mechanisms of field-free and field-enabled cVSSI with traditional ESI.
  • To determine how solvent systems (aqueous and methanol) affect these relationships.

Main Methods:

  • Analysis of model compounds using mass spectrometry (MS).
  • Comparison of ion intensities under field-free and field-enabled cVSSI modes.
  • Application of multiple regression analysis to correlate ion intensity with chemical properties (pKb, PA, log P).

Main Results:

  • For field-free cVSSI, ion intensity is primarily associated with log of the base dissociation constant (pKb) and proton affinity (PA) in both aqueous and methanol solutions.
  • For field-enabled cVSSI, the log of the partition coefficient (log P) becomes the dominant factor, especially in aqueous solutions.
  • In traditional ESI, pKb remains the dominant factor influencing ion signal across both solvent systems.

Conclusions:

  • The chemical property correlations with ion intensity differ significantly between cVSSI modes and ESI.
  • The shift in dominant factors suggests that different ionization mechanisms may be operative in cVSSI.
  • Field-enabled cVSSI may be more suitable for analyzing less polar compounds due to the influence of log P.