AI Article Synopsis
- A quantitative model for ionization in UV matrix-assisted laser desorption/ionization is expanded to include secondary ion-molecule reactions.
- The model uses a hard-sphere Arrhenius expression for charge-transfer kinetics and applies a nonlinear free energy relationship for determining activation energy.
- It accurately predicts matrix/analyte suppression effects, two-pulse yield curves, and the impacts of laser fluence, molecular weight, concentrations, and reaction energy on analyte yields without needing adjustable parameters.
Article Abstract
A quantitative model of ionization in ultraviolet matrix-assisted laser desorption/ionization (Knochenmuss, R. J. Mass Spectrom. 2002, 37, 867) is extended to include secondary ion-molecule reactions. Matrix-to-analyte charge-transfer reaction kinetics are described by a hard-sphere Arrhenius expression. The activation energy is derived from the reaction exoergicity using a nonlinear free energy relationship. The approach is applied to the specific case of proton-transfer reactions. With no adjustable parameters, the model correctly predicts the existence and characteristics of the matrix and analyte suppression effects, the shapes of the two-pulse time-delayed yield curves, and the dependence of analyte yields on laser fluence, molecular weight, relative concentrations, and reaction exoergicity.
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| http://dx.doi.org/10.1021/ac034032r | DOI Listing |
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