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Annual Review of Analytical Chemistry

Volume 9, 2016

The Coupled Chemical and Physical Dynamics Model of MALDI

Abstract

The coupled physical and chemical dynamics model of ultraviolet matrix-assisted laser desorption/ionization (MALDI) has reproduced and explained a wide variety of MALDI phenomena. The rationale behind and elements of the model are reviewed, including the photophysics, kinetics, and thermodynamics of primary and secondary reaction steps. Experimental results are compared with model predictions to illustrate the foundations of the model, coupling of ablation and ionization, differences between and commonalities of matrices, secondary charge transfer reactions, ionization in both polarities, fluence and concentration dependencies, and suppression and enhancement effects.

Keyword(s): coupled physical and chemical dynamics model, exciton pooling, ion-molecule reactions, ionization mechanisms, MALDI
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2016-06-12
2025-04-26
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/content/journals/10.1146/annurev-anchem-071015-041750
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The Coupled Chemical and Physical Dynamics Model of MALDI
Annual Review of Analytical Chemistry 9, 365 (2016); https://doi.org/10.1146/annurev-anchem-071015-041750
/content/journals/10.1146/annurev-anchem-071015-041750
/content/journals/10.1146/annurev-anchem-071015-041750
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Supplementary Data

  • Download the Supplemental Material as a PDF, including Supplemental Figures 1–16.

    Supplemental Video 1: Molecular dynamics CPCD simulation including 40 analyte polymers, each of 10 monomer units. The laser pulse width was 35 ps and the fluence was 40 mJ/cm2. Neutral matrix molecules are represented by gray dots, positive ions by red crosses, and negative ions by blue diamonds. Analyte monomers are amber circles. For visualization purposes the vertical, lateral axis is much more expanded that the horizontal, axial one, causing the analytes to appear flattened, but they are randomly folded. Lateral motion also appears faster than axial. The gas phase basicity of each analyte monomer was 50 kJ/mol, making the polymer rather basic. Several analytes become multiply positively charged, but none retains negative charge at longer times. Download Supplemental Video 1 file (MP4, 83MB).

  • Article Type: Review Article

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