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Title: Fluorescence spectroscopy of UV-MALDI matrices and implications of ionization mechanisms

Matrix-assisted laser desorption ionization (MALDI) has been widely used in the mass analysis of biomolecules; however, there are a lot of debates about the ionization mechanisms. Previous studies have indicated that S{sub 1}-S{sub 1} annihilation might be a key process in the generation of primary ions. This study investigates S{sub 1}-S{sub 1} annihilation by examining the time-resolved fluorescence spectra of 12 matrices. No S{sub 1}-S{sub 1} annihilation was observed in six of these matrices (3-hydroxy-picolinic acid, 6-aza-2-thiothymine, 2,4-dihydroxy-acetophenone, 2,6-dihydroxy-acetophenone, 2,4,6-trihydroxy-acetophenone, and ferulic acid). We observed two matrix molecules reacting in an electronically excited state (S{sub 1}) in five of these matrices (2,5-dihydroxybenzoic acid, α-cyano-4-hydroxycinnamic acid, 2,5-dihydroxy-acetophenone, 2,3-dihydroxybenzoic acid, and 2,6-dihydroxybenzoic acid), and S{sub 1}-S{sub 1} annihilation was a possible reaction. Among these five matrices, no S{sub 1}-S{sub 1} annihilation was observed for 2,3-dihydroxybenzoic acid in typical peak power region of nanosecond laser pulses in MALDI, but a very small value of reaction rate constant was observed only in the high peak power region. The excited-state lifetime of sinapinic acid was too short to determine whether the molecules reacted in an electronically excited state. No correlation was observed between the ion generation efficiency of MALDI and S{sub 1}-S{sub 1} annihilation. Themore » results indicate that the proposal of S{sub 1}-S{sub 1} annihilation is unnecessary in MALDI and energy pooling model for MALDI ionization mechanism has to be modified.« less
Authors:
; ; ; ;  [1] ; ; ;  [2] ;  [3]
  1. Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan (China)
  2. National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan (China)
  3. Department of Applied Chemistry, National Chiao Tung University, Hsinchu 30010, Taiwan (China)
Publication Date:
OSTI Identifier:
22310749
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 16; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACETOPHENONE; ANNIHILATION; DESORPTION; EFFICIENCY; EXCITED STATES; FLUORESCENCE SPECTROSCOPY; IONIZATION; LASERS; MOLECULES; PEAK LOAD; PICOLINIC ACID; PULSES; REACTION KINETICS