http://www.cnr.it/ontology/cnr/individuo/prodotto/ID195424

On the Primary IonizationMechanism(s) in Matrix-Assisted Laser Desorption Ionization (Articolo in rivista)

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On the Primary IonizationMechanism(s) in Matrix-Assisted Laser Desorption Ionization (Articolo in rivista) (literal)

Anno

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Alternative label

Molin L.; Seraglia R.; Czarnocki Z.; Maurin J.K.; Pluci?ski F.A.; Traldi P. (2012)
On the Primary IonizationMechanism(s) in Matrix-Assisted Laser Desorption Ionization
in Journal of Analytical Methods in Chemistry; Hindawi Publishing Corporation, New York (Stati Uniti d'America)
(literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori

Molin L.; Seraglia R.; Czarnocki Z.; Maurin J.K.; Pluci?ski F.A.; Traldi P. (literal)

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Note

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1,2,6 : National Council of Researches, Institute of Molecular Sciences and Technologies, Corso Stati Uniti 4, I35100 Padova, Italy / 3 : Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland / 4,5 : National Medicines Institute, Che?mska 30/34, 00-725 Warsaw, Poland / 4 : National Centre for Nuclear Research, 05-400 Otwock, ?wierk, Poland (literal)

Titolo

On the Primary IonizationMechanism(s) in Matrix-Assisted Laser Desorption Ionization (literal)

Abstract

A mechanism is proposed for the first step of ionization occurring in matrix-assisted laser desorption ionization, leading to protonated and deprotonated matrix (Ma) molecules ([Ma+H]+ and [Ma-H] -ions). It is based on observation that in solid state, for carboxyl-containing MALDI matrices, the molecules form strong hydrogen bonds and their carboxylic groups can act as both donors and acceptors. This behavior leads to stable dimeric structures. The laser irradiation leads to the cleavage of these hydrogen bonds, and theoretical calculations show that both [Ma+H]+ and [Ma-H]- ions can be formed through a two-photon absorption process. Alternatively, by the absorption of one photon only, a heterodissociation of one of the O-H bonds can lead to a stable structure containing both cationic and anionic sites. This structure could be considered an intermediate that, through the absorption of a further photon, leads to the formation of matrix ions. Some experiments have been performed to evaluate the role of thermal ionization and indicate that its effect is negligible. Some differences have been observed for different matrices in the formation of analyte molecule (M) ion [M+H] +, [M-H]-, M+o, and [M-2H]-o, and they have been explained in terms of ionization energies, pKa values, and thermodynamic stability. (literal)

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