Titel
Tailored photocleavable peptides: fragmentation and neutralization pathways in high vacuum
Autor*in
J. Schätti
Department of Chemistry, University of Basel
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Abstract
Photocleavable tags (PCTs) have the potential for excellent spatio-temporal control over the release of subunits of complex molecules. Here, we show that electrosprayed oligopeptides, functionalized by a tailored ortho-nitroarylether can undergo site-specific photo-activated cleavage under UV irradiation (266 nm) in high vacuum. The comparison of UV photodissociation (UVPD) and collision-induced dissociation (CID) points to the thermal nature of the cleavage mechanism, a picture corroborated by the temperature dependence of the process. Two competing photodissociation pathways can be identified. In one case a phenolate anion is separated from a neutral zwitterion. In the other case a neutral phenol derivative leaves a negatively charged peptide behind. To understand the factors favoring one channel over the other, we investigate the influence of the peptide length, the nature of the phenolic group and the position of the nitro-group (ortho vs. para). The observed gas phase cleavage of a para-nitro benzylic ether markedly differs from the established behavior in solution.
Objekt-Typ
Sprache
Englisch [eng]
Persistent identifier
https://phaidra.univie.ac.at/o:936649
Erschienen in
Titel
Physical Chemistry Chemical Physics
Band
20
Ausgabe
16
Seitenanfang
11412
Seitenende
11417
Verlag
Royal Society of Chemistry (RSC)
Projektnummer
320694 – European Union (all programmes)
Erscheinungsdatum
2018
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