Tailored photocleavable peptides: fragmentation and neutralization pathways in high vacuum

Debiossac, M. and Schätti, J. and Kriegleder, M. and Geyer, P. and Shayeghi, A. and Mayor, M. and Arndt, M. and Köhler, V.. (2018) Tailored photocleavable peptides: fragmentation and neutralization pathways in high vacuum. Physical Chemistry Chemical Physics, 20 (16). pp. 11412-11417.

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Official URL: https://edoc.unibas.ch/68424/

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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.
Faculties and Departments:05 Faculty of Science > Departement Chemie
05 Faculty of Science > Departement Chemie > Chemie > Molecular Devices and Materials (Mayor)
UniBasel Contributors:Mayor, Marcel and Schätti, Jonas and Köhler, Valentin
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Royal Society of Chemistry
Note:Publication type according to Uni Basel Research Database: Journal article
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Last Modified:03 Apr 2023 09:43
Deposited On:02 Jul 2019 10:59

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