Issue 16, 2018

Tailored photocleavable peptides: fragmentation and neutralization pathways in high vacuum

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.

Graphical abstract: Tailored photocleavable peptides: fragmentation and neutralization pathways in high vacuum

Supplementary files

Article information

Article type
Paper
Submitted
14 Feb 2018
Accepted
23 Mar 2018
First published
06 Apr 2018
This article is Open Access
Creative Commons BY-NC license

Phys. Chem. Chem. Phys., 2018,20, 11412-11417

Tailored photocleavable peptides: fragmentation and neutralization pathways in high vacuum

M. Debiossac, J. Schätti, M. Kriegleder, P. Geyer, A. Shayeghi, M. Mayor, M. Arndt and V. Köhler, Phys. Chem. Chem. Phys., 2018, 20, 11412 DOI: 10.1039/C8CP01058G

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements