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Issue 16, 2018
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Tailored photocleavable peptides: fragmentation and neutralization pathways in high vacuum

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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.

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

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Publication details

The article was received on 14 Feb 2018, accepted on 23 Mar 2018 and first published on 06 Apr 2018


Article type: Paper
DOI: 10.1039/C8CP01058G
Citation: Phys. Chem. Chem. Phys., 2018,20, 11412-11417
  • Open access: Creative Commons BY-NC license
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    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

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