Giving the Green Light to Photochemical Uncaging of Large Biomolecules in High Vacuum

Author(s)
Yong Hua, Marcel Strauss, Sergey Fisher, Martin F.X. Mauser, Pierre Manchet, Martina Smacchia, Philipp Geyer, Armin Shayeghi, Michael Pfeffer, Tim Henri Eggenweiler, Steven Daly, Jan Commandeur, Marcel Mayor, Markus Arndt, Tomáš Šolomek, Valentin Köhler
Abstract

The isolation of biomolecules in a high vacuum enables experiments on fragile species in the absence of a perturbing environment. Since many molecular properties are influenced by local electric fields, here we seek to gain control over the number of charges on a biopolymer by photochemical uncaging. We present the design, modeling, and synthesis of photoactive molecular tags, their labeling to peptides and proteins as well as their photochemical validation in solution and in the gas phase. The tailored tags can be selectively cleaved off at a well-defined time and without the need for any external charge-transferring agents. The energy of a single or two green photons can already trigger the process, and it is soft enough to ensure the integrity of the released biomolecular cargo. We exploit differences in the cleavage pathways in solution and in vacuum and observe a surprising robustness in upscaling the approach from a model system to genuine proteins. The interaction wavelength of 532 nm is compatible with various biomolecular entities, such as oligonucleotides or oligosaccharides.

Organisation(s)
Quantum Optics, Quantum Nanophysics and Quantum Information
External organisation(s)
Universität Basel, University of Amsterdam (UvA), MS Vision, Karlsruher Institut für Technologie, Sun Yat-sen University
Journal
JACS Au
Volume
3
Pages
2790-2799
No. of pages
10
ISSN
2691-3704
DOI
https://doi.org/10.26434/chemrxiv-2023-mgqg3
Publication date
10-2023
Peer reviewed
Yes
Austrian Fields of Science 2012
104017 Physical chemistry
Keywords
ASJC Scopus subject areas
Analytical Chemistry, Chemistry (miscellaneous), Physical and Theoretical Chemistry, Organic Chemistry
Portal url
https://ucrisportal.univie.ac.at/en/publications/giving-the-green-light-to-photochemical-uncaging-of-large-biomolecules-in-high-vacuum(cb0fbce0-85af-4e19-8ec2-aff1453f74a5).html