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Collision Induced Dissociation of the retinal chromophore Schiff base from sub-eV to keV collision energies
Stockholm University, Faculty of Science, Department of Physics.ORCID iD: 0000-0002-6770-1595
Stockholm University, Faculty of Science, Department of Physics.
Stockholm University, Faculty of Science, Department of Physics. Universität Innsbruck, Austria.ORCID iD: 0000-0003-1028-7976
Stockholm University, Faculty of Science, Department of Physics.ORCID iD: 0000-0003-0471-3844
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(English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215Article in journal (Refereed) Submitted
Abstract [en]

The gas-phase fragmentation of the protonated n-butylamine Schiff base of all-trans-retinal (NB-RPSB) was measured in low- and high-energy collisional activation modes. The protonated n-butyl β-ionone Schiff base (NB-BISB) peak at m/z = 248, known to be formed as a result of a complex gas-phase rearrangement reaction, has been reported to dominate in mass spectra of NB-RPSB after photo- and collisionally activated fragmentation processes. Earlier reported high-energy collision (50 keV) mass spectra have shown a broad distribution of the fragments with the peak at m/z = 248 present but not dominating. We observed the formation of a peak at m/z = 248 only in collisional activation of NB-RPSB parent ion below a few eV, which shows that the rearrangement process is extremely efficient and happens in a very narrow energy range. On the other hand, our high-energy collision induced dissociation experiments yielded fragmentation patterns, which are fully accounted for simple bond cleavages of the NB-RPSB molecular backbone. We do not observe any peak corresponding to the formation of NB-BISB in the 10 eV – 1 keV collision energy range. This leaves the question open why this fragment reappears in the mass spectra at much higher energies.

National Category
Physical Sciences
Research subject
Physics
Identifiers
URN: urn:nbn:se:su:diva-149529OAI: oai:DiVA.org:su-149529DiVA, id: diva2:1163263
Funder
Swedish Research Council, 2015-04990Swedish Research Council, 2014-04501Swedish Research Council, 2016-06625Swedish Research Council, 2016-04181Available from: 2017-12-06 Created: 2017-12-06 Last updated: 2022-02-28Bibliographically approved
In thesis
1. Energetic processing of complex molecules in the gas phase
Open this publication in new window or tab >>Energetic processing of complex molecules in the gas phase
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Collisions between molecules and gas phase targets often lead to various intriguing processes. Such collisions may induce fragmentation of molecules that can be divided into different subsets depending on the projectile, target, and collision energy. One major part of the present research is the exploration of astrophysical relevant collision mechanisms. In collisions between polycyclic aromatic hydrocarbon (PAH) molecules or fullerenes with, for example, helium, nuclear stopping can lead to the prompt knockout of a carbon atom from the molecule. Such a vacancy in the molecular carbon backbone can be highly reactive, and lead to the formation of larger molecules. The energy dependencies of such processes are important for the understanding of astrochemical molecular growth processes, which in turn may lead to the formation of larger and more complex molecules in space. In addition, hydrogenation of PAHs changes their structures and internal properties, including their resistance against fragmentation. To better understand the effects of hydrogenation on the fragmentation of PAHs, low energy photofragmentation experiments are presented along with the collision experiments, and a detailed comparison is made between the effects of these different types of energy transfer processes.

Besides astrophysically relevant research, studies on the response of biomolecules to collisions with gas phase targets are presented. Here, the energy dependence for formation of the protonated n-butyl β-ionone Schiff base through electrocyclization of the protonated n-butylamine Schiff base of all-trans-retinal in collisions is presented. The latter is a model compound for all-trans-retinal, the chromophore of the light sensitive opsin proteins, and such studies are essential for the understanding of the operation of mammal vision.

While our collision studies are very successful, they are sometimes also limited by the experimental timescale. Therefore, we have constructed an experimental setup for ion storage and fragmentation analysis. The goal of this new experiment is to store internally hot fragments to investigate their behavior on extended timescales and as functions of internal excitation energies.

Place, publisher, year, edition, pages
Department of Physics, Stockholm University, 2018
National Category
Physical Sciences
Research subject
Physics
Identifiers
urn:nbn:se:su:diva-149602 (URN)978-91-7797-083-5 (ISBN)978-91-7797-084-2 (ISBN)
Public defence
2018-01-31, FB52, AlbaNova Universitetscentrum, Roslagstullsbacken 21, Stockholm, 13:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 5: Submitted. Paper 6: Submitted.

Available from: 2018-01-08 Created: 2017-12-06 Last updated: 2022-02-28Bibliographically approved

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Kulyk, KostiantynWolf, MichaelGatchell, MichaelGiacomozzi, Lindade Ruette, NathalieSchmidt, T. HenningCederquist, HenrikZettergren, Henning

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