Electron-Induced Reactions in 3-Bromopyruvic Acid
- 3-Bromopyruvic acid (3BP) is a potential anticancer drug, the action of which on cellular metabolism is not yet entirely clear. The presence of a bromine atom suggests that it is also reactive towards low-energy electrons, which are produced in large quantities during tumour radiation therapy. Detailed knowledge of the interaction of 3BP with secondary electrons is a prerequisite to gain a complete picture of the effects of 3BP in different forms of cancer therapy. Herein, dissociative electron attachment (DEA) to 3BP in the gas phase has been studied both experimentally by using a crossed-beam setup and theoretically through scattering and quantum chemical calculations. These results are complemented by a vacuum ultraviolet absorption spectrum. The main fragmentation channel is the formation of Br- close to 0 eV and within several resonant features at 1.9 and 3-8 eV. At low electron energies, Br- formation proceeds through sigma* and pi* shape resonances, and at higher energies through core-excited resonances. It is found that the3-Bromopyruvic acid (3BP) is a potential anticancer drug, the action of which on cellular metabolism is not yet entirely clear. The presence of a bromine atom suggests that it is also reactive towards low-energy electrons, which are produced in large quantities during tumour radiation therapy. Detailed knowledge of the interaction of 3BP with secondary electrons is a prerequisite to gain a complete picture of the effects of 3BP in different forms of cancer therapy. Herein, dissociative electron attachment (DEA) to 3BP in the gas phase has been studied both experimentally by using a crossed-beam setup and theoretically through scattering and quantum chemical calculations. These results are complemented by a vacuum ultraviolet absorption spectrum. The main fragmentation channel is the formation of Br- close to 0 eV and within several resonant features at 1.9 and 3-8 eV. At low electron energies, Br- formation proceeds through sigma* and pi* shape resonances, and at higher energies through core-excited resonances. It is found that the electron-capture cross-section is clearly increased compared with that of non-brominated pyruvic acid, but, at the same time, fragmentation reactions through DEA are significantly altered as well. The 3BP transient negative ion is subject to a lower number of fragmentation reactions than those of pyruvic acid, which indicates that 3BP could indeed act by modifying the electron-transport chains within oxidative phosphorylation. It could also act as a radio-sensitiser.…
Author details: | Filipe Ferreira da SilvaORCiD, Marcio T. do N. Varella, Nykola C. JonesORCiD, Soren Vronning HoffmannORCiD, Stephan DeniflORCiD, Ilko BaldORCiDGND, Janina KopyraORCiD |
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DOI: | https://doi.org/10.1002/chem.201806132 |
ISSN: | 0947-6539 |
ISSN: | 1521-3765 |
Pubmed ID: | https://pubmed.ncbi.nlm.nih.gov/30706547 |
Title of parent work (English): | Chemistry - a European journal |
Publisher: | Wiley-VCH |
Place of publishing: | Weinheim |
Publication type: | Article |
Language: | English |
Date of first publication: | 2019/02/01 |
Publication year: | 2019 |
Release date: | 2021/03/04 |
Tag: | density functional calculations; dissociative electron attachment; drug discovery; gas-phase reactions; sensitizers |
Volume: | 25 |
Issue: | 21 |
Number of pages: | 9 |
First page: | 5498 |
Last Page: | 5506 |
Funding institution: | Deutsche Forschungsgemeinschaft (DFG)German Research Foundation (DFG) [230710387]; FWF, ViennaAustrian Science Fund (FWF) [P30332]; Sao Paulo Research FoundationFundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP) [2017/24145-9]; Brazilian National Council for Scientific and Technological DevelopmentNational Council for Scientific and Technological Development (CNPq) [305672/2014-2]; Portuguese National Funding Agency FCT-MCTES [IF-FCT IF/00380/2014, PTDC/FIS-AQM/31251/2017, UID/FIS/00068/2013]; Polish Ministry of Science and Higher EducationMinistry of Science and Higher Education, Poland [277/S/11] |
Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
DDC classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften |
Peer review: | Referiert |
Publishing method: | Open Access / Bronze Open-Access |