{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T09:13:57Z","timestamp":1760346837174,"version":"build-2065373602"},"reference-count":49,"publisher":"MDPI AG","issue":"24","license":[{"start":{"date-parts":[[2019,12,6]],"date-time":"2019-12-06T00:00:00Z","timestamp":1575590400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","doi-asserted-by":"publisher","award":["PD\/BD\/106038\/2015","UID\/FIS\/00068\/2019 (CEFITEC)","PTDC\/FIS-AQM\/31281\/2017","PD\/00193\/2012","UID\/Multi\/04378\/2013 (UCIBIO)"],"award-info":[{"award-number":["PD\/BD\/106038\/2015","UID\/FIS\/00068\/2019 (CEFITEC)","PTDC\/FIS-AQM\/31281\/2017","PD\/00193\/2012","UID\/Multi\/04378\/2013 (UCIBIO)"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100014440","name":"Ministerio de Ciencia, Innovaci\u00f3n y Universidades","doi-asserted-by":"publisher","award":["FIS2016-80440"],"award-info":[{"award-number":["FIS2016-80440"]}],"id":[{"id":"10.13039\/100014440","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100010190","name":"Grand \u00c9quipement National De Calcul Intensif","doi-asserted-by":"publisher","award":["A0030807662"],"award-info":[{"award-number":["A0030807662"]}],"id":[{"id":"10.13039\/501100010190","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["IJMS"],"abstract":"<jats:p>Electron transfer induced decomposition mechanism of nitroimidazole and a selection of analogue molecules in collisions with neutral potassium (K) atoms from 10 to 1000 eV have been thoroughly investigated. In this laboratory collision regime, the formation of negative ions was time-of-flight mass analyzed and the fragmentation patterns and branching ratios have been obtained. The most abundant anions have been assigned to the parent molecule and the nitrogen oxide anion (NO2\u2013) and the electron transfer mechanisms are comprehensively discussed. This work focuses on the analysis of all fragment anions produced and it is complementary of our recent work on selective hydrogen loss from the transient negative ions produced in these collisions. Ab initio theoretical calculations were performed for 4-nitroimidazole (4NI), 2-nitroimidazole (2NI), 1-methyl-4- (Me4NI) and 1-methyl-5-nitroimidazole (Me5NI), and imidazole (IMI) in the presence of a potassium atom and provided a strong basis for the assignment of the lowest unoccupied molecular orbitals accessed in the collision process.<\/jats:p>","DOI":"10.3390\/ijms20246170","type":"journal-article","created":{"date-parts":[[2019,12,6]],"date-time":"2019-12-06T10:41:44Z","timestamp":1575628904000},"page":"6170","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":15,"title":["Electron Transfer Induced Decomposition in Potassium\u2013Nitroimidazoles Collisions: An Experimental and Theoretical Work"],"prefix":"10.3390","volume":"20","author":[{"given":"M\u00f3nica","family":"Mendes","sequence":"first","affiliation":[{"name":"Atomic and Molecular Collisions Laboratory, CEFITEC, Department of Physics, Universidade NOVA de Lisboa, Campus de Caparica, 2829-516 Caparica, Portugal"}]},{"given":"Gustavo","family":"Garc\u00eda","sequence":"additional","affiliation":[{"name":"Instituto de F\u00edsica Fundamental, Consejo Superior de Investigaciones Cient\u00edficas, Serrano 113-bis, 28006 Madrid, Spain"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0958-2380","authenticated-orcid":false,"given":"Marie-Christine","family":"Bacchus-Montabonel","sequence":"additional","affiliation":[{"name":"Univ. Lyon, Universit\u00e9 Claude Bernard Lyon 1, CNRS, Institut Lumie\u0300re Matie\u0300re, 69622 Villeurbanne, France"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2696-1152","authenticated-orcid":false,"given":"Paulo","family":"Lim\u00e3o-Vieira","sequence":"additional","affiliation":[{"name":"Atomic and Molecular Collisions Laboratory, CEFITEC, Department of Physics, Universidade NOVA de Lisboa, Campus de Caparica, 2829-516 Caparica, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2019,12,6]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"397","DOI":"10.1016\/j.clon.2007.03.010","article-title":"Chemical Radiosensitizers for Use in Radiotherapy","volume":"19","author":"Wardman","year":"2007","journal-title":"Clin. Oncol."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"24","DOI":"10.1016\/j.tips.2017.11.003","article-title":"Cancer Radiosensitizers","volume":"39","author":"Wang","year":"2018","journal-title":"Trends Pharm. Sci."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"135","DOI":"10.1016\/S0167-8140(97)00220-X","article-title":"A randomized double-blind phase III study of nimorazole as a hypoxic radiosensitizer of primary radiotherapy in supraglottic larynx and pharynx carcinoma. Results of the Danish Head and Neck Cancer Study (DAHANCA) Protocol 5-85","volume":"46","author":"Overgaard","year":"1998","journal-title":"Radiother. Oncol."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"22","DOI":"10.1016\/j.radonc.2011.03.004","article-title":"Hypoxic modification of radiotherapy in squamous cell carcinoma of the head and neck\u2014A systematic review and meta-analysis","volume":"100","author":"Overgaard","year":"2011","journal-title":"Radiother. Oncol."},{"key":"ref_5","first-page":"56","article-title":"Formation of radical anions of radiosensitizers and related model compounds via electrospray ionization","volume":"365","author":"Albright","year":"2014","journal-title":"Int. J. Mass Spectrom."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"014302","DOI":"10.1063\/1.5062604","article-title":"Binding preference of nitroimidazolic radiosensitizers to nucleobases and nucleosides probed by electrospray ionization mass spectrometry and density functional theory","volume":"150","author":"Pandeti","year":"2019","journal-title":"J. Chem. Phys."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"9986","DOI":"10.1021\/acs.jpca.5b05950","article-title":"Photoelectron Spectra and Electronic Structures of the Radiosensitizer Nimorazole and Related Compounds","volume":"119","author":"Plekan","year":"2015","journal-title":"J. Phys. Chem. A"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"2388","DOI":"10.1038\/s41467-019-10340-8","article-title":"Low-energy electrons transform the nimorazole molecule into a radiosensitiser","volume":"10","author":"Fedor","year":"2019","journal-title":"Nat. Commun."},{"key":"ref_9","doi-asserted-by":"crossref","unstructured":"Mei\u00dfner, R., Feketeov\u00e1, L., Illenberger, E., and Denifl, S. (2019). Reactions in the Radiosensitizer Misonidazole Induced by Low-Energy (0\u201310 eV) Electrons. Int. J. Mol. Sci., 20.","DOI":"10.3390\/ijms20143496"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"12240","DOI":"10.1002\/anie.201407452","article-title":"Reactions in Nitroimidazole Triggered by Low-Energy (0\u20132 eV) Electrons: Methylation at N1-H Completely Blocks Reactivity","volume":"53","author":"Tanzer","year":"2014","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"6668","DOI":"10.1021\/acs.jpca.5b02721","article-title":"Reactions in Nitroimidazole and Methylnitroimidazole Triggered by Low-Energy (0\u20138 eV) Electrons","volume":"119","author":"Tanzer","year":"2015","journal-title":"J. Phys. Chem. A"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"114303","DOI":"10.1063\/1.4752654","article-title":"Experimental and theoretical studies of the decomposition of new imidazole based energetic materials: Model systems","volume":"137","author":"Yu","year":"2012","journal-title":"J. Chem. Phys."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"4031","DOI":"10.1021\/acs.jpca.8b01144","article-title":"Insights into 2- and 4(5)-Nitroimidazole Decomposition into Relevant Ions and Molecules Induced by VUV Ionization","volume":"122","author":"Cartoni","year":"2018","journal-title":"J. Phys. Chem. A"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"164310","DOI":"10.1063\/1.5005604","article-title":"How does methylation suppress the electron-induced decomposition of 1-methyl-nitroimidazoles?","volume":"147","author":"Kossoski","year":"2017","journal-title":"J. Chem. Phys."},{"key":"ref_15","doi-asserted-by":"crossref","unstructured":"Brown, E.G. (1998). Imidazoles and Benzimidazoles. Ring Nitrogen and Key Biomolecules, Springer.","DOI":"10.1007\/978-94-011-4906-8"},{"key":"ref_16","first-page":"1","article-title":"Studies on Imidazole and Its Derivatives with Particular Emphasis on Their Chemical\/biological Applications as Bioactive Molecules\/Intermediated to Bioactive Molecule","volume":"5","author":"Kumar","year":"2017","journal-title":"Curr. Synth. Syst. Biol."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"6406","DOI":"10.1039\/C6CP08773F","article-title":"Stripping off Hydrogens in Imidazole Triggered by the Attachment of a Single Electron","volume":"19","author":"Ribar","year":"2017","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"5721","DOI":"10.1021\/jp048759a","article-title":"Electron attachment to the aza-derivatives of furan, pyrrole, and thiophene","volume":"108","author":"Modelli","year":"2004","journal-title":"J. Phys. Chem. A"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"10662","DOI":"10.1021\/jp002157j","article-title":"Gas-phase experimental and theoretical studies of adenine, imidazole, pyrrole, and water non-covalent complexes","volume":"104","author":"Carles","year":"2000","journal-title":"J. Phys. Chem. A"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"11504","DOI":"10.1021\/jp053566o","article-title":"Photoelectron spectra and ion chemistry of imidazolide","volume":"109","author":"Gianola","year":"2005","journal-title":"J. Phys. Chem. A"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"191102","DOI":"10.1063\/1.4967770","article-title":"Communication: \u201cPosition\u201d does matter: The photofragmentation of the nitroimidazole isomers","volume":"145","author":"Bolognesi","year":"2016","journal-title":"J. Chem. Phys."},{"key":"ref_22","first-page":"151","article-title":"The Problem of the Tautomerism of 4(5)-Nitroimidazole\u2014A Theoretical and Experimental-Study","volume":"13","author":"Jimenez","year":"1989","journal-title":"New J. Chem."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"4068","DOI":"10.1021\/acs.jpca.9b02064","article-title":"Selective Bond Excision of Nitroimidazoles in Electron Transfer Experiments","volume":"123","author":"Mendes","year":"2019","journal-title":"J Phys Chem A"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"134301","DOI":"10.1063\/1.5021888","article-title":"Electron transfer driven decomposition of adenine and selected analogs as probed by experimental and theoretical methods","volume":"148","author":"Cunha","year":"2018","journal-title":"J. Chem. Phys."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"264","DOI":"10.3389\/fchem.2019.00264","article-title":"Ion-pair formation in neutral potassium-neutral pyrimidine collisions: Electron transfer experiments","volume":"7","author":"Mendes","year":"2019","journal-title":"Front. Chem."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/0370-1573(82)90092-8","article-title":"Vibronic Coupling At Intersections of Covalent and Ionic States","volume":"90","author":"Kleyn","year":"1982","journal-title":"Phys. Rep."},{"key":"ref_27","doi-asserted-by":"crossref","unstructured":"Lawley, K.P. (1980). Collisional Ionization. Advances in Chemical Physics (Potential Energy Surfaces), John Wiley & Sons Ltd.","DOI":"10.1002\/9780470142615"},{"key":"ref_28","unstructured":"(2019, September 01). NIST Chemistry WebBook, Available online: http:\/\/webbook.nist.gov\/chemistry\/."},{"key":"ref_29","unstructured":"Baumgartel, H., Frank, E.U., and Grunbein, W. (1992). Gaseous Molecular Ions: An Introduction to Elementary Processes Induced by Ionization, Steinkopff-Verlag. [1st ed.]."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"R1","DOI":"10.1088\/0953-4075\/34\/14\/201","article-title":"Negative ion formation in alkali-atom-molecule collisions","volume":"34","author":"Kleyn","year":"2001","journal-title":"J. Phys. B"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"054306","DOI":"10.1063\/1.2161217","article-title":"Dissociative ion-pair formation in collisions of fast potassium atoms with benzene and fluorobenzene","volume":"124","author":"Moutinho","year":"2006","journal-title":"J. Chem. Phys."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"12892","DOI":"10.1002\/chem.201702644","article-title":"Isomer Selectivity in Low-Energy Electron Attachment to Nitroimidazoles","volume":"23","author":"Ribar","year":"2017","journal-title":"Chem. Eur. J."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"9","DOI":"10.1016\/j.freeradbiomed.2010.03.025","article-title":"Oxidatively generated base damage to cellular DNA","volume":"49","author":"Cadet","year":"2010","journal-title":"Free Radic. Biol. Med."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1016\/j.mrfmmm.2011.02.004","article-title":"Measurement of oxidatively generated base damage in cellular DNA","volume":"711","author":"Cadet","year":"2011","journal-title":"Mutat. Res. Fundam. Mol. Mech. Mutagen."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"655","DOI":"10.2174\/156652412800792651","article-title":"Oxidatively Generated DNA Lesions as Potential Biomarkers of In Vivo Oxidative Stress","volume":"12","author":"Ravanat","year":"2012","journal-title":"Curr. Mol. Med."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"43","DOI":"10.3389\/fchem.2015.00043","article-title":"Understanding DNA under oxidative stress and sensitization: The role of molecular modeling","volume":"3","author":"Dumont","year":"2015","journal-title":"Front. Chem."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"15657","DOI":"10.1039\/c1cp21340g","article-title":"Electron transfer-induced fragmentation of thymine and uracil in atom-molecule collisions","volume":"13","author":"Almeida","year":"2011","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"021101","DOI":"10.1063\/1.5018401","article-title":"Communication: Site-selective bond excision of adenine upon electron transfer","volume":"148","author":"Cunha","year":"2018","journal-title":"J. Chem. Phys."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"12513","DOI":"10.1039\/c004467a","article-title":"Negative ion formation in potassium\u2013nitromethane collisions","volume":"12","author":"Antunes","year":"2010","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"6547","DOI":"10.1021\/jp503164a","article-title":"Potassium-uracil\/thymine ring cleavage enhancement as studied in electron transfer experiments and theoretical calculations","volume":"118","author":"Almeida","year":"2014","journal-title":"J. Phys. Chem. A"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"177","DOI":"10.1016\/j.comptc.2011.11.004","article-title":"Radiation damage on biomolecular systems: Dynamics of ion induced collision processes","volume":"990","author":"Tergiman","year":"2012","journal-title":"Comput. Theor. Chem."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"159","DOI":"10.1016\/j.cplett.2008.02.094","article-title":"Ab initio molecular treatment of charge transfer processes induced by collision of C2+ ions with the OH radical: A linear approach","volume":"455","author":"Bene","year":"2008","journal-title":"Chem. Phys. Lett."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"45","DOI":"10.1016\/j.cplett.2011.01.013","article-title":"Charge transfer dynamics of carbon ions with uracil and halouracil targets at low collision energies","volume":"503","author":"Tergiman","year":"2011","journal-title":"Chem. Phys. Lett."},{"key":"ref_44","unstructured":"Salem, L. (1982). Electrons in Chemical Reactions: First Principles, Wiley Interscience."},{"key":"ref_45","first-page":"8","article-title":"Anisotropic effect in the charge transfer of Cq+ ions with uracil","volume":"74","author":"Tergiman","year":"2006","journal-title":"Phys. Rev. A At. Mol. Opt. Phys."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"2380","DOI":"10.1021\/acs.jpca.5b12392","article-title":"Stepwise Hydration of 2-Aminooxazole: Theoretical Insight into the Structure, Finite Temperature Behavior and Proton-Induced Charge Transfer","volume":"120","author":"Calvo","year":"2016","journal-title":"J. Phys. Chem. A"},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"9761","DOI":"10.1039\/c1cp20503j","article-title":"An ab initio study of ion induced charge transfer dynamics in collision of carbon ions with thymine","volume":"13","author":"Tergiman","year":"2011","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_48","unstructured":"Werner, H.-J., Knowles, P.J., Knizia, G., Manby, F.R., Sch\u00fctz, M., Celani, P., Gy\u00f6rffy, W., Kats, D., Korona, T., and Lindh, R. MOLPRO, Version 2015.1 2015."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"8942","DOI":"10.1063\/1.468948","article-title":"Ab initio energy-adjusted pseudopotentials for the noble gases Ne through Xe: Calculation of atomic dipole and quadrupole polarizabilities","volume":"102","author":"Nicklass","year":"1995","journal-title":"J. Chem. Phys."}],"container-title":["International Journal of Molecular Sciences"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1422-0067\/20\/24\/6170\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T13:40:10Z","timestamp":1760190010000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1422-0067\/20\/24\/6170"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2019,12,6]]},"references-count":49,"journal-issue":{"issue":"24","published-online":{"date-parts":[[2019,12]]}},"alternative-id":["ijms20246170"],"URL":"https:\/\/doi.org\/10.3390\/ijms20246170","relation":{},"ISSN":["1422-0067"],"issn-type":[{"type":"electronic","value":"1422-0067"}],"subject":[],"published":{"date-parts":[[2019,12,6]]}}}