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Internal conversion and intersystem crossing pathways in UV excited, isolated uracils and their implications in prebiotic chemistry
The photodynamic properties of molecules determine their ability to survive in harsh radiation environments. As such, the photostability of heterocyclic aromatic compounds to electromagnetic radiation is expected to have been one of the selection pressures influencing the prebiotic chemistry on earl...
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Published in: | Physical chemistry chemical physics : PCCP 2016-07, Vol.18 (3), p.2168-2176 |
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container_title | Physical chemistry chemical physics : PCCP |
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creator | Yu, Hui Sanchez-Rodriguez, Jose A Pollum, Marvin Crespo-Hernández, Carlos E Mai, Sebastian Marquetand, Philipp González, Leticia Ullrich, Susanne |
description | The photodynamic properties of molecules determine their ability to survive in harsh radiation environments. As such, the photostability of heterocyclic aromatic compounds to electromagnetic radiation is expected to have been one of the selection pressures influencing the prebiotic chemistry on early Earth. In the present study, the gas-phase photodynamics of uracil, 5-methyluracil (thymine) and 2-thiouracil-three heterocyclic compounds thought to be present during this era-are assessed in the context of their recently proposed intersystem crossing pathways that compete with internal conversion to the ground state. Specifically, time-resolved photoelectron spectroscopy measurements evidence femtosecond to picosecond timescales for relaxation of the singlet
1
ππ* and
1
nπ* states as well as for intersystem crossing to the triplet manifold. Trapping in the excited triplet state and intersystem crossing back to the ground state are investigated as potential factors contributing to the susceptibility of these molecules to ultraviolet photodamage.
The photodynamic properties of molecules determine their ability to survive in harsh radiation environments. |
doi_str_mv | 10.1039/c6cp01790h |
format | article |
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1
ππ* and
1
nπ* states as well as for intersystem crossing to the triplet manifold. Trapping in the excited triplet state and intersystem crossing back to the ground state are investigated as potential factors contributing to the susceptibility of these molecules to ultraviolet photodamage.
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1
ππ* and
1
nπ* states as well as for intersystem crossing to the triplet manifold. Trapping in the excited triplet state and intersystem crossing back to the ground state are investigated as potential factors contributing to the susceptibility of these molecules to ultraviolet photodamage.
The photodynamic properties of molecules determine their ability to survive in harsh radiation environments.</description><subject>Femtosecond</subject><subject>Ground state</subject><subject>Heterocyclic compounds</subject><subject>Internal conversion</subject><subject>Manifolds</subject><subject>Pathways</subject><subject>Physical chemistry</subject><subject>Uracil</subject><issn>1463-9076</issn><issn>1463-9084</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2016</creationdate><recordtype>article</recordtype><recordid>eNqFkb1PwzAQxS0EoqWwsIM8IkTBjpPYGVEEtFIlGChr5DpnapQvbBfozD-O-0EZme7p7nfvpHsInVJyTQnLblSqOkJ5RuZ7qE_jlA0zIuL9neZpDx0590YIoQllh6gXcSoyKuI--h43HmwjK6za5gOsM22DZVNis-q7pfNQY2Vb50zzijvp559y6cIUT18wfCnjobzCxrWVDAovrFSmcmsHPwdjsam7yijpg-96rbMwM603Cqs51MZ5uzxGB1pWDk62dYCm93fP-Wg4eXwY57eToWJx5IdacJpEMtKp0CTikoNgCoKEjEMmYkLpLKFlSkspslmsVRyVnEqmudaaxwkboIuNb2fb9wU4X4T7CqpKNtAuXEEFS1LCWXjq_yjhCYtYKgJ6uUHXX7Kgi86aWtplQUmxyqfI0_xpnc8owOdb38WshnKH_gYSgLMNYJ3aTf8CZj_yjpdu</recordid><startdate>20160727</startdate><enddate>20160727</enddate><creator>Yu, Hui</creator><creator>Sanchez-Rodriguez, Jose A</creator><creator>Pollum, Marvin</creator><creator>Crespo-Hernández, Carlos E</creator><creator>Mai, Sebastian</creator><creator>Marquetand, Philipp</creator><creator>González, Leticia</creator><creator>Ullrich, Susanne</creator><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><orcidid>https://orcid.org/0000-0002-8711-1533</orcidid></search><sort><creationdate>20160727</creationdate><title>Internal conversion and intersystem crossing pathways in UV excited, isolated uracils and their implications in prebiotic chemistry</title><author>Yu, Hui ; Sanchez-Rodriguez, Jose A ; Pollum, Marvin ; Crespo-Hernández, Carlos E ; Mai, Sebastian ; Marquetand, Philipp ; González, Leticia ; Ullrich, Susanne</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c342t-f87152a2f68f027a7e83cef02e97e984011b51d61da89b4fc42d71a3f7fff7453</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2016</creationdate><topic>Femtosecond</topic><topic>Ground state</topic><topic>Heterocyclic compounds</topic><topic>Internal conversion</topic><topic>Manifolds</topic><topic>Pathways</topic><topic>Physical chemistry</topic><topic>Uracil</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Yu, Hui</creatorcontrib><creatorcontrib>Sanchez-Rodriguez, Jose A</creatorcontrib><creatorcontrib>Pollum, Marvin</creatorcontrib><creatorcontrib>Crespo-Hernández, Carlos E</creatorcontrib><creatorcontrib>Mai, Sebastian</creatorcontrib><creatorcontrib>Marquetand, Philipp</creatorcontrib><creatorcontrib>González, Leticia</creatorcontrib><creatorcontrib>Ullrich, Susanne</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Physical chemistry chemical physics : PCCP</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Yu, Hui</au><au>Sanchez-Rodriguez, Jose A</au><au>Pollum, Marvin</au><au>Crespo-Hernández, Carlos E</au><au>Mai, Sebastian</au><au>Marquetand, Philipp</au><au>González, Leticia</au><au>Ullrich, Susanne</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Internal conversion and intersystem crossing pathways in UV excited, isolated uracils and their implications in prebiotic chemistry</atitle><jtitle>Physical chemistry chemical physics : PCCP</jtitle><addtitle>Phys Chem Chem Phys</addtitle><date>2016-07-27</date><risdate>2016</risdate><volume>18</volume><issue>3</issue><spage>2168</spage><epage>2176</epage><pages>2168-2176</pages><issn>1463-9076</issn><eissn>1463-9084</eissn><abstract>The photodynamic properties of molecules determine their ability to survive in harsh radiation environments. As such, the photostability of heterocyclic aromatic compounds to electromagnetic radiation is expected to have been one of the selection pressures influencing the prebiotic chemistry on early Earth. In the present study, the gas-phase photodynamics of uracil, 5-methyluracil (thymine) and 2-thiouracil-three heterocyclic compounds thought to be present during this era-are assessed in the context of their recently proposed intersystem crossing pathways that compete with internal conversion to the ground state. Specifically, time-resolved photoelectron spectroscopy measurements evidence femtosecond to picosecond timescales for relaxation of the singlet
1
ππ* and
1
nπ* states as well as for intersystem crossing to the triplet manifold. Trapping in the excited triplet state and intersystem crossing back to the ground state are investigated as potential factors contributing to the susceptibility of these molecules to ultraviolet photodamage.
The photodynamic properties of molecules determine their ability to survive in harsh radiation environments.</abstract><cop>England</cop><pmid>27189184</pmid><doi>10.1039/c6cp01790h</doi><tpages>9</tpages><orcidid>https://orcid.org/0000-0002-8711-1533</orcidid></addata></record> |
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language | eng |
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source | Royal Society of Chemistry |
subjects | Femtosecond Ground state Heterocyclic compounds Internal conversion Manifolds Pathways Physical chemistry Uracil |
title | Internal conversion and intersystem crossing pathways in UV excited, isolated uracils and their implications in prebiotic chemistry |
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