Photoinduced Charge-Transfer Dehydrogenation in a Gas-Phase Metal-DNA Base Complex: Al-cytosine

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DOIResolve DOI: http://doi.org/10.1021/ja0122501
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TypeArticle
Journal titleJ. Am. Chem. Soc
ISSN00027863
Volume124
Issue23
Pages66866692; # of pages: 7
AbstractAn Al-cytosine association complex has been generated via laser ablation of a mixture of aluminum and cytosine powders that were pressed into a rod form. The ionization energy of the complex is found to be 5.16 ? 0.01 eV. The photoionization efficiency spectrum of Al-cytosine has also been collected. DFT calculations indicate that binding of Al to cytosine manifests a significant weakening of the N-H bond, predicted to have a strength of 1.5 eV in the complex, and a significant stabilization of the oxo tautomeric form relative to the hydroxy forms. The predicted ionization energy of 5.2 eV agrees well with the experimental value. The threshold for dehydrogenation/ionization of Al-cytosine, forming (Al-cytosine-H)+, is found to occur at photoexcitation energies between 11.4 and 12.8 eV. This is a two-photon process that is proposed to occur via photoinduced electron transfer from Al to an antibonding (*) orbital localized on N-H. In the context of this mechanism, this work constitutes the first time charge transfer between a metal and DNA base has been photoinitiated in the gas phase.
Publication date
AffiliationNational Research Council Canada; NRC Steacie Institute for Molecular Sciences
Peer reviewedNo
Identifier10072378
NPARC number12337981
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Record identifiere45afc7b-afb8-4da8-b458-02eb93a22aa5
Record created2009-09-10
Record modified2016-05-09
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