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Title: Tautomer-Specific Resonant Photoelectron Imaging of Deprotonated Cytosine Anions

Abstract

Tautomers of the nucleobases play fundamental roles in spontaneous mutations of DNA. Tautomers of neutral cytosine have been studied in the gas phase, but much less is known about charged species. In this paper, we report the observation and characterization of three tautomers of deprotonated cytosine anions, [trans-keto-amino-N3H-H8b] (tKAN3H8b–), [cis-keto-amino-N3H–H8a] (cKAN3H8a–) and [keto-amino–H] (KAN1–), produced by electrospray ionization. Excited dipole-bound states (DBSs) are uncovered for the three anions by photodetachment spectroscopy. Excitations to selected DBS vibrational levels of cKAN3H8a– and tKAN3H8b– yield tautomer-specific resonant photoelectron spectra. The current study provides further insight into tautomerism of cytosine and suggests a new method to study the tautomers of nucleobases using electrospray and anion spectroscopy.

Authors:
 [1];  [1]; ORCiD logo [1]
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  1. Brown Univ., Providence, RI (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Brown Univ., Providence, RI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1594594
Alternate Identifier(s):
OSTI ID: 1510100
Grant/Contract Number:  
SC0018679
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 58; Journal Issue: 23; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; anions; cytosine; dipole-bound states; photoelectron spectroscopy; tautomerism

Citation Formats

Zhu, Guo-Zhu, Qian, Chen-Hui, and Wang, Lai-Sheng. Tautomer-Specific Resonant Photoelectron Imaging of Deprotonated Cytosine Anions. United States: N. p., 2019. Web. doi:10.1002/anie.201903444.
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Zhu, Guo-Zhu, Qian, Chen-Hui, & Wang, Lai-Sheng. Tautomer-Specific Resonant Photoelectron Imaging of Deprotonated Cytosine Anions. United States. https://doi.org/10.1002/anie.201903444
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Zhu, Guo-Zhu, Qian, Chen-Hui, and Wang, Lai-Sheng. Tue . "Tautomer-Specific Resonant Photoelectron Imaging of Deprotonated Cytosine Anions". United States. https://doi.org/10.1002/anie.201903444. https://www.osti.gov/servlets/purl/1594594.
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@article{osti_1594594,
title = {Tautomer-Specific Resonant Photoelectron Imaging of Deprotonated Cytosine Anions},
author = {Zhu, Guo-Zhu and Qian, Chen-Hui and Wang, Lai-Sheng},
abstractNote = {Tautomers of the nucleobases play fundamental roles in spontaneous mutations of DNA. Tautomers of neutral cytosine have been studied in the gas phase, but much less is known about charged species. In this paper, we report the observation and characterization of three tautomers of deprotonated cytosine anions, [trans-keto-amino-N3H-H8b] (tKAN3H8b–), [cis-keto-amino-N3H–H8a] (cKAN3H8a–) and [keto-amino–H] (KAN1–), produced by electrospray ionization. Excited dipole-bound states (DBSs) are uncovered for the three anions by photodetachment spectroscopy. Excitations to selected DBS vibrational levels of cKAN3H8a– and tKAN3H8b– yield tautomer-specific resonant photoelectron spectra. The current study provides further insight into tautomerism of cytosine and suggests a new method to study the tautomers of nucleobases using electrospray and anion spectroscopy.},
doi = {10.1002/anie.201903444},
journal = {Angewandte Chemie (International Edition)},
number = 23,
volume = 58,
place = {United States},
year = {Tue Apr 30 00:00:00 EDT 2019},
month = {Tue Apr 30 00:00:00 EDT 2019}
}
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https://doi.org/10.1002/anie.201903444
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Figures / Tables:

Scheme 1 Scheme 1: The top seven tautomers of deprotonated cytosine anions in the gas phase. The values below the structures show the calculated relative stabilities in kcal/mol.
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