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Tautomer-Specific Resonant Photoelectron Imaging of Deprotonated Cytosine Anions

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [2];  [2]
  1. Brown Univ., Providence, RI (United States). Dept. of Chemistry; Brown University
  2. Brown Univ., Providence, RI (United States). Dept. of Chemistry
+ Show Author Affiliations
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.
Research Organization:
Brown Univ., Providence, RI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
SC0018679
OSTI ID:
1594594
Alternate ID(s):
OSTI ID: 1510100
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 23 Vol. 58; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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Figures / Tables (4)

Scheme 1(p. 2)figure Scheme 1
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Figure 2(p. 3)figure Figure 2
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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
anions
cytosine
dipole-bound states
photoelectron spectroscopy
tautomerism