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Tautomer‐Specific Resonant Photoelectron Imaging of Deprotonated Cytosine Anions
Author(s) -
Zhu GuoZhu,
Qian ChenHui,
Wang LaiSheng
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201903444
Subject(s) - tautomer , nucleobase , chemistry , deprotonation , cytosine , electrospray ionization , ionization , spectroscopy , ion , photochemistry , crystallography , computational chemistry , stereochemistry , dna , organic chemistry , biochemistry , physics , quantum mechanics
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. Here, 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 ionization and anion spectroscopy.