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Crystallographic evidence of Watson–Crick connectivity in the base pair of anionic adenine with thymine

Journal Article · · Proceedings of the National Academy of Sciences of the United States of America
 [1];  [2];  [3];  [2];  [2];  [3];  [4]
  1. Univ. of Alabama, Tuscaloosa, AL (United States); The University of Alabama
  2. Univ. of Alabama, Tuscaloosa, AL (United States)
  3. Stockholm Univ. (Sweden)
  4. Univ. of Alabama, Tuscaloosa, AL (United States); Stockholm Univ. (Sweden)
+ Show Author Affiliations
Utilizing an ionic liquid strategy, we report crystal structures of salts of free anionic nucleobases and base pairs previously studied only computationally and in the gas phase. Reaction of tetrabutylammonium ([N4444]+) or tetrabutylphosphonium ([P4444]+) hydroxide with adenine (HAd) and thymine (HThy) led to hydrated salts of deprotonated adenine, [N4444][Ad]·2H2O, and thymine, [P4444][Thy]·2H2O, as well as the double salt cocrystal, [P4444]2[Ad][Thy]·3H2O·2HThy. The cocrystal includes the anionic [Ad-(HThy)] base pair which is a stable formation in the solid state that has previously not even been suggested. It exhibits Watson–Crick connectivity as found in DNA but which is unusual for the free neutral base pairs. The stability of the observed anionic bases and their supramolecular formations and hydrates has also been examined by electronic structure calculations, contributing to more insight into how base pairs can bind when a proton is removed and highlighting mechanisms of stabilization or chemical transformation in the DNA chains.
Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Univ. of Alabama, Tuscaloosa, AL (United States)
Sponsoring Organization:
Royal Swedish Academy of Science; Swedish Research Council (VR); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-76RL01830; SC0019220
OSTI ID:
1657346
Alternate ID(s):
OSTI ID: 2565332
Report Number(s):
PNNL-SA--166564
Journal Information:
Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 31 Vol. 117; ISSN 0027-8424
Publisher:
National Academy of SciencesCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

59 BASIC BIOLOGICAL SCIENCES
DNA
anionic
crystal structure
hydrate
nucleobase