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Switching of Protonation Sites in Hydrated Nicotine via a Grotthuss Mechanism

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.3c08922· OSTI ID:2406154
 [1];  [2];  [1];  [3];  [1];  [1];  [4]
  1. Tokyo Institute of Technology (Japan)
  2. Univ. of Washington, Seattle, WA (United States)
  3. Univ. of Ioannina (Greece)
  4. Univ. of Washington, Seattle, WA (United States); Tokyo Institute of Technology (Japan); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
+ Show Author Affiliations
The switching of the protonation sites in hydrated nicotine, probed by experimental infrared (IR) spectroscopy and theoretical ab initio calculations, is facilitated via a Grotthuss instead of a bimolecular proton transfer (vehicle) mechanism at the experimental temperature (T = 130 K) as unambiguously confirmed by experiments with deuterated water. In contrast, the bimolecular vehicle mechanism is preferred at higher temperatures (T = 300 K) as determined by theory. Further, the Grotthuss mechanism for the concerted proton transfer results in the production of nicotine’s bioactive and addictive pyrrolidine-protonated (Pyrro-H+) protomer with just 5 water molecules. Theoretical analysis suggests that the concerted proton transfer occurs via hydrogen-bonded bridges consisting of a 3 water molecule “core” that connects the pyridine protonated (Pyri-H+) with the pyrrolidine-protonated (Pyrro-H+) protomers. Additional water molecules attached as acceptors to the hydrogen-bonded “core” bridge result in lowering the reaction barrier of the concerted proton transfer down to less than 6 kcal/mol, which is consistent with the experimental observations.
Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
2406154
Report Number(s):
PNNL-SA--186413
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 5 Vol. 146; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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