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Microhydration of the metastable N-Protomer of 4-Aminobenzoic acid by condensation at 80 K: H/D exchange without conversion to the more stable O-protomer

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0119027· OSTI ID:1885568
 [1];  [2];  [3];  [2];  [2]
  1. Yale Univ., New Haven, CT (United States); Yale University
  2. Yale Univ., New Haven, CT (United States)
  3. Fritz Haber Inst. of the Max Planck Society (Germany)
+ Show Author Affiliations
4-Aminobenzoic acid (4ABA) is a model scaffold for studying solvent-mediated proton transfer. Although protonation at the carboxylic group (O-protomer) is energetically favored in the gas phase, the N-protomer, where the proton remains on the amino group, can be kinetically trapped by electrospray ionization of 4ABA in an aprotic solvent such as acetonitrile. Here we report the formation of the hydrated deuterium isotopologues of the N-protomers, RND3+·(H2O)n=1-3, (R=C6H4COOD), which are generated by condensing water molecules onto the bare N-protomers in a liquid nitrogen cooled, radiofrequency octopole ion trap at 80 K. The product clusters are then transferred to a 20 K cryogenic ion trap where they are tagged with weakly bound D2 molecules. The structures of these clusters are determined by analysis of their vibrational patterns obtained by resonant IR photodissociation. The resulting patterns confirm that the metastable N-protomer configuration remains intact even when warmed by sequential condensation of water molecules. Attachment of H2O molecules onto the RND3+ head group also affords the opportunity to explore the possibility of H/D exchange between the acid scaffold and the proximal water network. The spectroscopic results establish that although the RND3+·(H2O)n=1,2 clusters are formed without H/D exchange, the n = 3 cluster exhibits about 10% H/D exchange as evidenced by the appearance of the telltale HOD bands. Furthermore, the site of exchange on the acid is determined to be the acidic OH by the emergence of the OH stretching fundamental in the -COOH motif.
Research Organization:
Yale Univ., New Haven, CT (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0021012
OSTI ID:
1885568
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 13 Vol. 157; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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  • Guevara-Vela, José Manuel; Romero-Montalvo, Eduardo; Mora Gómez, Víctor Arturo
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 29 https://doi.org/10.1039/c6cp00763e
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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
4-Aminobenzoic acid
Intermolecular proton translocation
cryogenic ion chemistry
isomer-selective
isotope exchange
mass spectrometry
para-Aminobenzoic acid
photofragmentation
protomer
vibrational spectroscopy