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Hydrogen-Bond Cooperativity in Formamide2 -Water: A Model for Water-Mediated Interactions. | LitMetric
The rotational spectrum of formamide2 -H2 O formed in a supersonic jet has been characterized by Fourier-transform microwave spectroscopy. This adduct provides a simple model of water-mediated interaction involving the amide linkages, as occur in protein folding or amide-association processes, showing the interplay between self-association and solvation. Mono-substituted (13) C, (15) N, (18) O, and (2) H isotopologues have been observed and their data used to investigate the structure. The adduct forms an almost planar three-body sequential cycle. The two formamide molecules link on one side through an N-H⋅⋅⋅O hydrogen bond and on the other side through a water-mediated interaction with the formation of C=O⋅⋅⋅H-O and O⋅⋅⋅H-N hydrogen bonds. The analysis of the quadrupole coupling effects of two (14) N-nuclei reveals the subtle inductive forces associated to cooperative hydrogen bonding. These forces are involved in the changes in the C=O and C-N bond lengths with respect to pure formamide.
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