The Characteristics of Disulfide‐Centered Hydrogen Bonds

Abstract

The disulfide‐centered hydrogen bonds in the three different model systems of diethyl disulfide⋅⋅⋅H2O/H2CO/HCONH2 clusters were characterized by high‐resolution Fourier transform microwave spectroscopy and quantum chemical computations. The global minimum energy structures for each cluster are experimentally observed and are characterized by one of the three different S−S⋅⋅⋅H−C/N/O disulfide‐centered hydrogen bonds and two O⋅⋅⋅H−C hydrogen bonds. Non‐covalent interaction and natural bond orbital analyses further confirm the experimental observations. The symmetry‐adapted perturbation theory (SAPT) analysis reveals that electrostatic is dominant in diethyl disulfide⋅⋅⋅H2O/HCONH2 clusters being consistent with normal hydrogen bonds, whilst dispersion takes over in diethyl disulfide⋅⋅⋅H2CO cluster. Our study gives accurate structural parameters for the disulfide bond involved non‐covalent clusters providing important benchmarking data for the theoretical evaluation of more complex systems.

Setting up the HyDRA blind challenge for the microhydration of organic molecules

“…43,110 It also includes the numerous systems where the global minimum structure involves water as a pure acceptor. In terms of acceptor elements beyond O and N, there are many extension possibilities towards S 84,111,112 which remain to be explored. For the structurally well characterised acid hydrates, 113,114 one may expect complex vibrational dynamics whenever the OH stretching excitation comes close to degenerate proton transfer barriers.…”

Investigating the hidden mechanism underlying the tau interaction by methylene blue

“…Recently, the importance of disul de-centered hydrogen bonds (DCHBs) with HC, HO, and HN (S S−S•••H−C/O/N) has been reported, and non-covalent interactions have been evaluated (HN, -27.7; HO, -16.9; HC, -3.1 kJ/mol) by natural bond orbital analysis. Additionally, HN acts as the strongest hydrogen bond donor among the studied clusters (Li et al, 2021). The disul de bond formation at C56 (2N4R-S56C) resulted in the exchange peak broadening of 1 H- 15 N HSQC in a relatively large area, even though no Arg/Lys residue was present within the ± 10 amino acid boundary of the mutated C56.…”

Three non-bonding interaction topologies of the thiazole–formaldehyde complex observed by rotational spectroscopy

“…11 The important roles of such HBs in determining the conformations of peptides have been recognized long ago, 12–14 and then extensively studied. 15–20 Nucleophiles such as the lone-pairs of carbonyl oxygen can interact with the π-antibonding orbital (π*) of a carbonyl group along the Bürgi–Dunitz trajectory. 21–23 This leads to the so-called n → π* interaction that attracted much attention and has been recognized as an important type of NCI.…”