RT info:eu-repo/semantics/doctoralThesis
T1 Non-covalent interactions in thiol aggregates and nucleoside-amino acid binding models
T2 Interacciones no covalentes en agregados de tioles y modelos de asociación nucleósido-aminoácido
A1 Saragi, Rizalina Tama
A2 Universidad de Valladolid. Facultad de Ciencias
K1 Thiol
K1 Tiol
K1 Non-Covalent Interactions
K1 Interacciones no covalentes
K1 23 Química
AB This thesis contains an experimental and computational investigation of non-covalent interactions in different thiol dimers and DNA-amino acid model complexes. The experiments used chirped-pulse broadband Fourier transform microwave spectroscopy in the cm-wave region (2-8 GHz), providing an accurate structural description of the target compounds. Several quantum mechanical methods including density-functional theory, energy decomposition by symmetry-adapted perturbation theory and topological analyses of the electronic density rationalized the experimental results. The studied thiol systems comprised the weakly-bound homodimers of thiophenol, benzyl mercaptan, 2-phenethyl mercaptan and 2-naphtalenethiol, which were generated in situ in the isolation conditions of a supersonic jet expansion. The thiol dimers were compared to their alcohol counterparts, offering insight into the electronic and structural characteristics of the non-covalent interactions to sulfur centers and, in particular, of the weak dispersive S-H···S hydrogen bond, seldom analysed in the gas phase. Additionally, several biologically relevant model clusters formed by nucleoside dimers and capped amino acids were investigated computationally, in order to improve our understanding of the DNA-amino acid interaction. These models illustrate the influence of sugar puckering in the amino acid conformation and the implication of the hydrogen bonds stabilizing the complexes. The results obtained in the thesis confirm the importance of the chemically specific reductionist approach and the benefits of a synergic combination of rotational data and computational calculations.
YR 2022
FD 2022
LK https://uvadoc.uva.es/handle/10324/52894
UL https://uvadoc.uva.es/handle/10324/52894
LA eng
NO Departamento de Química Física y Química Inorgánica
DS UVaDOC
RD 03-jun-2024