ABSTRACT
Conformational characterization of single α- and ß-epimers of galactosamine in solution still remains an intriguing task because of their flexibility and ability to interconvert. This difficulty was circumvented by recording several "snapshots" of the epimerization process by means of fast ESI vaporization of a galactosamine·HCl sample solution at different times. Consequently, the so generated gaseous mixtures were spectroscopically investigated and the specific conformational features of both α- and ß-epimers were assigned, despite the overlapping of several IR signals. Interestingly, from a comparison with time-resolved 1H-NMR data obtained for the same solutions, the catalyzing effect of the applied ESI technique in the anomerization process clearly emerges. Finally, the experimental data were supported using both the Density Functional Theory (DFT) and Block-Localized Wavefunction (BLW) approaches: the latter method was applied here for the first time for the investigation of charged species.
ABSTRACT
Efficient enantiodiscrimination of some alanine-containing di- and tri-peptides by using chiral protonated bis(diamido)-bridged basket resorcin[4]arenes depends on several factors, including the basicity of the amino acid residues at the C- and N-termini of the peptide.
Subject(s)
Alanine/chemical synthesis , Calixarenes/chemistry , Diamide/chemistry , Peptides/chemical synthesis , Phenylalanine/analogs & derivatives , Alanine/chemistry , Kinetics , Molecular Conformation , Peptides/chemistry , Phenylalanine/chemistry , Protons , Quantum Theory , StereoisomerismABSTRACT
The IRMPD spectrum of the G-quartet-Na(+) complex, in combination with an ab initio molecular dynamic simulation, revealed the presence of two metastable populations of conformers separated by a free energy barrier easily accessible at room temperature.
