Intrinsic Folding Proclivities in Cyclic β-Peptide Building Blocks: Configuration and Heteroatom Effects Analyzed by Conformer-Selective Spectroscopy and Quantum Chemistry.
This work describes the use of conformer-selective laser spectroscopy following supersonic expansion to probe the local folding proclivities of four-membered ring cyclic β-amino acid building blocks. Emphasis is placed on stereochemical effects as well as on the structural changes induced by the replacement of a carbon atom of the cycle by a nitrogen atom. The amide A IR spectra are obtained and interpreted with the help of quantum chemistry structure calculations. Results provide evidence that the building block with a trans-substituted cyclobutane ring has a predilection to form strong C8 hydrogen bonds. Nitrogen-atom substitution in the ring induces the formation of the hydrazino turn, with a related but distinct hydrogen-bonding network: the structure is best viewed as a bifurcated C8/C5 bond with the N heteroatom lone electron pair playing a significant acceptor role, which supports recent observations on the hydrazino turn structure in solution. Surprisingly, this study shows that the cis-substituted cyclobutane ring derivative also gives rise predominantly to a C8 hydrogen bond, although weaker than in the two former cases, a feature that is not often encountered for this building block.
['Alauddin|Mohammad|M|', 'Gloaguen|Eric|E|', 'Brenner|Valérie|V|', 'Tardivel|Benjamin|B|', 'Mons|Michel|M|', 'Zehnacker-Rentien|Anne|A|', 'Declerck|Valérie|V|', 'Aitken|David J|DJ|']
D000577:Amides D003503:Cyclobutanes D006860:Hydrogen Bonding D008958:Models, Molecular D010456:Peptides, Cyclic D011487:Protein Conformation D011789:Quantum Theory D013055:Spectrophotometry, Infrared
laser spectroscopy hydrogen bonds hydrazino turns amino acids conformation analysis