Inductive Effects on the Energetics of Prolyl Peptide Bond Isomerization: Implications for Collagen Folding and Stability.
TLDR
The hydroxylation of proline residues in collagen enhances the stability of the collagen triple helix and may have a significant impact on the folding and stability of collagen, which has a preponderance of hydroxyproline residues, all with peptide bonds in the trans conformation.Abstract:
The hydroxylation of proline residues in collagen increases the stability of the collagen triple helix. Previous X-ray diffraction analyses had demonstrated that the presence of an electron-withdrawing substituent on the pyrrolidine ring of proline residues has significant structural consequences [Panasik, N., Jr.; Eberhardt, E. S.; Edison, A. S.; Powell, D. R.; Raines, R. T. Int. J. Pept. Protein Res. 1994 , 44, 262−269]. Here, NMR and FTIR spectroscopy were used to ascertain kinetic and thermodynamic properties of N-acetyl-[β,γ-13C]d,l-proline methyl ester (1); N-acetyl-4(R)-hydroxy-l-proline [13C]methyl ester (2); and N-acetyl-4(R)-fluoro-l-proline methyl ester (3). The pKa's of the nitrogen atom in the parent amino acids decrease in the following order: proline (10.8) > 4(R)-hydroxy-l-proline (9.68) > 4(R)-fluoro-l-proline (9.23). In water or dioxane, amide I vibrational modes decrease in the following order: 1 > 2 > 3. At 37 °C in dioxane, the rate constants for amide bond isomerization are greater...read more
Citations
More filters
Journal ArticleDOI
Cis-trans isomerization of organic molecules and biomolecules: implications and applications.
Christophe Dugave,Luc Demange +1 more
TL;DR: This review focuses on the part of the molecule containing two atoms attached together by a double bond with substituents W-Z which may be found as two isomeric molecules.
Journal ArticleDOI
Review collagen-based biomaterials for wound healing
TL;DR: A review of the structure and molecular interactions of collagen in vivo can be found in this article, where the recent use of natural collagen in sponges, injectables, films and membranes, dressings, and skin grafts; and the ongoing development of synthetic collagen mimetic peptides as pylons to anchor cytoactive agents in wound beds.
Journal ArticleDOI
Prolyl 4-hydroxylase
Kelly L. Gorres,Ronald T. Raines +1 more
TL;DR: The enzymic catalysts of prolyl hydroxylation are reviewed, along with the chemical and biochemical consequences of this subtle but abundant posttranslational modification.
Journal ArticleDOI
Conformational Stability of Collagen Relies on a Stereoelectronic Effect
TL;DR: It is demonstrated for the first time that a stereoelectronic effect is critical for the conformational stability of a protein, which comprises one-third of the protein in humans and threefourths of the weight of human skin.
Journal ArticleDOI
Fluorinated amino acids: compatibility with native protein structures and effects on protein–protein interactions
TL;DR: This critical review covers the literature dealing with investigations of peptides and proteins containing fluorinated analogues of the canonical amino acids published over the course of the past decade including the late nineties, and focuses on side-chain fluorinated amino acids.
References
More filters
Journal ArticleDOI
The Use and Misuse of FTIR Spectroscopy in the Determination of Protein Structure
TL;DR: This review critically assess the application of FTIR spectroscopy to the determination of protein structure by outlining the principles underlying protein secondary structure determination by FTIRSpectroscopy, and highlighting the situations in which FTIR Spectroscopy should be considered the technique of choice.
Journal ArticleDOI
Study of Moderately Rapid Chemical Exchange Reactions by Means of Nuclear Magnetic Double Resonance
Sture Forsén,Ragnar A. Hoffman +1 more
TL;DR: In this paper, a nuclear magnetic double resonance method for the determination of chemical exchange rates has been developed, which is applicable to systems in which a nuclear spin is reversibly transferred between two nonequivalent sites, A and B, and is obtained through the study of the decay to a new equilibrium value of Signal A upon the sudden saturation of Signal B.
Journal ArticleDOI
Consideration of the possibility that the slow step in protein denaturation reactions is due to cis-trans isomerism of proline residues
TL;DR: Since the present model assumes that only one of the major kinetic phases seen in denaturation reactions is concerned with the denaturation process per se, it is in agreement with numerous thermodynamic studies which show consistency with the two-state model for unfolding.
Journal ArticleDOI
Crystal and molecular structure of a collagen-like peptide at 1.9 A resolution.
TL;DR: The structure of a protein triple helix has been determined by x-ray crystallographic studies of a collagen-like peptide containing a single substitution of the consensus sequence, which adopts a triple-helical structure that confirms the basic features determined from fiber diffraction studies on collagen.