title: Hydrogen bonding monitored by deuterium isotope effects on carbonyl 13C chemical shift in BPTI: intra-residue hydrogen bonds in antiparallel beta-sheet.
abstract: Deuterium isotope effects on carbonyl 13C magnetic shielding were measured for the backbone carbonyl groups in BPTI (basic pancreatic trypsin inhibitor), and interpreted as a measure of hydrogen bond energies. The effects originate from peptide amide proton deuterium substitution and were observed on carbonyl carbons separated by two or three covalent bonds from the amide H/D. Two-bond isotope effects depend on the energy of the hydrogen bond donated by NH/D. Calibration of the effect with model compound data leads to hydrogen bond enthalpies less than 4.7 kcal/mol. Isotope effects over three bonds from the amide H/D to the carbonyl carbon of the same amino acid residue are observed for seven carbonyl resonances in BPTI. The three-bond isotope effects are highly related to the various backbone conformations. The largest effects are observed for residues with an approximate syn- periplanar conformation of the H-N-C alpha-C = O atoms, as realized for many residues in the BPTI antiparallel beta-sheet. The residues that show measurable three-bond effects have unusually short distances between H and O. The size of this effect decreases rapidly with increased O..H distance in the open five-membered ring. This observation suggests appreciable interactions in these rings.
authors.affiliation: Institute of Life Sciences and Chemistry, Roskilde University, Denmark.
authors.forename: E
authors.initials: E
authors.lastname: Tüchsen
authors.forename: P E
authors.initials: PE
authors.lastname: Hansen
mesh_terms: D000577:Amides; D000595:Amino Acid Sequence; D007611:Aprotinin / Q000737:chemistry*; D002247:Carbon Isotopes; D003903:Deuterium / Q000737:chemistry; D006860:Hydrogen Bonding; D007554:Isotopes; D009682:Magnetic Resonance Spectroscopy; D008280:Magnetics; D008433:Mathematics; D008958:Models, Molecular; D008969:Molecular Sequence Data; D011487:Protein Conformation; D011522:Protons; D013816:Thermodynamics
chemical_list: D000577:Amides; D002247:Carbon Isotopes; D007554:Isotopes; D011522:Protons; D007611:Aprotinin; D003903:Deuterium