title: Conformational preferences of chondroitin sulfate oligomers using partially oriented NMR spectroscopy of 13C-labeled acetyl groups.
abstract: A new method is presented for the retrieval of information on the conformation of glycosaminoglycan oligomers in solution. The method relies on the replacement of acetyl groups in isolated native oligomers with 13C labeled acetyl groups and the extraction of orientational constraints from residual dipolar couplings (RDCs) and chemical shift anisotropy (CSA) offsets observed in NMR spectra of partially oriented samples. A novel method for assignment of resonances based on the correlation of resonance intensities with isotope ratios determined from mass spectrometric analysis is also presented. The combined methods are used in conjunction with more traditional NMR structural data to determine the solution structure of a pentasaccharide, GalNAc6S(beta1-4)GlcA(beta1-3)GalNAc4S(beta1-4)GlcA(beta1-3)GalNAc4S-ol, derived by enzymatic hydrolysis of chondroitin sulfate. The geometry derived is compared to that for similar molecules that have been reported in the literature, and prospects for use of the new types of data in the study of protein-bound oligosaccharides are discussed.
authors.affiliation: Complex Carbohydrate Research Center and Department of Chemistry, University of Georgia, Athens, Georgia 30602-4712, USA.
authors.forename: Fei
authors.initials: F
authors.lastname: Yu
authors.forename: Jeremy J
authors.initials: JJ
authors.lastname: Wolff
authors.forename: I Jonathan
authors.initials: IJ
authors.lastname: Amster
authors.forename: James H
authors.initials: JH
authors.lastname: Prestegard
mesh_terms: D000107:Acetylation; D016880:Anisotropy; D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D002247:Carbon Isotopes / Q000737:chemistry; D002809:Chondroitin Sulfates / Q000737:chemistry*; D003198:Computer Simulation; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D009844:Oligosaccharides / Q000737:chemistry*; D053719:Tandem Mass Spectrometry
chemical_list: D002247:Carbon Isotopes; D009844:Oligosaccharides; D002809:Chondroitin Sulfates