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Nonconventional NMR Spin-Coupling Constants in Oligosaccharide Conformational Modeling: Structural Dependencies Determined from Density Functional Theory Calculations

Journal Article · · ACS Omega
 [1];  [2];  [2]
  1. University of Notre Dame, IN (United States); Notre Dame Univ., IN (United States)
  2. University of Notre Dame, IN (United States)
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Nonconventional NMR spin-coupling constants were investigated to determine their potential as conformational constraints in MA’AT modeling of the O-glycosidic linkages of oligosaccharides. Four (1JC1',H1', 1JC1',C2', 2JC1',H2', and 2JC2',H1') and eight (1JC4,H4, 1JC3,C4, 1JC4,C5, 2JC3,H4, 2JC4,H3, 2JC5,H4, 2JC4,H5, and 2JC3,C5) spin-couplings in methyl β-d-galactopyranosyl-(1→4)-β-d-glucopyranoside (methyl β-lactoside) were calculated using density functional theory (DFT) to determine their dependencies on O-glycosidic linkage C–O torsion angles, $$\phi$$ and ψ, respectively. Long-range 4JH1',H4 was also examined as a potential conformational constraint of either $$\phi$$ or ψ. Secondary effects of exocyclic (hydroxyl) C–O bond rotation within or proximal to these coupling pathways were investigated. Based on the findings of methyl β-lactoside, analogous J-couplings were studied in five additional two-bond O-glycosidic linkages [βGlcNAc-(1→4)-βMan, 2-deoxy-βGlc-(1→4)-βGlc, αMan-(1→3)-βMan, αMan-(1→2)-αMan, and βGlcNAc(1→2)-αMan] to determine whether the coupling behaviors observed in methyl β-lactoside were more broadly observed. Of the 13 nonconventional J-couplings studied, 7 exhibit properties that may be useful in future MA’AT modeling of O-glycosidic linkages, none of which involve coupling pathways that include the linkage C–O bonds. The findings also provide new insights into the general effects of exocyclic C–O bond conformation on the magnitude of experimental spin-couplings in saccharides and other hydroxyl-containing molecules.

Research Organization:
University of Notre Dame, IN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Omicron Biochemicals, Inc.
Grant/Contract Number:
FC02-04ER15533
OSTI ID:
1904718
Report Number(s):
NDRL 5326
Journal Information:
ACS Omega, Journal Name: ACS Omega Journal Issue: 27 Vol. 7; ISSN 2470-1343
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (48)

Conformational Studies of Oligosaccharides journal July 2020
A1H NMR Spectroscopic Approach to the Unambiguous Determination of Glycosyl Linkage Positions in Oligosaccharides journal February 1998
Long-Range4Jand5J, IncludingInterglycosidic Correlations in Gradient-Enhanced Homonuclear COSY Experiments of Oligosaccharides journal November 1995
Verification of the Projection Resultant Method for Two-Bond13C–13C Coupling Sign Determinations in Carbohydrates journal July 1996
An examination of the nature of localized molecular orbitals and their value in understanding various phenomena that occur in organic chemistry journal December 2018
13C-1H spin-coupling constants in carbohydrates: magnitude and sign determinations via 2D NMR methods journal June 1994
Two-bond 13C-13C spin-coupling constants in carbohydrates: effect of structure on coupling magnitude and sign journal January 1996
Two-bond 13C–13C spin-coupling constants in carbohydrates: New measurements of coupling signs journal May 1998
Heteronuclear coupling constants of hydroxyl protons in a water solution of oligosaccharides: trehalose and sucrose journal August 1999
Extended hückel theory MO calculations of proton-proton coupling constants—II journal January 1971
Use of Circular Statistics To Model αMan-(1→2)-αMan and αMan-(1→3)-α/βMan O -Glycosidic Linkage Conformation in 13 C-Labeled Disaccharides and High-Mannose Oligosaccharides journal December 2018
Predicting the Structures of Glycans, Glycoproteins, and Their Complexes journal June 2018
Comparison of Carbohydrate Force Fields in Molecular Dynamics Simulations of Protein–Carbohydrate Complexes journal March 2021
Synthesis and O -Glycosidic Linkage Conformational Analysis of 13 C-Labeled Oligosaccharide Fragments of an Antifreeze Glycolipid journal January 2019
O -Acetyl Side-Chains in Monosaccharides: Redundant NMR Spin-Couplings and Statistical Models for Acetate Ester Conformational Analysis journal December 2016
Conformational Populations of β-(1→4) O -Glycosidic Linkages Using Redundant NMR J -Couplings and Circular Statistics journal March 2017
Conformational Sampling of Oligosaccharides Using Hamiltonian Replica Exchange with Two-Dimensional Dihedral Biasing Potentials and the Weighted Histogram Analysis Method (WHAM) journal January 2015
Observation of hydroxyl protons of sucrose in aqueous solution: no evidence for persistent intramolecular hydrogen bonds journal June 1992
Torsional effects on the one-bond 13C-13C spin coupling constant in ethylene glycol: insights into the behavior of 1JCC in carbohydrates journal November 1993
[13C]Enriched Methyl Aldopyranosides: Structural Interpretations of 13C-1H Spin-Coupling Constants and 1H Chemical Shifts journal August 1995
Conformational dependence and mechanisms for long-range hydrogen-hydrogen coupling constants over four bonds journal March 1975
Correlated C−C and C−O Bond Conformations in Saccharide Hydroxymethyl Groups:  Parametrization and Application of Redundant 1 H− 1 H, 13 C− 1 H, and 13 C− 13 C NMR J -Couplings journal December 2004
Geminal 2 J CCH Spin−Spin Coupling Constants as Probes of the φ Glycosidic Torsion Angle in Oligosaccharides journal June 2005
Three-Bond C−O−C−C Spin-Coupling Constants in Carbohydrates:  Development of a Karplus Relationship journal November 1998
Hydroxymethyl Group Conformation in Saccharides: Structural Dependencies of 2 J HH , 3 J HH , and 1 J CH Spin−Spin Coupling Constants journal February 2002
DFT and NMR Studies of 2 J COH , 3 J HCOH , and 3 J CCOH Spin-Couplings in Saccharides:  C−O Torsional Bias and H-Bonding in Aqueous Solution journal September 2007
13 C− 13 C NMR Spin−Spin Coupling Constants in Saccharides:  Structural Correlations Involving All Carbons in Aldohexopyranosyl Rings journal September 2007
Fast Evaluation of Geometries and Properties of Excited Molecules in Solution:  A Tamm-Dancoff Model with Application to 4-Dimethylaminobenzonitrile journal June 2000
DFT Calculation of NMR J FF Spin−Spin Coupling Constants in Fluorinated Pyridines journal June 2002
NMR spectroscopy of hydroxyl protons in supercooled carbohydrates journal April 1994
NMR spectroscopy of hydroxy protons of 3,4-disubstituted methyl α-D-galactopyranosides in aqueous solution journal January 1998
Rabbit-ears hybrids, VSEPR sterics, and other orbital anachronisms journal January 2014
13 C– 13 C spin-coupling constants in crystalline 13 C-labeled saccharides: conformational effects interrogated by solid-state 13 C NMR spectroscopy journal January 2019
Reconciling MA′AT and molecular dynamics models of linkage conformation in oligosaccharides journal January 2020
Comprehensive characterization of oligosaccharide conformational ensembles with conformer classification by free-energy landscape via reproductive kernel Hilbert space journal January 2021
Nuclear magnetic resonance spin–spin coupling constants from coupled perturbed density functional theory journal September 2000
Analytical calculation of nuclear magnetic resonance indirect spin–spin coupling constants at the generalized gradient approximation and hybrid levels of density-functional theory journal December 2000
Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules journal March 1972
A new mixing of Hartree–Fock and local density‐functional theories journal January 1993
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
A new integral equation formalism for the polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics journal August 1997
1 H NMR Studies of Hydroxy Protons of ASN- and Ser-Linked Disaccharides in Aqueous Solution journal January 2000
CHARMM-GUI Glycan Modeler for modeling and simulation of carbohydrates and glycoconjugates journal February 2019
A new look at the statistical model identification journal December 1974
The Perlin Effect: bond lengths, bond strengths, and the origins of stereoelectronic effects upon one-bond C–H coupling constants journal July 1990
New NMR Tools for Characterizing the Dynamic Conformations and Interactions of Oligosaccharides journal December 2013
Investigation of Carbohydrate Recognition via Computer Simulation journal April 2015
Two- and Three-bond 13C--1H Couplings in Some Carbohydrates. journal January 1977

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