Intramolecular hydrogen bonding in 1'-sucrose derivatives determined by SIMPLE proton NMR spectroscopy

Christofides, John C.; Davies, David B.; Martin, Julie A.; Rathbone, Elner B.

doi:10.1021/ja00279a013

Cited by 42 publications

(14 citation statements)

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“…8). Although not novel, studies of these effects by other investigators (Lemieux and Bock, 1984: Reuben, 1984: Christofides et al, 1986 were performed in DMSO solution in order to eliminate the chemical exchange of labile protons. To our knowledge, our efforts are the first that have been successful in observing isotope shift effects in pure aqueous solution, where chemical exchange phenomena severely restrict their study.…”

Section: Discussionmentioning

confidence: 99%

“…In order to obtain additional evidence for the intramolecular hydrogen bonds in S6L, we studied extensively the deuterium isotope effects on 13C chemical shifts (Reuben, 1984;Christofides et al, 1986). Our findings on S6L imply that at low temperatures (248 K-268 K) at neutral pH values (pH 7.0_+0.5), the exchange of S6L hydroxyl protons in water is slow enough to observe short-range deuterium isotope shifts of carbon resonances.…”

Section: Hltranlolecular Hych'ogen Bondsmentioning

confidence: 94%

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The solution conformation of sialyl-α(2→6)-lactose studied by modern NMR techniques and Monte Carlo simulations

et al. 1992

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We present a comprehensive strategy for detailed characterization of the solution conformations of oligosaccharides by NMR spectroscopy and force-field calculations. Our experimental strategy generates a number of interglycosidic spatial constraints that is sufficiently large to allow us to determine glycosidic linkage conformations with a precision heretofore unachievable. In addition to the commonly used [1H,1H] NOE contacts between aliphatic protons, our constraints are: (a) homonuclear NOEs of hydroxyl protons in H2O to other protons in the oligosaccharide, (b) heteronuclear [1H,13C] NOEs, (c) isotope effects of O1H/O2H hydroxyl groups on 13C chemical shifts, and (d) long-range heteronuclear scalar couplings across glycosidic bonds. We have used this approach to study the trisaccharide sialyl-alpha (2----6)-lactose in aqueous solution. The experimentally determined geometrical constraints were compared to results obtained from force-field calculations based on Metropolis Monte Carlo simulations. The molecule was found to exist in 2 families of conformers. The preferred conformations of the alpha (2----6)-linkage of the trisaccharide are best described by an equilibrium of 2 conformers with phi angles at -60 degrees or 180 degrees and of the 3 staggered rotamers of the omega angle with a predominant gt conformer. Three intramolecular hydrogen bonds, involving the hydroxyl protons on C8 and C7 of the sialic acid residue and on C3 of the reducing-end glucose residue, contribute significantly to the conformational stability of the trisaccharide in aqueous solution.

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Section: Discussionmentioning

confidence: 99%

Section: Hltranlolecular Hych'ogen Bondsmentioning

confidence: 94%

The solution conformation of sialyl-α(2→6)-lactose studied by modern NMR techniques and Monte Carlo simulations

et al. 1992

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“…Structures of carbohydrates such as gangliosides and many different kinds of disaccharides or trisaccharides have been determined in water or DMSO by NMR spectroscopy. [1][2][3][4][5][16][17][18][19][20] Water molecule is well known to make strong hydrogen bond with carbohydrate in the aqueous solution because it is very polar and small enough to be inserted deep into the disaccharide and weaken the intramolecular hydrogen bonds in carbohydrates. DMSO is much bigger than water and it is not easy to be inserted deep into the disaccharide.…”

Section: Resultsmentioning

confidence: 99%

“…24 We collected a TOCSY spectrum with a mixing time of 80 msec and a 1 H- 13 C heteronuclear multiple quantum coherence (HMQC) spectrum to aid the spectral assignments. 25 16,18 Molecular dynamics simulations of GlcNAc(β1,3)-Gal(β)OMe. In order to investigate the dynamic behavior of the GlcNAc(β1,3)Gal(β)OMe, molecular dynamics simulations on GlcNAc(β1,3)Gal(β)OMe in DMSO was proceeded.…”

Section: Methodsmentioning

confidence: 99%

“…14,15 NMR techniques such as chemical shift variation, temperature coefficients, nuclear Overhauser effects, and coupling constant have been used to investigate the hydrogen bonds in carbohydrate structures. 3,[16][17][18][19][20] Here, we studied the hydrogen bond existed in the structure of GlcNAc(β1,3)Gal(β)OMe in DMSO. Repeating units of this disaccharide are present in certain mucins, membrane glycoproteins, and polyglycosylceramides where they are associated with the i-antigenic structures and serve as precursors of the ABH, Lewis, and P1 blood group antigens.…”

Section: Introductionmentioning

confidence: 99%

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Hydrogen Bonds in GlcNAc( β1,3)Gal( β)OMe in DMSO Studied by NMR Spectroscopy and Molecular Dynamics Simulations

2004

Bulletin of the Korean Chemical Society

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Hydrogen bond is an important factor in the structures of carbohydrates. Because of great strength, short range, and strong angular dependence, hydrogen bonding is an important factor stabilizing the structure of carbohydrate. In this study, conformational properties and the hydrogen bonds in GlcNAc(β1,3)Gal(β)OMe in DMSO are investigated through NMR spectroscopy and molecular dynamics simulation. Lowest energy structure in the adiabatic energy map was utilized as an initial structure for the molecular dynamics simulations in DMSO. NOEs, temperature coefficients, SIMPLE NMR data, and molecular dynamics simulations proved that there is a strong intramolecular hydrogen bond between O7' and HO3' in GlcNAc(β1,3)Gal(β)OMe in DMSO. In aqueous solution, water molecule makes intermolecular hydrogen bonds with the disaccharides and there was no intramolecular hydrogen bonds in water. Since DMSO molecule is too big to be inserted deep into GlcNAc(β1,3)Gal(β)OMe, DMSO can not make strong intermolecular hydrogen bonding with carbohydrate and increases the ability of O7' in GlcNAc(β1,3)Gal(β)OMe to participate in intramolecular hydrogen bonding. Molecular dynamics simulation in conjunction with NMR experiments proves to be efficient way to investigate the intramolecular hydrogen bonding existed in carbohydrate.

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Conformational Analysis in Solution by NMR

Homans¹

2000

Carbohydrates in Chemistry and Biology

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Of the functions that have been ascribed to oligosaccharides [ 11, their role in molecular recognition appears to be a repetitive theme in many biological processes. Recent work on the molecular genetics of glycosylation has indicated that oligosaccharides exhibit a particularly prominent role in the development of multicellular organisms [2-91. Morever, it has been known for many years that oligosaccharides are important for the invasion, infectivity and survival of parasites [ 101 and pathogens [ 111 in host cells. There is therefore compelling evidence to suggest that a role in cell-cell communication might be the primary function of oligosaccharides. This might explain the apparent lack of function of these moieties when examined at the level of a protein or indeed an individual cell.In order to understand the molecular basis of oligosaccharide-mediated recognition phenomena, we need to have knowledge of the structure and dynamics of the free carbohydrate ligand in addition to the ligand-receptor complex. In this Chapter, I shall review current knowledge on the former. A discussion of ligand-receptor complexes can be found elsewhere in this volume. Solution Conformations of Oligosaccharides The NMR TechniqueSince oligosaccharides in general fail to crystallize, the only technique that is able reliably to offer information on the structure of oligosaccharides in solution at atomic resolution is nuclear magnetic resonance (NMR) spectroscopy [ 12-1 51. There are three NMR parameters that are relevant to the structural analysis of oli- Carbohydrates in Chemistry

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Intramolecular hydrogen bonding in 1'-sucrose derivatives determined by SIMPLE proton NMR spectroscopy

Cited by 42 publications

References 2 publications

The solution conformation of sialyl-α(2→6)-lactose studied by modern NMR techniques and Monte Carlo simulations

The solution conformation of sialyl-α(2→6)-lactose studied by modern NMR techniques and Monte Carlo simulations

Hydrogen Bonds in GlcNAc( β1,3)Gal( β)OMe in DMSO Studied by NMR Spectroscopy and Molecular Dynamics Simulations

Conformational Analysis in Solution by NMR

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