Comparative 1H NMR and molecular modeling study of hydroxy protons of β-d-Galp-(1→4)-β-d-GlcpNAc-(1→2)-α-d-Manp-(1→O)(CH2)7CH3 analogues in aqueous solution

Rohfritsch, Philippe F.; Frank, Martin; Sandström, Corine; Kenne, Lennart; Vliegenthart, Johannes F.G.; Kamerling, Johannis P.

doi:10.1016/j.carres.2006.07.003

Cited by 8 publications

(3 citation statements)

References 32 publications

(112 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…6 Furthermore, protonation of GlcA carboxylate groups by decreasing the pH was seen to perturb the amide proton temperature coefficients, consistent with data from molecular dynamics simulations that a transient and sparsely populated hydrogen bond may exist between these groups. 6 Enlarging the previous data set, we have now measured temperature coefficients in a variety of HA oligosaccharides (3)(4)(5)(6)(7)(8)10). These data provide reference values for temperature coefficients measured in other acetamido-sugars.…”

Section: Introductionmentioning

confidence: 90%

Temperature dependencies of amide ¹H‐ and ¹⁵N‐chemical shifts in hyaluronan oligosaccharides

Blundell

Almond

2007

Magnetic Reson in Chemistry

View full text Add to dashboard Cite

Temperature coefficients (Deltadelta/DeltaT) of amide chemical shifts of N-acetylglucosamine residues have been measured in a range of oligosaccharides of the important vertebrate polysaccharide hyaluronan. Odd- and even-numbered oligosaccharides with glucuronic acid, Delta-4,5-unsaturated glucuronic acid and N-acetylglucosamine at the termini were investigated. All amide proton temperature coefficients were only slightly less negative (-6.9 to - 9.1 ppb/ degrees C) than those of amide protons in free exchange with water (approximately equal to -11 ppb/ degrees C), indicating an absence of persistent intramolecular hydrogen bonds. With the exception of amide groups in reducing-terminal N-acetylglucosamine rings, all amide proton environments have the same temperature coefficient (-6.9 ppb/ degrees C), irrespective of differences in amide group chemical shifts and (3)J(HH) coupling constants, i.e. they do not sense subtle differences in orientation of the amide group. Amide nitrogen temperature coefficients report the same phenomena but with greater sensitivity. These data provide a set of reference values for temperature coefficients measured in other carbohydrates with acetamido sugars.

show abstract

Section: Introductionmentioning

confidence: 90%

Temperature dependencies of amide ¹H‐ and ¹⁵N‐chemical shifts in hyaluronan oligosaccharides

Blundell

Almond

2007

Magnetic Reson in Chemistry

View full text Add to dashboard Cite

show abstract

“…Even thought he HO3-O3-C3-H3 torsion angle adopts preferentially an antiperiplanar conformation,t he combined data did not support apersistentO5'···HO3 hydrogen bond. [71] In a-d-Glcp-(1!4)-b-d-Glcp-OMe (3), the sub-state with f/ y %À178/À188 has the O2'···HO3 hydrogen bond present to 23 %, whereas the reverse directiono ft he hydrogen bond, O3···HO2',i sp opulated to 9% butt hen f/y %À48/18,a ne ssentially eclipsed conformation at both of the glycosidic torsions. The O6' atom acts as an acceptor to HO6 in a syn-conformation and to HO3 in an anti-conformation, both of which occur only marginally,t hat is,t o% 2%.T he result of the MD simulation with as ignificant hydrogen bond present for O2'···HO3 is in agreementw ith the existence of this hydrogen bond proven by NMR spectroscopy (see above).…”

Section: Molecular Dynamics Simulations Of Disaccharidesmentioning

confidence: 99%

Inter‐residual Hydrogen Bonding in Carbohydrates Unraveled by NMR Spectroscopy and Molecular Dynamics Simulations

et al. 2019

View full text Add to dashboard Cite

Carbohydrates, also known as glycans in biological systems, are omnipresent in nature where they as glycoconjugates occur as oligo‐ and polysaccharides linked to lipids and proteins. Their three‐dimensional structure is defined by two or three torsion angles at each glycosidic linkage. In addition, transglycosidic hydrogen bonding between sugar residues may be important. Herein we investigate the presence of these inter‐residue interactions by NMR spectroscopy in D2O/[D6]DMSO (70:30) or D2O and by molecular dynamics (MD) simulations with explicit water as solvent for disaccharides with structural elements α‐d‐Manp‐(1→2)‐d‐Manp, β‐d‐GlcpNAc‐(1→2)‐d‐Manp, and α‐d‐Glcp‐(1→4)‐β‐d‐Glcp, all of which have been suggested to exhibit inter‐residue hydrogen bonding. For the disaccharide β‐d‐GlcpNAc‐(1→2)‐β‐d‐Manp‐OMe, the large extent of O5′⋅⋅⋅HO3 hydrogen bonding as seen from the MD simulation is implicitly supported by the 1H NMR chemical shift and 3JHO3,H3 value of the hydroxy proton. In the case of α‐d‐Glcp‐(1→4)‐β‐d‐Glcp‐OMe, the existence of a transglycosidic hydrogen bond O2′⋅⋅⋅HO3 was proven by the presence of a cross‐peak in 1H,13C HSQC‐TOCSY experiments as a result of direct TOCSY transfer between HO3 of the reducing end residue and H2′ (detected at C2′) of the terminal residue. The occurrence of inter‐residue hydrogen bonding, albeit transient, is judged important for the stabilization of three‐dimensional structures, which may be essential in maintaining a conformational state for carbohydrate–protein interactions of glycans to take place in biologically important environments.

show abstract

“…The second option is to acquire the NMR spectrum from a supercooled aqueous solution, − in which the rate of −OH exchange has been slowed sufficiently that the hydroxyl groups can be resolved . Most investigators consider this to be the better alternative because it favors the observation of more stable conformations already present in aqueous solution; however, both techniques have found quite considerable application in conformational studies of hydrogen bonding. − Because there are also some precedents for using supercooled aqueous solutions in NMR structural studies of biologically active proteins and RNA, − we have adopted this second approach, when exploring this alternative to the conventional NMR strategy for determining the covalent structure of carbohydrates in solution. We have probed the feasibility of using this alternative technique for elucidation of the chemical structure of the monosaccharide glucose, which is treated as if it were an unknown.…”

Section: Introductionmentioning

confidence: 99%

A Solution NMR Approach To Determine the Chemical Structures of Carbohydrates Using the Hydroxyl Groups as Starting Points

et al. 2018

View full text Add to dashboard Cite

An efficient NMR approach is described for determining the chemical structures of the monosaccharide glucose and four disaccharides, namely, nigerose, gentiobiose, leucrose and isomaltulose. This approach uses the 1 H resonances of the −OH groups, which are observable in the NMR spectrum of a supercooled aqueous solution, as the starting point for further analysis. The 2D-NMR technique, HSQC-TOCSY, is then applied to fully define the covalent structure (i.e., the topological relationship between C–C, C–H, and O–H bonds) that must be established for a novel carbohydrate before proceeding to further conformational studies. This process also leads to complete assignment of all 1 H and 13 C resonances. The approach is exemplified by analyzing the monosaccharide glucose, which is treated as if it were an “unknown”, and also by fully assigning all the NMR resonances for the four disaccharides that contain glucose. It is proposed that this technique should be equally applicable to the determination of chemical structures for larger carbohydrates of unknown composition, including those that are only available in limited quantities from biological studies. The advantages of commencing the structure elucidation of a carbohydrate at the −OH groups are discussed with reference to the now well-established 2D-/3D-NMR strategy for investigation of peptides/proteins, which employs the −NH resonances as the starting point.

show abstract

Comparative 1H NMR and molecular modeling study of hydroxy protons of β-d-Galp-(1→4)-β-d-GlcpNAc-(1→2)-α-d-Manp-(1→O)(CH2)7CH3 analogues in aqueous solution

Cited by 8 publications

References 32 publications

Temperature dependencies of amide ¹H‐ and ¹⁵N‐chemical shifts in hyaluronan oligosaccharides

Temperature dependencies of amide ¹H‐ and ¹⁵N‐chemical shifts in hyaluronan oligosaccharides

Inter‐residual Hydrogen Bonding in Carbohydrates Unraveled by NMR Spectroscopy and Molecular Dynamics Simulations

A Solution NMR Approach To Determine the Chemical Structures of Carbohydrates Using the Hydroxyl Groups as Starting Points

Contact Info

Product

Resources

About

Comparative 1H NMR and molecular modeling study of hydroxy protons of β-d-Galp-(1→4)-β-d-GlcpNAc-(1→2)-α-d-Manp-(1→O)(CH2)7CH3 analogues in aqueous solution

Cited by 8 publications

References 32 publications

Temperature dependencies of amide 1H‐ and 15N‐chemical shifts in hyaluronan oligosaccharides

Temperature dependencies of amide 1H‐ and 15N‐chemical shifts in hyaluronan oligosaccharides

Inter‐residual Hydrogen Bonding in Carbohydrates Unraveled by NMR Spectroscopy and Molecular Dynamics Simulations

A Solution NMR Approach To Determine the Chemical Structures of Carbohydrates Using the Hydroxyl Groups as Starting Points

Contact Info

Product

Resources

About

Temperature dependencies of amide ¹H‐ and ¹⁵N‐chemical shifts in hyaluronan oligosaccharides

Temperature dependencies of amide ¹H‐ and ¹⁵N‐chemical shifts in hyaluronan oligosaccharides