Structure cristalline de l'α-<scp>D</scp>-mannopyrannose

Longchambon, F.; Avenel, D.; Neuman, A.

doi:10.1107/s0567740876006468

Cited by 35 publications

(17 citation statements)

References 2 publications

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“…An ability to determine a preferred orientation relative to a liquid crystal axis, or a micelle surface, can be demonstrated. In addition, it can be demonstrated that the observed set of quadrupole splittings is consistent with the known crystal structure for this compound (13). This set of experiments can be viewed as a step toward the study of more complex oligosaccharides.…”

supporting

confidence: 73%

“…In the cases presented, basic structures are known from x-ray diffraction work (13), and the fact that we were able to find an orientation that reproduces most splittings by using carbon-deuterium bond vectors derived from the crystal structure shows the solution structure to be in approximate agreement with the crystal structure. The departure of calculated from observed quadrupole splittings is, however, well beyond experimental precision (±20 Hz).…”

Section: Figurementioning

confidence: 81%

“…The calculation requires a knowledge of the relative orientation of each carbon-deuterium bond. In the case of the a anomer, a crystal structure exists from which the relative orientations can be derived (13). For the anomer, the same relative orientations were assumed to For the 8 anomer, a best solution is found with the direction of the ordering axis as indicated in Fig.…”

Section: Figurementioning

confidence: 99%

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Deuterium NMR as a structural probe for micelle-associated carbohydrates: D-mannose.

Prestegard¹,

Miner²,

Tyrell³

1983

Proc. Natl. Acad. Sci. U.S.A.

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Residual quadrupole splittings for deuterons on perdeuterated a-and (3-D-mannose oriented in a potassium laurate liquid crystal have been measured. Multiple quantum two-dimensional NMR spectroscopy at high magnetic field is used to gain sufficient resolution to assign splittings to specific sites within these molecules. The assigned splittings are interpreted in terms of molecular geometries and preferred orientations of the molecules relative to the surface of the potassium laurate micelles that make up the liquid crystalline phase.The three-dimensional structures of complex carbohydrates and constituent sugars have become a topic of considerable interest over the last several years. It is now recognized that these molecules play central roles in cellular biology as structural components, as protective layers, as cell surface receptors, and as antigenic determinants (1, 2). Yet these molecules are among the least well characterized of biological macromolecules. Recent advances in high-resolution NMR, mass spectrometry, and diffraction studies (2-6) are providing new primary and secondary structural features, but progress toward an understanding of long-range folding in solution or the nature of membrane surface interactions is slow. Improved analytical methods capable of providing such information would be extremely valuable.Deuterium NMR has shown substantial promise as a probe of structural properties of both large and small molecules. This derives from the fact that this spin one nucleus displays both magnetic field-nuclear magnetic moment interactions and electric field gradient-nuclear quadrupole moment interactions. The former are defined in the laboratory frame by the application of a magnetic field. The latter are defined in the molecular frame by the distribution of electrons in chemical bonds, for example, a deuterium-carbon bond. In ordered systems, the manner in which the two interactions combine depends on the orientation of the bond relative to a molecular frame and on an order parameter matrix describing ordering of the molecule relative to the magnetic field. The interactions lead to two observable transitions for each site. At high field, for an axially symmetric bond in an axially ordered system, these transitions are split by 3e2qQ AVQ = 4h (1 -3 cos2)Sz. [1] e2qQ/h is a constant for a given bond type (170 kHz for deuterium bound to aliphatic carbons), 6 is the angle between the bond and averaging axis, and Sz is an order parameter (7). It is clear that information concerning orientation of molecular bonds or molecular order can be extracted from observation of deuterium spectra.Most applications of deuterium spectroscopy to date have used a known molecular geometry to extract order parameters. In a few liquid crystal studies, molecular geometries have been deduced (8)(9)(10)(11) Approximately 15 mg of mannose in 0.04 ml of H20 was added to 1.5 ml of this phase. The sample in a 10 mm NMR tube was placed in an 11.7-T superconducting magnet and allowed to equilibrate at 318 K for -1 hr...

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supporting

confidence: 73%

Section: Figurementioning

confidence: 81%

Section: Figurementioning

confidence: 99%

See 1 more Smart Citation

Deuterium NMR as a structural probe for micelle-associated carbohydrates: D-mannose.

Prestegard¹,

Miner²,

Tyrell³

1983

Proc. Natl. Acad. Sci. U.S.A.

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“…The average bond lengths for C-C and C-O bonds in furanose ring are nearly identical with those in pyranose ring (Ishii et al 2014; Ishii et al 2015; Longchambon et al 1976; McDonald and Beevers 1952; Ohanessian et al 1977; Ohanessian and Gillierpandraud 1976). Therefore, the bond length parameters for furanose ring were imported from GLYCAM06, and simulations with these parameters demonstrated good agreement with the corresponding crystallographic values (Table S3 and Table S4).…”

Section: Resultsmentioning

confidence: 72%

Insights into furanose solution conformations: beyond the two-state model

Wang

Woods

2016

J Biomol NMR

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A two-state model is commonly used for interpreting ring conformations of furanoses based on NMR scalar 3J-coupling constants, with the ring populating relatively narrow distributions in the North and the South of the pseudorotation itinerary. The validity of this simple approach has been questioned, and is examined here in detail employing molecular dynamics (MD) simulations with a new GLYCAM force field parameter set for furanoses. Theoretical 3J-coupling constants derived from unrestrained MD simulations with the new furanose-specific parameters agreed with the experimental coupling constants to within 1 Hz on average. The results confirm that a two state model is a reasonable description for the ring conformation in the majority of methyl furanosides. However, in the case of methyl α-D-arabinofuranoside the ring populates a continuum of states from North to South via the eastern side of the pseudorotational itinerary. Two key properties are responsible for these differences. Firstly, East and West regions in β- and α-anomers, respectively, are destabilized by the absence of the anomeric effect. And, secondly, East or West conformations can be further destabilized by repulsive interactions among vicinal hydroxyl groups and ring oxygen atoms when the vicinal hydroxyl groups are in syn-configurations (such as in ribose and lyxose) more so than when in anti (arabinose, xylose).

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“…Fortunately, this class covers more than 90% of the entries in the Cambridge Structural Database (Padmaja, Ramakumar & Viswamitra, 1990), although this percentage may be lower for hydrogenbonded molecules (Gavezzotti & Filippini, 1994). Six out of the seven reported hexopyranose structures fall into this category, the exception being c~-D-mannose (Longchambon, Avenel & Neuman, 1976). They all crystallize in space group P212121 and we based our strategy on this knowledge.…”

Section: Introductionmentioning

confidence: 99%

Attempted prediction of the crystal structures of six monosaccharides

Eijck¹,

Mooij²,

Kroon³

1995

Acta Crystallogr Sect B

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A method is reported to generate possible crystal structures of the six hexopyranoses where comparison with an X-ray determination is possible. In these molecules, internal degrees of freedom are all-important. Using essentially only the information that the space group is P2~2~2~ with one molecule in the asymmetric unit, a systematic search was made for all low-energy crystal structures of these substances. The energies were minimized with respect to nine lattice and rigid-body parameters and six intramolecular dihedral angles. The number of possible structures within the range 10 kcal mo1-1 is of the order 1000. In all cases, the experimental structure was among them, and in four cases this was either the structure with the lowest energy or only a few tenths of a kcal mol -~ higher. However, in the two other cases the relative energy of the experimental structure was over 5 kcal mol -l. Such calculations can provide a sensitive test for force fields.

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Structure cristalline de l'α-D-mannopyrannose

Cited by 35 publications

References 2 publications

Deuterium NMR as a structural probe for micelle-associated carbohydrates: D-mannose.

Deuterium NMR as a structural probe for micelle-associated carbohydrates: D-mannose.

Insights into furanose solution conformations: beyond the two-state model

Attempted prediction of the crystal structures of six monosaccharides

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