Carbon-13-carbon-13 spin coupling constants in aldoses enriched with 13C at the terminal hydroxymethyl carbon: effect of coupling pathway structure of JCC in carbohydrates.

Wu, Jian; Bondo, Paul B.; Vuorinen, Tapani; Serianni, Anthony S.

doi:10.1021/ja00035a051

Cited by 43 publications

(45 citation statements)

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“…30,105,106 The same pathway bearing out-of-plane terminal oxygen substituents appeared to exert the same effect on 3 J CC magnitude as the pathway devoid of terminal oxygen substituents. 30 The C2′–C1′–O1’–C4 coupling pathway pertinent to 3 J C2′,C4 orients the coupled carbons antiperiplanar at ϕ = 60°.…”

Section: Resultsmentioning

confidence: 79%

Conformational Populations of β-(1→4) O-Glycosidic Linkages Using Redundant NMR J-Couplings and Circular Statistics

et al. 2017

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Twelve disaccharides containing β-(1→4) linkages and displaying systematic structural variations in the vicinity of these linkages were selectively labeled with 13C to facilitate measurements of multiple NMR spin–spin (scalar; J) coupling constants (JCH and JCC values) across their O-glycosidic linkages. Ensembles of spin-couplings (2JCOC,3JCOCH, 3JCOCC) sensitive to the two linkage torsion angles, phi (ϕ) and psi (ψ), were analyzed by using parametrized equations obtained from density functional theory (DFT) calculations, Fredholm theory, and circular statistics to calculate experiment-based rotamer populations for ϕ and ψ in each disaccharide. With the statistical program MA’AT, torsion angles ϕ and ψ were modeled as a single von Mises distribution, which yielded two parameters, the mean position and the circular standard deviation (CSD) for each angle. The NMR-derived rotamer populations were compared to those obtained from 1 μs aqueous molecular dynamics (MD) simulations and crystallographic database statistical analyses. Conformer populations obtained exclusively from the MA’AT treatment of redundant J-couplings were in very good agreement with those obtained from the MD simulations, providing evidence that conformational populations can be determined by NMR for mobile molecular elements such as O-glycosidic linkages with minimal input from theory. The approach also provides an experimental means to validate the conformational preferences predicted from MD simulations. The conformational behaviors of ϕ in the 12 disaccharides were very similar, but those of ψ varied significantly, allowing a classification of the 12 disaccharides based on preferred linkage conformation in solution.

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Section: Resultsmentioning

confidence: 79%

Conformational Populations of β-(1→4) O-Glycosidic Linkages Using Redundant NMR J-Couplings and Circular Statistics

et al. 2017

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“…The inherent difficulty in the conformational description of furanose sugars in solution based only on vicinal 1H-IH J-couplings was early recognized by Jardetzky [12] and largely by the work of Serianni and co-workers [13][14][15]. They introduced the analysis of the 13C-~3C and 13C-1H spin coupling in aldoses and erythro-nucleosides enfiched with 13C in addition to the set of 1HJH coupling constants.…”

Section: Discussionmentioning

confidence: 99%

Conformational analysis by NMR spectroscopy of 2′-deoxy-2′-C-alkylnucleosides: Building blocks of new antisense fragments

1994

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The conformafion in solution of new modified nucleosides bearing branched-chain sugars used as building blocks for antisense oligonucleotides is investigated by NMR spectroscopy. Within a classical approach to the conformational study of these molecules, a new methodology is adopted, which is capable of exploring all the possibilities, for a given conformational model, that are compatible with the experimental data. The relationship between conformation of the monomers and hyb¡ properties of the corresponding oligonucleotides is examined. IntroducflonThe field of Nucleic Acids and their chemical and biochemical applications, the development of the so called antisense strategy occupies a well-defined place.Basically, the principle is based on the recognition of complementary sequences through base pair interactions, and the final goal is the inhibition of the expression of a target gene. Therefore, ah antisense fragrnent is a synthetic oligonucleotide carrying a sequence which is complementary (antisense) to a portion of a target m-RNA. This oligonucleotide will hybridize with this RNA molecule and block its translation [1]. This strategy has very important applications not only in molecular biology but also in the development of new therapeutic principles [2].Some features ate characteristic of a sultable antisense fragment. The most important ones are: good up-take by cells, resistance to nucleases, and good hyb¡ properties.In order to obtain stable oligonucleotides with regard to the action of nucleases, it is necessary to introduce chemical modifications. These modifications, though, must not

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“…The 2 J CC and 3 J CC values measured for the α and β anomers of the latter substrate were in good agreement with those reported by Serianni and coworkers, on the basis of direct, 1D 13 C NMR of single-site, 13 C-enriched glucoses. 119,120 Correlation of the 3 J CC couplings of the J22 polysaccharide was made by reference to the geometries of a three-conformation model determined by CHARMM molecular modeling. 117 Xu and Bush did not distinguish 3 J CCOC and 3 J CCCC , but instead formulated 116 a combination equation:

{{}^{3}J}_{CC} = 2.24 {cos}^{2} ϕ - 1.3 cos ϕ + 0.5

…”

Section: Vicinal Coupling Constantsmentioning

confidence: 99%

“…synthesized eight aldohexoses, four aldopentoses, and two aldotetroses, all substituted with 13 C at the terminal hydroxymethyl carbon atom. 120 Interpretation of the 13 C NMR spectra measured at 75 and 125 MHz was assisted by 1D INADEQUATE 13 C spectra, which can sometimes alleviate problems of spectral overlap, and enhance the detection of small 13 C– 13 C couplings. 120 In the aldohexopyranoses, the dihedral angle ϕ C-3–C-4–C-5–C-6 has a relatively fixed value of ~180°, and, therefore, these compounds provide a good model for the study of substituent effects along the coupling pathway.…”

Section: Vicinal Coupling Constantsmentioning

confidence: 99%

Chapter 3 Developments in the Karplus Equation as they Relate to the NMR Coupling Constants of Carbohydrates

Coxon

2009

Advances in Carbohydrate Chemistry and Biochemistry

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Carbon-13-carbon-13 spin coupling constants in aldoses enriched with 13C at the terminal hydroxymethyl carbon: effect of coupling pathway structure of JCC in carbohydrates.

Cited by 43 publications

References 0 publications

Conformational Populations of β-(1→4) O-Glycosidic Linkages Using Redundant NMR J-Couplings and Circular Statistics

Conformational Populations of β-(1→4) O-Glycosidic Linkages Using Redundant NMR J-Couplings and Circular Statistics

Conformational analysis by NMR spectroscopy of 2′-deoxy-2′-C-alkylnucleosides: Building blocks of new antisense fragments

Chapter 3 Developments in the Karplus Equation as they Relate to the NMR Coupling Constants of Carbohydrates

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