Separation of the α- and β-Anomers of Carbohydrates by Diffusion-Ordered NMR Spectroscopy

Yamanoi, Takahiro; Oda, Yoshiki; Katsuraya, Kaname

doi:10.3390/magnetochemistry3040038

Cited by 6 publications

(4 citation statements)

References 23 publications

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“…Differentiation of maltooligosaccharides with a degree-of-polymerization (dp) of 3–4 and arabinoglycan with dp > 50 in beer, as well as analysis of glucose in fruit juices, have utilized DOSY NMR experiments to this end. 2D-DOSY experiments were also successfully used to differentiate the α- and β-anomeric forms of d -glucose, other monosaccharides, the anomeric forms of cellobiose, and different phenyl d -glucosides . The additional use of transverse ( x , y ) pulsed-field gradients (PFGs) in conjunction with the standard z -axis PFG can be used to reduce the impact of sample convection and to minimize gradient-dependent line shape distortions in 2D-DOSY NMR experiments, as exemplified for a mixture of mono- and oligosaccharides …”

Section: Nmr Experiments For Resonance and Sequence Assignmentsmentioning

confidence: 99%

“…2D-DOSY experiments were also successfully used to differentiate the αand β-anomeric forms of D-glucose, other monosaccharides, the anomeric forms of cellobiose, and different phenyl D-glucosides. 418 The additional use of transverse (x,y) pulsed-field gradients (PFGs) in conjunction with the standard z-axis PFG can be used to reduce the impact of sample convection and to minimize gradient-dependent line shape distortions in 2D-DOSY NMR experiments, as exemplified for a mixture of mono-and oligosaccharides. 419 In cases where the translational diffusion coefficients are closely similar and a DOSY experiment will not differentiate the components, one would need to rely on a different physicochemical property such as NMR spin relaxation, referred to as relaxation-ordered spectroscopy (ROSY).…”

Section: Carbohydrate Mixturesmentioning

confidence: 99%

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Primary Structure of Glycans by NMR Spectroscopy

Fontana

Widmalm

2023

Chem. Rev.

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Glycans, carbohydrate molecules in the realm of biology, are present as biomedically important glycoconjugates and a characteristic aspect is that their structures in many instances are branched. In determining the primary structure of a glycan, the sugar components including the absolute configuration and ring form, anomeric configuration, linkage(s), sequence, and substituents should be elucidated. Solution state NMR spectroscopy offers a unique opportunity to resolve all these aspects at atomic resolution. During the last two decades, advancement of both NMR experiments and spectrometer hardware have made it possible to unravel carbohydrate structure more efficiently. These developments applicable to glycans include, inter alia, NMR experiments that reduce spectral overlap, use selective excitations, record tilted projections of multidimensional spectra, acquire spectra by multiple receivers, utilize polarization by fast-pulsing techniques, concatenate pulse-sequence modules to acquire several spectra in a single measurement, acquire pure shift correlated spectra devoid of scalar couplings, employ stable isotope labeling to efficiently obtain homo-and/or heteronuclear correlations, as well as those that rely on dipolar cross-correlated interactions for sequential information. Refined computer programs for NMR spin simulation and chemical shift prediction aid the structural elucidation of glycans, which are notorious for their limited spectral dispersion. Hardware developments include cryogenically cold probes and dynamic nuclear polarization techniques, both resulting in enhanced sensitivity as well as ultrahigh field NMR spectrometers with a 1 H NMR resonance frequency higher than 1 GHz, thus improving resolution of resonances. Taken together, the developments have made and will in the future make it possible to elucidate carbohydrate structure in great detail, thereby forming the basis for understanding of how glycans interact with other molecules.

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Section: Nmr Experiments For Resonance and Sequence Assignmentsmentioning

confidence: 99%

Section: Carbohydrate Mixturesmentioning

confidence: 99%

Primary Structure of Glycans by NMR Spectroscopy

Fontana

Widmalm

2023

Chem. Rev.

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“…При этом компоненты фракционирования могут иметь одинаковые ММ и лишь незначительно различаться по форме молекул. Например, в публикации [34] представлены результаты успешного применения метода DOSY для разделения α and βаномерных изомеров различных углеводов (арбутина, фенилглюкопиранозида, Dглюкопиранозы, Dгалактопиранозы, Dманнопиранозы, целлобиозы). Характерно, что в большинстве исследований природных смесей компонентный анализ методом DOSY проводят одновременно с идентификацией строения этих компонентов с помощью комплекса традиционных методов ЯМР ( 1 Н, 13…”

Section: анализ многокомпонентных смесей полисахаридовunclassified

Diffusion-Ordered NMR Spectroscopy Application for Analysis of Polysaccharides

Кузьмина¹,

Moiseev²,

Severinova³

et al. 2022

Vedomosti Nauchnogo tsentra ekspertizy sredstv meditsinskogo pr

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Diffusion-ordered nuclear magnetic resonance spectroscopy (DOSY) is a molecular transport method in analytical chemistry, based on experimental recording of the molecules’ translational mobility at thermodinamic equilibrium in a solution. The translational mobility is characterised quantitatively by a self-diffusion coefficient. The aim of the study was to summarise the main trends in application of DOSY for the analysis of natural and modified natural polysaccharides used in pharmaceuticals and pharmaceutical biotechnology. The review shows that this method is an effective instrument for monitoring fractionation during isolation of polysaccharides from a natural mixture, for estimating their average molecular weight and molecular weight distribution, and for studying the formation of supramolecular systems based on polysaccharides. The paper describes main issues of the precise measurement of polysaccharide macromolecules self-diffusion coefficients and provides the correction factors to compensate for errors caused by fluctuations in temperature and viscosity of solutions. The observed scatter of self-diffusion coefficients of narrowly dispersed polymer macromolecules nuclei is explained using the polyphase concept. The paper illustrates ways of describing translational mobility of a polyphase polymer macromolecule as a whole. The authors summarise values of the gradient pulse sequence parameters used in quantitative measurements of self-diffusion coefficients of linear, low-branched, and branched polysaccharides.

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“…DOSY requires sufficiently large differences in diffusion coefficients, especially when there is signal overlap, which is not straightforward for anomers. Nevertheless, there exists some precedence for separation of the pyranose anomer spectra of glucose and mannose. , The resolving power can be improved upon by including relaxation encoding and parallel factor analysis , or by avoiding overlap by including pure shift resolution, , but limitations remain in cases of compounds with similar chemical shifts and also with large concentration differences. Alternatively, well-resolved and recognizable individual proton signals of the various compounds can be selectively excited, followed by a TOCSY (total correlation spectroscopy) mixing step to spread its polarization to the rest of the spin system (Figure a); if needed, it can be augmented with relaxation or diffusion encoding and/or pure shift resolution. − …”

Section: Introductionmentioning

confidence: 99%

Obtaining Pure ¹H NMR Spectra of Individual Pyranose and Furanose Anomers of Reducing Deoxyfluorinated Sugars

Poškaitė,

Wheatley,

Wells

et al. 2023

J. Org. Chem.

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Due to tautomeric equilibria, NMR spectra of reducing sugars can be complex with many overlapping resonances. This hampers coupling constant determination, which is required for conformational analysis and configurational assignment of substituents. Given that mixtures of interconverting species are physically inseparable, easy-to-use techniques that enable facile full 1 H NMR characterization of sugars are of interest. Here, we show that individual spectra of both pyranoside and furanoside forms of reducing fluorosugars can be obtained using 1D FESTA. We discuss the unique opportunities offered by FESTA over standard sel-TOCSY and show how it allows a more complete characterization. We illustrate the power of FESTA by presenting the first full NMR characterization of many fluorosugars, including of the important fluorosugar 2-deoxy-2-fluoroglucose. We discuss in detail all practical considerations for setting up FESTA experiments for fluorosugars, which can be extended to any mixture of fluorine-containing species interconverting slowly on the NMR frequency–time scale.

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Separation of the α- and β-Anomers of Carbohydrates by Diffusion-Ordered NMR Spectroscopy

Cited by 6 publications

References 23 publications

Primary Structure of Glycans by NMR Spectroscopy

Primary Structure of Glycans by NMR Spectroscopy

Diffusion-Ordered NMR Spectroscopy Application for Analysis of Polysaccharides

Obtaining Pure ¹H NMR Spectra of Individual Pyranose and Furanose Anomers of Reducing Deoxyfluorinated Sugars

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Separation of the α- and β-Anomers of Carbohydrates by Diffusion-Ordered NMR Spectroscopy

Cited by 6 publications

References 23 publications

Primary Structure of Glycans by NMR Spectroscopy

Primary Structure of Glycans by NMR Spectroscopy

Diffusion-Ordered NMR Spectroscopy Application for Analysis of Polysaccharides

Obtaining Pure 1H NMR Spectra of Individual Pyranose and Furanose Anomers of Reducing Deoxyfluorinated Sugars

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Obtaining Pure ¹H NMR Spectra of Individual Pyranose and Furanose Anomers of Reducing Deoxyfluorinated Sugars