Getting to know the nitrogen next door: HNMBC measurements of amino sugars

Limtiaco, John F. K.; Langeslay, Derek J.; Béni, Szabolcs; Larive, Cynthia K.

doi:10.1016/j.jmr.2011.01.029

Cited by 21 publications

(30 citation statements)

References 33 publications

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“…The 15 N chemical shifts of the α-GlcN (34.4 ppm) and α-GlcN3S (36.2 ppm) are alsoconsistently larger than the corresponding β-GlcN (32.9 ppm) and β-GlcN3S (34.5 ppm) due to deshielding by nearby OH1 oxygen in the α-anomer. Overall, the 15 N chemical shifts measured in this work are slightly larger than the values previously reported using HMBC, most likely due to temperature differences between the two sets of measurements 36. Detection by HSQC through one-bond 1 H-15 N couplings is much more sensitive than indirect detection by HMBC through long-range couplings.…”

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confidence: 65%

¹H and ¹⁵N NMR Characterization of the Amine Groups of Heparan Sulfate Related Glucosamine Monosaccharides in Aqueous Solution

Beecher

Larive

2015

Anal. Chem.

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Glucosamine is an important constituent of the heterogeneous glycosaminoglycans heparin and heparan sulfate occurring in N-acetylated and N-sulfated forms, and as the unmodified amine. Though the (1)H and (15)N NMR chemical shifts of N-acetyl- and N-sulfoglucosamine residues have been extensively characterized, this study provides the first direct NMR characterization of the amine groups of glucosamine and 3-O-sulfoglucosamine in aqueous solution. The solvent exchange properties of the amine protons are examined, and the possibility of a salt bridge between the sulfate and amine groups of 3-O-sulfoglucosamine is explored through (1)H NMR pKa measurements but is not supported by the experimental results.

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confidence: 65%

¹H and ¹⁵N NMR Characterization of the Amine Groups of Heparan Sulfate Related Glucosamine Monosaccharides in Aqueous Solution

Beecher

Larive

2015

Anal. Chem.

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“…The different chemical shifts of the 15 N nuclei (α = 93.71 ppm, β = 93.32 ppm) shown in Figure 2 are consistent with the values we reported previously using longrange 15 NÀ 1 H couplings measured with the [ 1 H, 15 N] heteronuclear multiple-bond coherence (HMBC) experiment using carbon-bound protons and confirms the 1 H resonance assignments of the two GlcNS anomers. 37 Although detection of the GlcNS sulfamate 1 H and 15 N resonances is interesting, to be useful for GAG characterization the 1 H and/or 15 N NMR chemical shifts must be sensitive to subtle structural differences. We selected the synthetic heparin mimic fondaparinux to probe the potential value of [ 1 H, 15 N]-HSQC NMR spectra for heparin and HS structural characterization.…”

Section: ' Resultsmentioning

confidence: 99%

Detection of the ¹H and ¹⁵N NMR Resonances of Sulfamate Groups in Aqueous Solution: A New Tool for Heparin and Heparan Sulfate Characterization

2011

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Sulfamate (NHSO(3)(-)) groups are critically important structural elements of the glycosaminoglycans heparin and heparan sulfate (HS). Experimental conditions are presented for detection of the sulfamate (1)H NMR resonances in aqueous solution. NMR spectra reported for N-sulfoglucosamine (GlcNS) and the synthetic pentasaccharide drug fondaparinux demonstrate the broad utility of the sulfamate group (1)H chemical shifts to reflect differences in molecular structure. The sulfamate protons also provide an efficient route for detection of (15)N chemical shifts through proton-nitrogen correlations measured with the heteronuclear single quantum coherence (HSQC) experiment. The HSQC spectra of GlcNS, fondaparinux, and the low-molecular weight heparin enoxaparin illustrate the power of the (1)H and (15)N chemical shifts of the sulfamate NH groups for the structural characterization of heparin and HS.

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“…One of the main utilizations of the fast repetition NMR methods is to increase the sensitivity per unit of time. One of the first implementations of this strategy is for the detection of 15 N in amino sugars in mixtures . The 1 H– 15 N IMPACT HMBC was slightly modified by removing the 1 J NH preparation filter for giving the 1 H– 15 N IMPACT HNMBC.…”

Section: Applications Of Fast Repetition Techniquesmentioning

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How to face the low intrinsic sensitivity of 2D heteronuclear NMR with fast repetition techniques: go faster to go higher!

Farjon

2017

Magnetic Reson in Chemistry

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Nuclear magnetic resonance (NMR) is one of the most widely used analytical techniques in numerous domains where molecules are objects of investigation. However, major limitations of multidimensional NMR experiments come from their low sensitivity and from the long times needed for their acquisition. In order to overcome such limitations, fast repetition NMR techniques allowed for the reduction of 2D experimental time and for the conversion of the gained time into a higher number of scans leading to a better sensitivity. Thus, fast repetition 2D heteronuclear NMR techniques have allowed new advances in NMR, especially to access infomation on low abundant nuclei, to enhance the detection of low concentrated compounds and to probe weak interactions like hydrogen bonds at natural abundance. Copyright © 2017 John Wiley & Sons, Ltd.

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Getting to know the nitrogen next door: HNMBC measurements of amino sugars

Cited by 21 publications

References 33 publications

¹H and ¹⁵N NMR Characterization of the Amine Groups of Heparan Sulfate Related Glucosamine Monosaccharides in Aqueous Solution

¹H and ¹⁵N NMR Characterization of the Amine Groups of Heparan Sulfate Related Glucosamine Monosaccharides in Aqueous Solution

Detection of the ¹H and ¹⁵N NMR Resonances of Sulfamate Groups in Aqueous Solution: A New Tool for Heparin and Heparan Sulfate Characterization

How to face the low intrinsic sensitivity of 2D heteronuclear NMR with fast repetition techniques: go faster to go higher!

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Getting to know the nitrogen next door: HNMBC measurements of amino sugars

Cited by 21 publications

References 33 publications

1H and 15N NMR Characterization of the Amine Groups of Heparan Sulfate Related Glucosamine Monosaccharides in Aqueous Solution

1H and 15N NMR Characterization of the Amine Groups of Heparan Sulfate Related Glucosamine Monosaccharides in Aqueous Solution

Detection of the 1H and 15N NMR Resonances of Sulfamate Groups in Aqueous Solution: A New Tool for Heparin and Heparan Sulfate Characterization

How to face the low intrinsic sensitivity of 2D heteronuclear NMR with fast repetition techniques: go faster to go higher!

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¹H and ¹⁵N NMR Characterization of the Amine Groups of Heparan Sulfate Related Glucosamine Monosaccharides in Aqueous Solution

¹H and ¹⁵N NMR Characterization of the Amine Groups of Heparan Sulfate Related Glucosamine Monosaccharides in Aqueous Solution

Detection of the ¹H and ¹⁵N NMR Resonances of Sulfamate Groups in Aqueous Solution: A New Tool for Heparin and Heparan Sulfate Characterization