Nuclear magnetic resonance in carbohydrate chemistry

Kotowycz, George; Lemieux, R. U.

doi:10.1021/cr60286a004

Cited by 144 publications

(38 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Other forms of this equation have been proposed but in all cases these equations must be used with care in determining torsion angles from coupling constants due to the difficulties in determining values for the constants for any one specific kind of structure (17,18). Observed values of vicinal coupling constants for chair forms of a variety of carbohydrates have been tabulated ( 19).…”

Section: Discussionmentioning

confidence: 99%

“…These range from 1.7 to 2.2 x 10-lo s for all protons listed in the table at both TXB, concentrations. The one exception is for protons [17][18][19] at the lower TXB, concentration, where only a small frequency dependence for T , , was observed, and a correlation time of -1 x 10-lo s is calculated. In addition, these protons have the same chemical shift and this may affect the relaxation times.…”

Section: Affects the H-8 H-loa And The H-1op Resonances And Confirmmentioning

confidence: 91%

“…Data are not reported where there was significant overlap of resonances corresponding to different protons. The one exception is for protons [17][18][19], which have identical chemical shifts. The relaxation rate for these protons is reported as it provides aprobe of the mobility of this side chain.…”

Section: Materals and Methodsmentioning

confidence: 99%

See 2 more Smart Citations

A high field proton magnetic resonance study of the solution conformation of thromboxane B₂

Kotovych¹,

Aarts²

1980

Can. J. Chem.

View full text Add to dashboard Cite

The solution conformation of thromboxane B2 (TXB2) has been studied using high-field nuclear magnetic resonance techniques. In CDCl3, both anomers are present in solution with 76% 11α-OH TXB2 and 24% 11β-OH TXB2. In CD3OD, the predominant anomer is 11β-OH TXB2 (80%) while the concentration of 11α-OH TXB2 is 20%. The proton resonances were assigned at 400 MHz using double resonance techniques. The analysis of the vicinal coupling constants indicates that the six-membered ring is present in solution in a chair conformation with both of the aliphatic side chains equatorial. Proton longitudinal relaxation times were measured at 25 °C in CDCl3 for H-2, H-11β, H-12, H-13, H-14, and H-17 to H-19, both at 200 MHz and at 400 MHz. From the frequency dependence of these dipolar relaxation times, the rotational correlation times were evaluated. Within experimental error, all of the values are similar in magnitude (~ 2.0 × 10−10 s) indicating that this is the molecular rotational correlation time.

show abstract

Section: Discussionmentioning

confidence: 99%

Section: Affects the H-8 H-loa And The H-1op Resonances And Confirmmentioning

confidence: 91%

See 1 more Smart Citation

A high field proton magnetic resonance study of the solution conformation of thromboxane B₂

Kotovych¹,

Aarts²

1980

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…5A). Each peak is assigned to ␣6 (1.24 ppm), ␤6 (1.28 ppm), ␤2 (3.46 ppm), ␤3 (3.66 ppm), ␤4 (35). Comparing those peaks with the sample spectrum (Fig.…”

Section: Purification and Characterization Of Enzymes Involved In Thementioning

confidence: 99%

A Novel NDP-6-deoxyhexosyl-4-ulose Reductase in the Pathway for the Synthesis of Thymidine Diphosphate-d-fucose

Yamaguchi¹,

Nakano²,

Noji

et al. 1999

Journal of Biological Chemistry

View full text Add to dashboard Cite

The serotype-specific polysaccharide antigen of Actinobacillus actinomycetemcomitans Y4 (serotype b) consists of D-fucose and L-rhamnose. Thymidine diphosphate (dTDP)-D-fucose is the activated nucleotide sugar form of D-fucose, which has been identified as a constituent of structural polysaccharides in only a few bacteria. In this paper, we show that three dTDP-D-fucose synthetic enzymes are encoded by genes in the gene cluster responsible for the synthesis of serotype b-specific polysaccharide in A. actinomycetemcomitans. The first and second steps of the dTDP-D-fucose synthetic pathway are catalyzed by D-glucose-1-phosphate thymidylyltransferase and dTDP-D-glucose 4,6-dehydratase, which are encoded by rmlA and rmlB in the gene cluster, respectively. These two reactions are common to the well studied dTDP-L-rhamnose synthetic pathway. However, the enzyme catalyzing the last step of the dTDP-Dfucose synthetic pathway has never been reported. We identified the fcd gene encoding a dTDP-4-keto-6-deoxy-D-glucose reductase. After purifying the three enzymes, their enzymatic activities were analyzed by reversedphase high performance liquid chromatography. In addition, nuclear magnetic resonance analysis and gasliquid chromatography analysis proved that the fcd gene product converts dTDP-4-keto-6-deoxy-D-glucose to dTDP-D-fucose. Moreover, kinetic analysis of the enzyme indicated that the K m values for dTDP-4-keto-6-deoxy-Dglucose and NADPH are 97.3 and 28.7 M, respectively, and that the enzyme follows the sequential mechanism. This paper is the first report on the dTDP-D-fucose synthetic pathway and dTDP-4-keto-6-deoxy-D-glucose reductase.Capsular polysaccharides are the outermost structures on a bacterial cell and play a critical role in the interactions of the cell with the environment (1). These molecules are prominent, structurally and serologically diverse antigens that are involved in pathogenic processes and in mediating resistance to important host defense mechanisms. In the case of human pathogens, a large number of different capsule serotypes have been identified (1). Previously, we reported that the serotype b-specific antigen of Actinobacillus actinomycetemcomitans Y4 is a capsular polysaccharide-like antigen consisting of two deoxyhexoses, L-rhamnose and D-fucose (2).A. actinomycetemcomitans is a nonmotile, Gram-negative, capnophilic, fermentative coccobacillus that has been implicated in the etiology and pathogenesis of localized juvenile periodontitis (3-5), adult periodontitis (6), and severe nonoral human infections (7). A. actinomycetemcomitans strains isolated from the human oral cavity are divided into five serotypes, a, b, c, d, and e (8 -10). The serologic specificity is defined by the polysaccharide on the surface of this organism (11), and the serotype-specific antigen is one of the immunodominant antigens in the organism (12, 13).In general, L-rhamnose is a component of many bacterial polysaccharides (14). The synthesis of thymidine diphosphate (dTDP) 1 -L-rhamnose, which is the activated nuc...

show abstract

“…Can It is well known that the pmr spectra of alcohols (1, 2) and carbohydrates (3)(4)(5)(6)(7)(8)(9) in dimethyl sulfoxide (DMSO) solution display well resolved signals of the hydroxyl groups and that the derived coupling constants JFI-c--H provide valuable information on configuration and conformation of these compounds (2-9).…”

Section: Y~t a R Omentioning

confidence: 99%

Hydroxyl proton resonances of methyl 4,6-O-benzyIidene-α- and β-D-glucopyranosides and their derivatives in dimethyl sulfoxide solution

Kondo¹,

Kitamura²

1977

Can. J. Chem.

View full text Add to dashboard Cite

Proton magnetic resonance spectra of methyl 4,6-O-benzylidene-α- and β-D-glucopyranosides (1 and 10) and their mono-substituted derivatives are determined in dimethyl sulfoxide solution. Assignments of the hydroxyl group resonances of 1 and 10 are confirmed by means of INDOR techniques. It is shown that the position of the hydroxyl substituent of the mono-substituted derivatives of 1 and 10 can be determined by using the coupling constants JH—C—O—H. It is proposed that the vicinal diols of 1 and 10 give 1:1 associations with dimethyl sulfoxide molecules, and the C—H and O—H bonds at position 2 of the mono-substituted derivatives of 1 are approximately anti.

show abstract

Nuclear magnetic resonance in carbohydrate chemistry

Cited by 144 publications

References 30 publications

A high field proton magnetic resonance study of the solution conformation of thromboxane B₂

A high field proton magnetic resonance study of the solution conformation of thromboxane B₂

A Novel NDP-6-deoxyhexosyl-4-ulose Reductase in the Pathway for the Synthesis of Thymidine Diphosphate-d-fucose

Hydroxyl proton resonances of methyl 4,6-O-benzyIidene-α- and β-D-glucopyranosides and their derivatives in dimethyl sulfoxide solution

Contact Info

Product

Resources

About

Nuclear magnetic resonance in carbohydrate chemistry

Cited by 144 publications

References 30 publications

A high field proton magnetic resonance study of the solution conformation of thromboxane B2

A high field proton magnetic resonance study of the solution conformation of thromboxane B2

A Novel NDP-6-deoxyhexosyl-4-ulose Reductase in the Pathway for the Synthesis of Thymidine Diphosphate-d-fucose

Hydroxyl proton resonances of methyl 4,6-O-benzyIidene-α- and β-D-glucopyranosides and their derivatives in dimethyl sulfoxide solution

Contact Info

Product

Resources

About

A high field proton magnetic resonance study of the solution conformation of thromboxane B₂

A high field proton magnetic resonance study of the solution conformation of thromboxane B₂