13C-n.m.r. studies of d-glucose and d-galactose monosulphates

Archbald, P.Jane; Fenn, M. David; Roy, A.B.

doi:10.1016/s0008-6215(00)80847-2

Cited by 64 publications

(18 citation statements)

References 25 publications

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“…1 B) are shown. Assignments GlcN-6S I 1350 for GlcNAc-6S have been reported previously [14] and ours G1cNS-6S 11 16 GlcNAc-6S TIT 54 are in agreement (Fig. 1 C).…”

Section: Purifi'cution Uf'6-o-sulpliur~~sesupporting

confidence: 90%

Flavobacterium heparinum 6-O-sulphatase for N-substituted glucosamine 6-O-sulphate

et al. 1985

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A specific glyco-6-0-sulphatase has been purified to homogeneity from Fluvohacteriurn heparinurn. The enzyme hydrolyses the 6-0-sulphates of 2-deoxy-2-sulphamido-6-0-sulpho-~-glucose (GIcNS-~S), 2-acetamido-2-dcoxy-6-0-sulpho-~-glucose (GlcNAc-6s) and 2-amino-2-deoxy-6-0-sulphato-u-glucose .The activity was purified 2100-fold by successive chromatography on CM-Sepharose CL-6B, Sepharose CL-4B, hydroxyapatite and blue-Sepharose CL-6B. Sodium dodecyl sulphate/polyacrylamide gel electrophoresis showed a protein of relative molecular mass 64000. Four novel assays were developed using 3sS-labelled and I4C-labelled monosaccharides.The purified enzyme was free of all other known heparin-degrading enzymes. In particular this was the first resolution of the 6-0-sulphatase from the sulphamidase. Optimal activity was a t pH 7.5. Enzyme activity was virtually unaffected by Na' and K + ions. Enhancements of activity of 12% and 30% were effccted by Mgz+ and CaZt ions respectively. Inorganic phosphate and sulphate (both 0.005 mol dm-3) inhibited activity by 48% and 50% respectively. The K, value for the free amino substrate GlcN-6S was 1.35 mmol dm-3. In contrast the K,,, values for the GlcNAc-6S and GlcNS-6S were 54 pmol dm-3 and 16 pmol dm-3 respectively.The growth of Fluvohacteriurn liepurinurn on heparin is accompanied by the production of enzymes capable of degrading heparin, heparitin sulphate and the chondroitin sulphates. The existence of 0-sulphatase and sulphamidase enzymes was suggested by Korn and Payza [l].Linker and coworkers found N and 0-sulphated monosaccharides and oligosaccharides in digests of heparin [2] and heparitin sulphate [3]. Dietrich [4] reported that 2-deoxy-2-sulphamido-6-0-sulpho-o-glucose (GlcNS-6s) was a substrate for both the C'arrespondence to M. W. McLean, Department or Biochemistry. University of Aberdeen, Marischal College, Aberdeen, Scotland AB9 1 AS Ahhreviutions. GlcNCbz, 2-[(benzyloxycarbonyI)amino]-2-dcoxy-D-glucose; GlcN-6S, 2-amino-2-deoxy-6-0-sulpho-u-glucose; GlcNS6s. 2-deoxy-2-sulphamido-6-0-sulpho-~-glucose; GlcNAc-6S, 2-acetamido-2-deoxy-6-0-suIpho-~-glucose; GlcNS, 2-deoxy-2-sulphamido-D-glucose; GlcN, 2-amino-2-deoxy-~-glucose; GalN-6S, 2-amino-2-deoxy-6-0-sulpho-~-galactose; GalNAc-6S, 2-acetamido-2-deoxy-6-#-sulpho-u-galactose; SDS ; Ad,5glycuronidase, glycuronidase for (4-deoxy-rx-~-threo-hex-4-cnopyranosyluronic acid)-( 1 +4)-2-deoxy-2-sulphamido-6-0-sulpho-D-glucose, dUA+GlcNS-6S (EC 3.2.1. -); 2-0-sulphatasc for (4-deoxy-2-#-sulpho-a-~-~~~~~-hex-4-enopyranosyluronic acid)-( 1 4 4 ) -2-deoxy-2-sulphamido-6-0-sulpho-~-glucose, dUA-2S+GlcNS-6S (EC 3.1.6. -); 6-0-sulphatase for 2-deoxy-2-sulphamido-6-0-sulpho-D-glucose (EC 3.1.6.11) and 2-acelamido-2-deoxy-6-0-sulpho-~-glucose (EC 3.1.6. -); 2-deoxy-2-sulphamido-~-glucose sulphamidase (EC 3.1 0.1 .I); 2-acetamido-2-deoxy-6-0-sulpho-~-galactosc 6-0-sulphatase (EC 3.1.6. -); 3-0-sulphatase for 2-acetamido-2-deoxy-3-0-sulpho-D-glucose; 2-deoxy-2-sulpharnido-3-0-sulpho-~-glucose sulpharnidase and the 6-0-sulphatase. These enz...

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“…1 B) are shown. Assignments GlcN-6S I 1350 for GlcNAc-6S have been reported previously [14] and ours G1cNS-6S 11 16 GlcNAc-6S TIT 54 are in agreement (Fig. 1 C).…”

Section: Purifi'cution Uf'6-o-sulpliur~~sesupporting

confidence: 90%

Flavobacterium heparinum 6-O-sulphatase for N-substituted glucosamine 6-O-sulphate

et al. 1985

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“…Their structures were confirmed by both 1 H and 13 C NMR spectra, and the interpretation of these spectra was established by 1 H, 13 C HMQC NMR experiment, which helped the assignment of both proton and carbon signals (Scheme 2). The presence of 13 in the pyranosyl form was deduced by comparing its 13 C NMR spectrum with those of α-and β-D-galactopyranose 15 and 16, [22][23][24] and 1-(1β-Dgalactopyranosyl)-2-isonicotinoylhydrazine (17). 25 Substitution of the hydroxyl group at C-1 of 16 with the hydrazine residue causes a shift for all carbon signals of 13, but with a small effect on the magnitude of chemical shifts of C-3 and C-5 because they have the same stereochemical relationship to the anomeric C-1, consequently C-3 and C-5 can be identified at δ c 72.81 and 77.00, respectively.…”

Section: Results and Disscussionmentioning

confidence: 99%

“…The aromatic and thiazole carbons were resonated in the range of δ c 104.46-175.28. [22] 62.00 [23] 61.90 [24] 61.90 [22] 61.81 [23] 61.70 [24] 60.55 [25] 61.15…”

Section: Results and Disscussionmentioning

confidence: 99%

Synthesis of Biologically Active [4‐(4‐Bromophenyl)‐2‐thiazolyl]hydrazones and their D‐Galactose Derivatives

Ramadan¹

2010

Chin. J. Chem.

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Benzaldehyde [4-(4-bromophenyl)thiazol-2-yl]hydrazones 5a-5d were prepared by reacting the thiosemicarbazones 2a-2d with 2,4'-dibromoacetophenone (1) in absolute ethanol. Acetylation of 5a and 5b with Ac 2 O/Py at room temperature gave the N-acetyl derivatives 6a and 6b. 4-Methyl-2-pentanone/cyclopentanone [4-(4-bromophenyl)thiazol-2-yl]hydrazones (8a) and (8b) were similarly obtained from the reaction of 1 with the thiosemicarbazones 7a and 7b, respectively. Cyclization of D-galactose thiosemicarbazone (9) and its tautomers 10 and 11 with 1 afforded an equilibrium mixture of the acyclic 2-thiazolylhydrazone 12, together with its respective cyclic galactosyl derivatives 13 and 14, whose structures were studied by using 1 H and 13 C NMR spectra. The antimicrobial activity of the synthesized thiazole derivatives was evaluated in vitro by using an agar diffusion technique, and some of these compounds showed potential activity against Candida albicans.

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“…Detritylation of 13 with a solution of chloroform saturated with hydrogen chloride gas at O°C, followed by quenching the reaction with saturated aqueous sodium bicarbonate, led exclusively to the formation of methyl 2,3,6-tri-0-acetyl-a-D-galactopyranoside 14. This C4 + C6 base-catalysed transesterification is well documented in the glucose series (21,22). However, in the galactose series, attempts to prepare 1,2,3,6-tetra-O-acetyl-galactose from the corresponding 1,2,3,4-tetra-O-acetyl compound by acetyl migration in dilute alkali have led to complex mixtures of products (21).…”

Section: Introductionmentioning

confidence: 92%

Novel Synthesis of monosulphated methyl α-D-galactopyranosides

Rashid¹,

Mackie²,

Colquhoun³

et al. 1990

Can. J. Chem.

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DORIANO LAMBA. Can. J. Chem. 68, 1122Chem. 68, (1990. The syntheses of the methyl u-D-galactopyranoside 2-, 3-, 4-, and 6-sulphates (11, 12, 16, and 21 respectively) have been achieved using trimethylamine -sulphur trioxide as the sulphating agent. The procedure used is high yielding and requires shorter reaction times than reported previously. Each compound was obtained in a crystalline form as the potassium salt. Improved syntheses are described of the 3,4-isopropylidene acetal2 of the methyl u-D-galactopyranoside and methyl.2-O-acetyl 4,6-O-benzylidene a-D-galactopyranoside 8, which are starting materials in the preparation of the 2-and 3-sulphates (11 and 12 respectively). An efficient route has been devised for the synthesis of methyl 2,3,6-tri-O-acetyl-a-D-galactopyranoside 14 using a base-catalysed transesterification (C4-OH+ C6-OH).

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13C-n.m.r. studies of d-glucose and d-galactose monosulphates

Cited by 64 publications

References 25 publications

Flavobacterium heparinum 6-O-sulphatase for N-substituted glucosamine 6-O-sulphate

Flavobacterium heparinum 6-O-sulphatase for N-substituted glucosamine 6-O-sulphate

Synthesis of Biologically Active [4‐(4‐Bromophenyl)‐2‐thiazolyl]hydrazones and their D‐Galactose Derivatives

Novel Synthesis of monosulphated methyl α-D-galactopyranosides

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