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13C NMR Studies on Trifluoroacetyl Derivatives of 2-Acetamido-2-deoxyhexoses

The effect of trifluoroacetylation on the 13C chemical shifts of 2-acetamido-2-deoxyhexoses was examined.Studies of the 2-acetamido derivatives of glucose, galactose and mannose established that no regular trend in the 13C shifts occured on trifluoroacetylation.This was in marked contrast to the results obtained for the 1H chemical shifts.

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Tetrahydropyran – Wikipedia,
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An acceptor analogue of beta-1,4-galactosyltransferase: Substrate, inhibitor, or both?

Many glycosyltransferase inhibitors in the literature are structurally derived from the donor or acceptor substrate of the respective enzyme. A representative example is 2-naphthyl beta-D-GlcNAc, a synthetic GlcNAc glycoside that has been reported as a galactosyltransferase inhibitor. This GlcNAc derivative is attractive as a chemical tool compound for biological and biochemical studies because of its reported potency as an inhibitor, and its short and straightforward synthesis from readily available starting materials. We report that in our hands, 2-naphthyl beta-D-GlcNAc behaved, unexpectedly, as an acceptor substrate of the inverting beta-1,4-galactosyltransferase (beta-1,4-GalT) from bovine milk. This substrate activity has not previously been described. We found that 2-naphthyl beta-D-GlcNAc can be an acceptor substrate both for recombinantly expressed beta-1,4-GalT, and for a commercial batch of the same enzyme, and both in the presence and absence of bovine serum albumin (BSA). As expected for a full acceptor substrate, this substrate activity was time- and concentration-dependent. Additional experiments show that the observed inhibitor/substrate switch is facilitated by a phosphatase that is an essential component of our enzyme-coupled glycosyltransferase assay. These findings suggest that the behaviour of 2-naphthyl beta-D-GlcNAc and related acceptor-based glycosyltransferase inhibitors is strongly dependent on the individual assay conditions. Our results therefore have important implications for the use of 2-naphthyl beta-D-GlcNAc and related glycosides as tool compounds in glycobiology and glycobiochemistry.

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Tetrahydropyran – Wikipedia,
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Distribution of glycolipid and unsaturated fatty acids in human hair

It has been recognized that human hair lipids play crucial roles in the integrity of cells and matrices, while the details of distribution and structure of the minor lipids are hardly known. Here we investigated the lipids at the hair surface, at the interface between cuticle and cortex and in the interior of hair (cortex, medulla and melanin granules). Hair lipids and fatty acids and their metabolites were detected and characterized by using infrared spectroscopy and several mass spectrometry techniques (FTIR, ToF-SIMS, GCMS, and ESI-MS). As a result, it was found that unsaturated fatty acids were present more in the cortex of hair than at the hair surface. At the interface between cuticle and cortex, it is suggested that steryl glycoside-like lipids containing N-acetylglucosamine were present, and contributing to the adhesion between the cuticle and cortex of hair. Oxidative metabolites derived from integral fatty acids such as linoleic and alpha-linolenic acids were found in the hair bulb and melanin granules. Especially the oxidative metabolites of alpha-linolenic acid were integrated into the lipids non-covalently and tightly bound to melanin granules (namely, melanin lipids) and suggested as being involved in the biosynthetic processes of melanosome.

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Tetrahydropyran – Wikipedia,
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C-glycosides by aqueous condensation of beta-dicarbonyl compounds with unprotected sugars

Condensation of 1,3-diketones with unprotected aldoses in water, under mildly alkaline conditions, provides a convenient and effective route to C-glycosidic ketones in high yields. Reactions usually proceed with high beta-‘anomeric’ stereoselectivity because product composition is determined by thermodynamic control. Mechanistically, the condensation follows a typical Knoevenagel scheme, after which an intramolecular oxa-Michael cyclization determines C-glycoside configuration by following an exo- or endo-trig pathway. With open-chain 1,3-diketones, an ensuing retro-Claisen fragmentation occurs to furnish simple glycosyl monoketones. The C-glycosides then slowly further dehydrate under the reaction conditions to give 2,5-disubstituted furans.

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A new multi-enzyme system for a one-pot synthesis of sialyl oligosaccharides: Combined use of beta-galactosidase and alpha(26)-sialyltransferase coupled with regeneration in situ of CMP-sialic acid

An irreversible one-pot enzymatic synthesis of sialyl oligosaccharides has been achieved with a beta-galactosidase-catalyzed galactosylation of an acceptor followed by a sialyltransferase-catalyzed sialylation with regeneration in situ of CMP-sialic acid.

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Lectin-like protein fractions in lactic acid bacteria isolated from chickens

Agglutination of fifty bacterial strains isolated from gastric- intestinal tract of chickens with yeasts treated with glutaraldehyde and glycine was assayed to study possible adhesion mechanisms to epithelia. It was found that Lactobacillus, fermentum, Lactobacillus fermentum subsp. cellobiosus and Lactobacillus animalis glutinated yeasts massively and this agglutination was inhibited in each strain by different representative sugars: agglutination was inhibited in three selected strains with 0.2 M mannose. The three strains agglutinated chicken red blood cells, but did not agglutinate human red blood cells, whereas the agglutinating capacity for other animal erythrocytes was variable. The lectins were partially purified on a Sephadex G-75 column and affinity chromatography. The molecular weight of each of the protein subunits was estimated as about 50-67 kDa using electrophoretic techniques. After treatment with lipase and metaperiodate modifications bacterial superficies and/or liberation of some structures produced an unspecific interaction with increase in the yeast agglutination and hemagglutination. The optimal conditions of work were: pH 6-7, Ca2+ 1 mM, Mg2+ 2 mM and 37-42 C.

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Metal chelation by the common 2-amino-2-deoxy-, 2-N-acetylamino-2-deoxy-, and 2-deoxy-hexoses

The chelating properties of the common aldohexoses d-glucose, d-mannose, and d-galactose are characteristically modified in 2-substituted derivatives. The 2-amino-2-deoxy-aldohexoses provide mono- and bis-metallisable anionic ligands after their reaction with metal probes of the PdIIN 2 type (N2 = bidentate nitrogen ligand). The 2-amino function reliably participates in metal binding of the, mostly pyranoidic, carbohydrate chelators. Acetylation of the amino function yields the biologically important 2-N-acetylamino-2-deoxy-hexoses (GlcNAc, ManNAc, and GalNAc). On reaction with the palladium probe, the metal-binding properties of the deprotonated acetylamino function depends on the steric requirements introduced by the acetyl residue which is forced into a coplanar arrangement with the chelate ring. In the two 2-deoxy-aldohexoses, 2-deoxy-arabino-d-hexose (the 2-deoxy derivative of both d-glucose and d-mannose, ‘2-deoxy-glucose’) and 2-deoxy-lyxo-d-hexose (‘2-deoxy galactose’), the 2-position cannot contribute to metal binding. As a result, furanose-1,3 chelation becomes an important metal-binding mode. Due to the decreased acidity of the 2-deoxy-glycose’s 1-hydroxy function, monometallation also takes place at the pyranose’s 3,4-site.

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Efficient preparation of three building blocks for the synthesis of heparan sulfate fragments: Towards the combinatorial synthesis of oligosaccharides from hypervariable regions

New, multigram routes to suitably protected L-iduronyl monosaccharide donors 4 and 5 and 2-azidoglucose acceptors 6 and 7 are described. The L-iduronyl and D-glucuronyl disaccharides 1-3 were then prepared from these compounds, by means of efficient and regioselective protective group manipulations. These disaccharides form the basis of a combinatorial approach toward the synthesis of heparan sulfate fragments representative of the heterogeneous regions of this polysaccharide. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)Introduction.

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Tetrahydropyran – Wikipedia,
Tetrahydropyran – an overview | ScienceDirect Topics

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Temperature dependencies of amide1H- and15N-chemical shifts in hyaluronan oligosaccharides

Temperature coefficients (Deltadelta/DeltaT) of amide chemical shifts of N-acetylglucosamine residues have been measured in a range of oligosaccharides of the important vertebrate polysaccharide hyaluronan. Odd- and even-numbered oligosaccharides with glucuronic acid, A-4,5-unsaturated glucuronic acid and N-acetylglucosamine at the termini were investigated. All amide proton temperature coefficients were only slightly less negative (-6.9 to -9.1 ppb/C) than those of amide protons in free exchange with water (?-11 ppb/C), indicating an absence of persistent intramolecular hydrogen bonds. With the exception of amide groups in reducing-terminal N-acetylglucosamine rings, all amide proton environments have the same temperature coefficient (-6.9 ppb/C), irrespective of differences in amide group chemical shifts and 3JHH coupling constants, i.e. they do not sense subtle differences in orientation of the amide group. Amide nitrogen temperature coefficients report the same phenomena but with greater sensitivity. These data provide a set of reference values for temperature coefficients measured in other carbohydrates with acetamido sugars. Copyright

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Tetrahydropyran – Wikipedia,
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High-performance liquid chromatographic determination of chitin in the snow crab, Chionoecetes opilio

A HPLC method was developed for the determination of glucosamine in crab shells. The amount of glucosamine residue can be used to estimate the amount of chitin in analyzed material. Crab samples were hydrolysed with 6 M HCl at 100 C for 13 h and the released glucosamine was determined by HPLC using refractive index (RI) detection. Separations were performed using an ODS-2 column with an isocratic mobile phase consisting of 10% methanol, 90% hexanesulfonate, pH 2.1. Glucosamine identification was carried out not only on basis of retention time, but also with respect to mass spectra, which were acquired by HPLC-MS.

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