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Synthesis and Study of Molecular Assemblies Formed by 4,6-O-(2-Phenylethylidene)-Functionalized d -Glucosamine Derivatives

Low-molecular-weight gelators are interesting small molecules with potential applications as advanced materials. Carbohydrate-based small molecular gelators are especially useful because they are derived from renewable resources and are more likely to be biocompatible and biodegradable. Various 4,6-benzylidene acetal protected alpha-methyl 2-d-glucosamine derivatives have been found to be effective low-molecular-weight gelators. To understand the influence of the 4,6-benzylidene acetal functional group toward molecular self-assembly and to obtain effective molecular gelators, we synthesized and analyzed a new series of d-glucosamine derivatives in which the phenyl group of the acetal is replaced by a benzyl group. The homologation of the acetal protection from aromatic to aliphatic functional groups allows us to probe the effect of increasing structural flexibility on molecular self-assembly and gelation. In this study, nine representative amides and nine urea analogs were synthesized, and their gelation properties were analyzed in a series of organic solvents and aqueous solutions. The resulting amide and urea derivatives are versatile organogelators forming gels in toluene, ethanol, isopropanol, ethylene glycol, and aqueous mixtures of organic solvents. More interestingly, the amide analogs are also effective gelators for pump oil and engine oil. NMR spectroscopy at variable temperatures was used to analyze the molecular assemblies and intermolecular forces. The selected gelators with several drug and dye molecules in DMSO and water were studied for their effectiveness of encapsulation and release of these agents.

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A novel method for synthesis of chitobiose via enzymatic glycosylation using a sugar oxazoline as glycosyl donor

A convenient method for synthesis of N,N’-diacetylchitobiose, an important building block for oligo and polysaccharide synthesis, has been developed by using a 1,2-oxazoline derivative of N-acetylglucosamine as new glycosyl donor for chitinase.

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Synthesis and growth inhibitory properties of glucosamine-derived glycerolipids.

[figure: see text] 2-Amino C-glycerolipid 1b was synthesized by using the Ramberg-Baecklund rearrangement as the key step. beta-C-Glycerolipid 1b exhibits in vitro antiproliferative effects strikingly similar to those of O-glycoside analogue 1a.

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Tetrahydropyran – Wikipedia,
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Discovery of N-((2S,3R,4R,5R,6R)-2,4,5-Trihydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-3-yl)acetamide

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Aniphiphilic and mesogenic carbohydrates. 10. Change of the type of the mesophase by variation of the acyl chain of amphiphilic tetradecyl (N-acylamino)-2-deoxy-1-thio-beta-D-glucopyranosides

The homologous amphiphilic tetradecyl-2-(N-alkanoylamino)-2-deoxy-1-thio-beta-D-glucopyranosides 5a-f were synthesized from the 2-(N-alkanoylamino)-2-deoxy-D-glucopyranoses 1a-f via the glucosyl chlorides 2a-f, the glucosyl isothiuronium chlorides 3a-f, and the acetylated thioglucosides 4a-f. On heating the amphiphiles 5a-f form different types of liquid crystalline phases in dependence of the length of the acyl chain, i.e. 5a and 5b form smectic phases, 5d-f form columnar mesophases. Polarisation microscopy, DSC-measurements and contact preparations were used to characterise the liquid crystalline phases.

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NOVEL MURAMYL PEPTIDE DERIVATIVE COMPOUND, SYNTHESIS AND USES THEREOF

The invention relates to novel Muramyl Dipeptide (MDP) derivative compound of structural Formula-VIII, a process for synthesis, intermediates used in the synthesis and use thereof. R = alkyl (both linear and branched), aryl, substituted aryl, alkoxy alkyl Wherein, R can be both linear and branched alkyl, aryl, substituted aryl and alkoxy alkyl. These compounds possess excellent pharmacological properties, in particular immunomodulating properties for use as adjuvant in vaccine formulations. These compounds are, particularly useful as adjuvants in vaccines.

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Tetrahydropyran – Wikipedia,
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The reaction of hyaluronic acid and its monomers, glucuronic acid and N- acetylglucosamine, with reactive oxygen species

Synovial fluid is a ~0.15% (w/v) aqueous solution of hyaluronic acid (HA), a polysaccharide consisting of alternating units of GlcA and GlcNAc. In synovial fluid of patients suffering from rheumatoid arthritis, HA is thought to be degraded either by radicals generated by Fenton chemistry (Fe2+/H2O2) or by NaOCl generated by myeloperoxidase. We investigated the course of model reactions of these two reactants in physiological buffer with HA, and with the corresponding monomers GlcA and GlcNAc. meso-Tartaric acid, arabinuronic acid, arabinaric acid and glucaric acid were identified by GC-MS as oxidation products of glucuronic acid. When GlcNAc was oxidised, erythronic acid, arabinonic acid, 2-acetamido-2-deoxy-gluconic acid, glyceric acid, erythrose and arabinose were formed. NaOCl oxidation of HA yielded meso-tartaric acid; in addition, arabinaric acid and glucaric acid were obtained by oxidation with Fe2+/H2O2. These results indicate that oxidative degradation of HA proceeds primarily at glucuronic acid residues. meso-Tartaric acid may be a useful biomarker of hyaluronate oxidation since it is produced by both NaOCl and Fenton chemistry.

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Tetrahydropyran – Wikipedia,
Tetrahydropyran – an overview | ScienceDirect Topics

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SYNTHESIS OF 2-ACETAMIDO-4-O-(2-ACETAMIDO-2-DEOXY-beta-D-GLUCOPYRANOSYL)-2-DEOXY-6-O-(alpha-L-FUCOPYRANOSYL)-D-GLUCOPYRANOSE (6-O-alpha-L-FUCOPYRANOSYL-DI-N-ACETYLCHITOBIOSE)

Benzyl 3,3′,4′,6′-tetra-O-benzoyl-beta-di-N-acetylchitobioside (8) was prepared in 5 steps from 3,3′,4′,6′-tetra-O-acetyl-1,6-anhydro-beta-di-N-acetylchitobiose by the following series of reactions; de-O-acetylation, benzoylation, acetolysis of the 1,6-anhydro-beta-ring, benzyl glycosidation via oxazoline, and selective de-O-acetylation.Reaction of 8 with 2,3,4-tri-O-benzyl-alpha-L-fucopyranosyl bromide by a bromide ion-catalyzed reaction afforded benzyl 3,3′,4′,6′-tetra-O-benzoyl-6-O-(2″,3″,4″-tri-O-benzyl-alpha-L-fucopyranosyl)-beta-di-N-acetylchitobioside (10) in 83.4 percent yield.After removal of the protecting groups of 10,6-O-alpha-L-fucopyranosyl-di-N-acetyl chitobiose (11) was obtained as needles. (13)C-NMR spectra data for 11 are presented.Keywords: – synthesis; 6-O-alpha-L-fucopyranosyl-di-N-acetylchitobiose; 1,6-anhydro-di-N-acetylchitobiose derivative; oxazoline glycosidation method; benzyl di-N-acetyl-chitobioside derivative; bromide ion-catalyzed glycosidation; selective de-O-acetylation; (13)C-NMR

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Tetrahydropyran – Wikipedia,
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Rapid-throughput competitive colorimetric assay based on monosaccharide-capped gold nanoparticles for detecting lectin-protein interactions

Identification of protein binding partners is one of key challenges in proteomics. A rapid-throughput competitive colorimetric assay is presented that uses gold nanoparticles capped by sugars such as mannopyranoside (Man-GNPs), N-acetylglucosamine (GlcNAc-GNPs), glucose (Glc-GNPs), or N-acetylgalactosamine (GalNAc-GNPs). The assay expediently detects protein- protein interactions in solution, particularly protein-lectin interactions. The competitive assays were conducted in microtiter plates; ten proteins (two glycoproteins and eight lectins) and three sugar-binding lectins (concanavalin A (ConA), wheat germ agglutinin (WGA), and Ricinus communis agglutinin (RCA120)) were combinatorially arranged in a 30-well plate, and constant concentrations of the monosaccharide-capped GNPs (sugar-GNPs) were added to each well. If interactions occurred between the proteins, the sugar-GNPs retained their burgundy color. If no interactions occurred between the proteins, the sugar-GNPs were agglomerated by the corresponding binding lectin, thus producing a blue color. Several new binding pairs were identified for the first time by using this assay, and the binding constants and stoichiometric ratios were determined on the basis of the wavelength shifts. The results were further verified by sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) and fluorescence resonance energy transfer (FRET) spectroscopy. The assay is very sensitive, requiring only nanomolar protein concentrations.

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The synthesis and biological activities of anomeric butyl glycosides of muramyl dipeptide

The synthesis of anomeric butyl glycosides of muramyl dipeptide was reported. alpha-Butyl glycoside of N-acetyl-D-glucosamine was 3-O-benzylidenated and the benzylidene derivative was 3-O-alkylated by the Williamson reaction with sodium (S)-2-chloropropionate. The resulting protected alpha-butyl glycoside of muramic acid was then condensed with L-Ala-D-iGln-OBzl by the DCC-HOSu method. Mild acidic hydrolysis and subsequent catalytic hydrogenolysis of the resulting glycopeptide yielded the target alpha-butyl glycoside of N-acetyl-Lralanyl-D-isoglutamine. In the synthesis of beta-butyl glycoside of N-acetylmuramyl-L-alanyl-D-isoglutamine, 2-acetamido-4,6-di-O-acetyl-2-deoxy-3-O-[(R)-1-(methoxycarbonyl)ethyl]-alpha- D-glucopyranose, a 1-OH derivative of muramic acid, was the key compound. Its interaction with the excess thionyl chloride resulted in the corresponding glycosyl halide, which was condensed with n-butanol according to Helferich. O-Deacetylation, 4,6-isopropylidenation, and subsequent alkaline hydrolysis of the resulting compound gave the protected beta-butyl glycoside of muramic acid. Its activation and condensation with L-Ala-D-iGln-OBzl and the subsequent removal of protective groups were performed in the same manner as the reactions in the synthesis of alpha-butyl glycoside of N-acetylmuramyl-L-alanyl-D-isoglutamine. The adjuvant activity of the butyl glycosides to HIV proteins rgp160 and rgp120 and their ability to affect in vitro HIV replication and the proliferation of mouse spleen T-cells were examined. The biological activity of anomeric muramyl dipeptides was shown to depend essentially on the configuration of their anomeric center.

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Chemical synthesis of N-acetylglucosamine derivatives and their use as glycosyl acceptors by the Mesorhizobium loti chitin oligosaccharide synthase NodC

Rhizobial bacteria synthesize lipo-chitin oligosaccharide signal molecules (Nod factors) that are essential for the formation of symbiotic organs on the roots of host plants, a process known as nodulation. Biosynthesis of the chitin oligosaccharide moiety in Nod factors is carried out by the rhizobial N-acetylglucosaminyltransferase NodC. The initial acceptor or primer used for the synthesis of chitin oligosaccharides in vivo is unknown. To investigate the acceptor specificity of NodC, we have synthesized derivatives of N-acetylglucosamine (GlcNAc) with different aglycones and tested whether they are acceptors for NodC in vitro using a membrane preparation of an Escherichia coli strain expressing the Mesorhizobium loti chitin oligosaccharide synthase NodC. Analysis of reaction products using thin-layer chromatography shows that GlcNAc derivatives containing simple alkyl chains or other hydrophobic groups linked to C-1 are acceptors for NodC. The enzyme appears to be specific for acceptors in which the aglycone is beta-linked. GlcNAc derivatives in which the methyl group of the N-acetyl moiety of GlcNAc is replaced by an allyloxy or benzyloxy group are still used as acceptors by NodC. The original methyl group at this position therefore does not appear to be essential for the interaction between NodC and GlcNAc. A NodC-dependent reaction product that is more hydrophobic than GlcNAc was detected in reaction mixtures containing 5% methanol but lacking an exogenously added acceptor. This may be due to the presence of a natural hydrophobic glycosyl acceptor for NodC in the membranes of E. coli, but the structure of this reaction product remains to be investigated.

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Tetrahydropyran – Wikipedia,
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