Complex mixtures of carbohydrates pose distinct challenges in routine and high-throughput analysis, so that only a few carbohydrate components are routinely resolved and identified in biofluids, extracts, foods and other complex mixtures. Here, we conduct precise measurements of (1)H and (13)C anomeric chemical shifts to construct a reference library of specific carbohydrate signals with high-r...

The vanadium-based catalyst, acts as a homogeneous catalyst for the selective oxidation of various kinds of sulfides with 30% aqueous H2O2. Vanadium-based catalyst was successfully used as the oxygen source for the oxidation of sulfides to sulfoxides for the first time. The sulfoxides were obtained in a good way to high yields without any detectable over-oxidation to sulfones under normal condi...

Solid-phase oligosaccharide synthesis offers the promise of providing libraries of oligosaccharides for glycomics research. A major stumbling block to solid-phase oligosaccharide synthesis has been a lack of general methods for the stereoselective installation of 1,2-cis-glycosides, and intractable mixtures of compounds are obtained if several such glycosides need to be installed. We have prepa...

The stereochemistry of the ketosidic bond of sialic acid has been elucidated by a study of the two anomeric methyl ketosides. Isomer I was prepared by Koenig.+Knorr synthesis, and isomer II by direct methylation with methanol and an acid catalyst. These two anomeric configurations were established by conversion with periodate-borohydride to III and IV, respectively, followed by lactonization of...

There has been increasing interest in the construction of liposomes containing a targeting reagent for target-specific drug delivery. Glycoconjugates that can be recognized by transmembrane glycoprotein receptors have been extensively used to form glyco-liposomal drug carriers. However, the impact of anomerism, which is a common identity of natural glycoconjugates, on the glyco-liposomal proper...

In aqueous solution Dfructose 1,6-bisphosphate (FBP)? exists as equilibrium mixture of 20 + 4% a-D-fructofuranose 1,6-bisphosphate, 80 f 10% /3-Dfructofuranose 1,6-bisphosphate, and less than 1.5% of the open chain [l-4] . The two anomeric forms are spontaneously interconvertible via the open chain tautomer. The first order rate constant for the ring opening of the o!-D-fructofuranose 1,6-bisph...

Disaccharides tagged with p-aminobenzoic acid (ABA) were separated by capillary electrophoresis (CE) and analyzed on-line with negative ion electrospray ionization tandem mass spectrometry (ESI/MS/MS). The formation of glycosylamine instead of reductive amination was selected as the derivatization reaction. In negative ion ESI, the glycosylamine approach provides more information on linkage and...

A new and completely diastereoselective method for the introduction of fluorine into a noncarbohydrate sugar ring precursor has been developed. The use of N-fluorodibenzenesulfonimide (5) for the electrophilic fluorination of chiral lactone 4, which is derived from L-glutamic acid, yields the key intermediate 6. This is transformed into an anomeric acetate 8 and is used for the synthesis of a n...

Retaining glycosyltransferase enzymes retain the stereochemistry of the donor glycosidic linkage after transfer to an acceptor molecule. The mechanism these enzymes utilize to achieve retention of the anomeric stereochemistry has been a matter of much debate. Re-analysis of previously released structural data from retaining and inverting glycosyltransferases allows competing mechanistic proposa...