Advances in Carbohydrate Chemistry and Biochemistry

Proteoglycans (PGs) are an essential family of glycoproteins, which can play roles in many important biological events including cell proliferation, cancer development, and pathogen infections. Proteoglycans consist of a core protein with one or multiple glycosaminoglycan (GAG) chains, which are covalently attached to serine residues of serine-glycine dipeptide within the core protein through a common tetrasaccharide linkage. In the past three decades, four key glycosyl transferases involved in the biosynthesis of PG linkage have been discovered and investigated...

The approaches in this article seek to enhance understanding of cellulose at the molecular level, independent of the source and the particular crystalline form of cellulose. Four main areas of structure research are reviewed. Initially, the molecular shape is inferred from the crystal structures of many small molecules that have β-(1→4) linkages. Then, conformational analyses with potential energy calculations of cellobiose are covered, followed by the use of Atoms-In-Molecules theory to learn about interactions in experimental and theoretical structures...

Heparin and heparan sulfate are members of the glycosaminoglycan family that are involved in a multitude of biological processes. The great interests in the anticoagulant properties of heparin have stimulated major advances in synthetic strategies toward clinically effective analogues, as demonstrated importantly by the approval of the fully synthetic pentasaccharide fragment, termed fondaparinux (Arixtra®), of the heparin macromolecule for treatment of deep-vein thrombosis. Given the highly complex nature of heparin and heparan sulfate, the chemical synthesis of their components is a challenging endeavor...

Over the last decade, the structural refinement of cellulose allomorphs and their analogs has been advanced using high-resolution fiber diffraction. This also includes structures of crystals complexed with small molecules, which can inherently involve disorders. Computational methods, including density functional theory, in combination with molecular modeling are leading to improved structural analyses. Spectroscopic techniques such as vibrational spectroscopy give quantitative and robust data directly related to structural insights on cellulose...

No abstract text is available yet for this article.

Saponins are a large family of amphiphilic glycosides of steroids and triterpenes found in plants and some marine organisms. By expressing a large diversity of structures on both sugar chains and aglycones, saponins exhibit a wide range of biological and pharmacological properties and serve as major active principles in folk medicines, especially in traditional Chinese medicines. Isolation of saponins from natural sources is usually a formidable task due to the microheterogeneity of saponins in Nature. Chemical synthesis can provide access to large amounts of natural saponins as well as congeners for understanding their structure-activity relationships and mechanisms of action...

Saponins, as secondary metabolites in terrestrial plants and marine invertebrate, constitute one of the largest families of natural products. The long history of folk medicinal applications of saponins makes them attractive candidates for innovative drug design and development. Chemical synthesis has become a practical alternative to the availability of the natural saponins and their modified analogs, so as to facilitate SAR studies and the discovery of optimal structures for clinical applications. The recent achievements in the synthesis of these complex saponins reflect the advancements of both steroid/triterpene chemistry and carbohydrate chemistry...

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Increasing demands for molecules with skeletal complexity, including those of stereochemical diversity, require new synthetic strategies. Carbohydrates have been used extensively as chiral building blocks for the synthesis of various complex molecules. On the other hand, the vinyl sulfone group has been identified as a unique functional group, which acts either as a Michael acceptor or a 2π partner in cycloaddition reactions. A combination of the high reactivity of the vinyl sulfone group and the in-built chiralities of carbohydrates has the potential to function as a powerful tool to generate a wide variety of enantiomerically pure reactive intermediates...

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Mucopolysaccharidosis type II (MPS II, Hunter syndrome) is a rare X-linked lysosomal storage disease caused by mutations of the gene encoding the lysosomal enzyme iduronate-2-sulfatase (IDS), the role of which is to hydrolytically remove O-linked sulfates from the two glycosaminoglycans (GAGs) heparan sulfate (HS) and dermatan sulfate (DS). HS and DS are linear, heterogeneous polysaccharides composed of repeating disaccharide subunits of l-iduronic acid (IdoA) or d-glucuronic acid, (1→4)-linked to d-glucosamine (for HS), or (1→3)-linked to 2-acetamido-2-deoxy-d-galactose (N-acetyl-d-galactosamine) (for DS)...

This article presents a selection of topics from Professor Frieder W. Lichtenthaler's scientific lifework. It describes his contributions to, and further development of, the nitromethane cyclization of dialdehydes leading to amino sugars and amino nucleosides, as well as a new coupling methodology for purine nucleosides. A number of chiral building blocks derived from sugars like the "sugar enolones," enollactones, hydroxyhexenals, and their synthetic applications in natural product syntheses are covered...

The synthesis of a carbohydrate building block usually starts with introduction of a temporary protecting group at the anomeric center and ends with its selective cleavage for further transformation. Thus, the choice of the anomeric temporary protecting group must be carefully considered because it should retain intact during the whole synthetic manipulation, and it should be chemoselectively removable without affecting other functional groups at a late stage in the synthesis. Etherate groups are the most widely used temporary protecting groups at the anomeric center, generally including allyl ethers, MP (p-methoxyphenyl) ethers, benzyl ethers, PMB (p-methoxybenzyl) eithers, and silyl ethers...

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Sialic acid-based glycoconjugates cover the surfaces of many different cell types, defining key properties of the cell surface such as overall charge or likely interaction partners. Because of this prominence, sialic acids play prominent roles in mediating attachment and entry to viruses belonging to many different families. In this review, we first describe how interactions between viruses and sialic acid-based glycan structures can be identified and characterized using a range of techniques. We then highlight interactions between sialic acids and virus capsid proteins in four different viruses, and discuss what these interactions have taught us about sialic acid engagement and opportunities to interfere with binding...

Gangliosides comprise a varied family of glycosphingolipid structures bearing one or more sialic acid residues. They are found in all mammalian tissues but are most abundant in the brain, where they represent the quantitatively major class of sialoglycans. As prominent molecular determinants on cell surfaces, they function as molecular-recognition partners for diverse glycan-binding proteins ranging from bacterial toxins to endogenous cell-cell adhesion molecules. Gangliosides also regulate the activity of plasma membrane proteins, including protein tyrosine kinases, by lateral association in the same membranes in which they reside...

Sialic acid (Sia) is involved in many biological activities and commonly occurs as a monosialyl residue at the nonreducing terminal end of glycoconjugates. The loss of activity of UDP-GlcNAc2-epimerase/ManNAc kinase, which is a key enzyme in Sia biosynthesis, is lethal to the embryo, which clearly indicates the importance of Sia in embryogenesis. Occasionally, oligo/polymeric Sia structures such as disialic acid (diSia), oligosialic acid (oligoSia), and polysialic acid (polySia) occur in glycoconjugates. In particular, polySia, a well-known epitope that commonly occurs in neuroinvasive bacteria and vertebrate brains, is one of the most well-known and biologically/neurologically important glycotopes in vertebrates...

No abstract text is available yet for this article.

Investigations of methodologies aimed on improving the stereoselective synthesis of sialosides and the efficient assembly of sialic acid glycoconjugates has been the mission of dedicated research groups from the late 1960s. This review presents major accomplishments in the field, with the emphasis on significant breakthroughs and influential synthetic strategies of the last decade.

Sialic acids are cytoprotectors, mainly localized on the surface of cell membranes with multiple and outstanding cell biological functions. The history of their structural analysis, occurrence, and functions is fascinating and described in this review. Reports from different researchers on apparently similar substances from a variety of biological materials led to the identification of a 9-carbon monosaccharide, which in 1957 was designated "sialic acid." The most frequently occurring member of the sialic acid family is N-acetylneuraminic acid, followed by N-glycolylneuraminic acid and O-acetylated derivatives, and up to now over about 80 neuraminic acid derivatives have been described...