Advances in carbohydrate chemistry and biochemistry最新文献

This article describes the detection and characterization of oxo-Cr(V)-saccharide coordination compounds, produced during chromic oxidation of carbohydrates by Cr(VI) and Cr(V), using electron paramagnetic resonance (EPR) spectroscopy. After an introduction into the main importance of chromium (bio)chemistry, and more specifically the oxo-chromium(V)-sugar complexes, a general overview is given of the current state-of-the-art EPR techniques. The next step reviews which types of EPR spectroscopy are currently applied to oxo-Cr(V) complexes, and what information about these systems can be gained from such experiments. The advantages and pitfalls of the different approaches are discussed, and it is shown that the potential of high-field and pulsed EPR techniques is as yet still largely unexploited in the field of oxo-Cr(V) complexes. Subsequently, the discussion focuses on the analysis of oxo-Cr(V) complexes of different types of sugars and the implications of the results in terms of understanding chromium (bio)chemistry.

Seven-atom ring sugars, called septanoses, are increasingly the focus of scientific inquiries because of their potential biological activities. This article details the synthesis, conformational analysis, and protein-binding properties of septanose carbohydrates. A distinction is drawn between septanoses that are substituted in the 6-position of the ring and those that are not. When a C-6 substituent is absent, the structure is essentially that of an aldohexose in its septanose, rather than furanose or pyranose, ring form; they may play as-of-yet unexplored roles in glycobiology. Septanoses having a hydroxymethyl group at C-6, on the other hand, are ring-expanded analogues of pyranoses. Syntheses have moved beyond the preparation of seven-membered ring monosaccharides to the development of septanosyl donors. These donors have been used in the synthesis of novel di- and trisaccharides that contain septanoses as well as a variety of glycoconjugates. Low-energy conformations adopted by septanoses have been organized based on ring substitution and stereochemistry. Instances where septanoses have been demonstrated to bind to natural proteins are presented and analyzed. The major conclusion drawn in the chapter is that advances in the synthesis of septanose carbohydrates now enable a detailed investigation of their activity in a number of biological contexts.

An account is given of the life, scientific contributions, and passing of Laurance David Hall (1938-2009), including his early history and education at the University of Bristol, UK, and the synthesis and NMR spectroscopy of carbohydrates and other natural products during ∼20 years of research and teaching at the University of British Columbia in Vancouver, Canada. Lists of graduate students, post-doctoral fellows, and sabbatical visitors are provided for this period. Following a generous endowment by Dr. Herchel Smith, Professor Hall built a new Department of Medicinal Chemistry at Cambridge University, UK, and greatly expanded his researches into the technology and applications of magnetic resonance imaging (MRI) and zero quantum NMR. MRI technology was applied both to medical problems such as the characterization of cartilage degeneration in knee joints, the measurement of ventricular function, lipid localization in animal models of atherosclerosis, paramagnetic metal complexes of polysaccharides as contrast agents, and studies of many other anatomical features, but also to several aspects of materials analysis, including food analyses, process control, and the elucidation of such physical phenomena as the flow of liquids through porous media, defects in concrete, and the visualization of fungal damage to wood. Professor Hall's many publications, patents, lectures, and honors and awards are described, and also his successful effort to keep the Asilomar facility in Pacific Grove, California as the alternating venue for the annual Experimental NMR Conference. Two memorial services for Professor Hall are remembered.

Red algae (Rhodophyta) are known as the source of unique sulfated galactans, such as agar, agarose, and carrageenans. The wide practical uses of these polysaccharides are based on their ability to form strong gels in aqueous solutions. Gelling polysaccharides usually have molecules built up of repeating disaccharide units with a regular distribution of sulfate groups, but most of the red algal species contain more complex galactans devoid of gelling ability because of various deviations from the regular structure. Moreover, several red algae may contain sulfated mannans or neutral xylans instead of sulfated galactans as the main structural polysaccharides. This chapter is devoted to a description of the structural diversity of polysaccharides found in the red algae, with special emphasis on the methods of structural analysis of sulfated galactans. In addition to the structural information, some data on the possible use of red algal polysaccharides as biologically active polymers or as taxonomic markers are briefly discussed.

Forty years of discoveries and research on imino sugars, which are carbohydrate analogues having a basic nitrogen atom instead of oxygen in the sugar ring and, acting as potent glycosidase inhibitors, have made considerable impact on our contemporary understanding of glycosidases. Imino sugars have helped to elucidate the catalytic machinery of glycosidases and have refined our methods and concepts of utilizing them. A number of new aspects have emerged for employing imino sugars as pharmaceutical compounds, based on their profound effects on metabolic activities in which glycosidases are involved. From the digestion of starch to the fight against viral infections, from research into malignant diseases to potential improvements in hereditary storage disorders, glycosidase action and inhibition are essential issues. This account aims at combining general developments with a focus on some niches where imino sugars have become useful tools for glycochemistry and glycobiology.

Trehazolin is a natural pseudodisaccharide obtained from Micromonospora strain SANK 62390 and Amycolaptosis trehalostatica, and later on it was found to be widely distributed in microorganisms, insects, plants, and animals. It has received much attention because of its importance as an inhibitor of the enzyme trehalase. This article is focused on the synthesis of natural trehazolin and its analogues, with details of the synthetic methods. Sufficient information is given to permit the selection of a suitable synthetic route for trehazolin and/or its analogues. Various approaches are provided for the synthesis of natural trehazolin and its analogues in a way that enables the researcher to decide whether to use a certain procedure, modify it, or propose a new synthetic methodology.

Silicon-based materials, namely zeolites, clays, and silica gel have been widely used in organic synthesis, allowing mild reaction conditions and environmentally friendly methodologies. These heterogeneous catalysts are easy to handle, possess nontoxic and noncorrosive character and offer the possibility of recovery and reuse, thus contributing to clean and sustainable organic transformations. Moreover, they present shape-selective properties and provide stereo- and regiocontrol in chemical reactions. Herein, we survey the most significant applications of silicon-based materials as catalysts in carbohydrate chemistry, to mediate important transformations such as glycosylation, sugar protection and deprotection, and hydrolysis and dehydration. Emphasis is placed on their promising synthetic potential in comparison with conventional catalysts.