Crystallographic studies of carbohydrates

Abstract

The monosaccharides which constitute the monomer units of many important industrial and biological macromolecules are well represented among the 2000 crystal structures of the carbohydrate class 45 of the Cambridge Structural Database. There are few examples of crystal structure analyses of the corresponding acids, but many of their calcium salts and calcium salt complexes. With the exception of the disaccharides and cyclodextrins, the oligosaccharides are not well represented, with less than ten trisaccharides, one tetrasaccharide and one hexasaccharide-iodide complex. Two important conformational factors are the Hassel-Ottar effect and the anomeric effect, both of which have been studied using crystallographic data. Hydrogen bonding is ubiquitous in carbohydrate crystals and generally involves all the hydroxyls as both donors and acceptors, and some of the ring and glycosidic oxygens as acceptors. These hydrogen bonds tend to form finite or infinite chains. In hydrates, these chains are linked through the water molecules to form networks. Cyclic hydrogen-bond systems are observed in the cyclodextrins. Long-chain alkylated carbohydrates provide a large class of thermotropic and lyotropic liquid crystals, and some non-ionic surfactants which have been shown to be useful for membrane-protein solubilization and crystallization.