Ozonolytic depolymerization of polysaccharides in aqueous solution.
The selective oxidation of beta-D-glycosidic linkages of polysaccharides by ozone has great utility as a general method for depolymerization of polysaccharides. Here we describe a 'one-step' method whereby polysaccharides dissolved in water or basic solutions are depolymerized by ozonolysis. The oxidation of glycosidic linkages of unprotected carbohydrates by ozone is complicated by several side reactions. We describe here optimized conditions for carrying out ozonolysis degradation. We also characterize the major pathways for unwanted degradation by various side reactions. In the preferred oxidation pathway, the aldosidic linkage is oxidized to an aldonic ester function that hydrolyzes under the basic conditions employed to give a free aldonate, with cleavage of the polysaccharide chain. Nonselective degradation pathways include oxidative degradation by radical species that oxidize glycosyl residues to formic, acetic, and oxalic acids. The nonselective degradation caused by acids is minimized by basic buffers. The products of polysaccharide depolymerization form a size distribution around a nominal molecular weight, and the average molecular weight of the products can be controlled by the rate or amount of ozone passed through the reaction mixture. The ozonolysis method described herein provides a convenient, inexpensive, and controllable means for generating small polysaccharides or large oligosaccharide fragments.
Wang
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Channing Laboratory, Department of Medicine, Brigham and Women's Hospital, Harvard Medical School, Boston, MA 02115, USA. ywang@channing.harvard.edu
Hollingsworth
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Kasper
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D016667:Bacterial Capsules / Q000737:chemistry; D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D008969:Molecular Sequence Data; D008970:Molecular Weight; D010126:Ozone / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry*; D011135:Polysaccharides, Bacterial / Q000737:chemistry*; D012996:Solutions; D013292:Streptococcus agalactiae / Q000737:chemistry; D013296:Streptococcus pneumoniae / Q000737:chemistry; D014867:Water / Q000737:chemistry*
D011108:Polymers; D011135:Polysaccharides, Bacterial; D012996:Solutions; D014867:Water; D010126:Ozone