Glucose oxidation with periodate

Figure I. Structural modifications of the nonreducing and reducing terminal glucose units of a linear P-1,3-glucan, as a result of oxidation with periodate and reduction with borohydride (151)...

Oxidation of A. niger D-glucose oxidase with periodate indicated that the carbohydrate component (12% by weight) stabilizes the protein, although it has neither catalytic nor immunological activity and is not involved in maintaining the conformation of the molecule. ... 

As a preparatory method, oxidation with periodic acid is of particular importance for the preparation of short-chain sugars. For example, 2,3-0-benzylidene-D-arabitol (I) consumes one mole of periodic acid and yields 2,3-0-benzylidine-D-threose (II) which can be converted to a crystalline isopropylidene derivative 226), The oxidation of aldoses by one mole of lead tetraacetate in acetic acid will cause degradation to aldoses containing one less carbon thus, D-arabinose and D-lyxose have been prepared in yields of more than 35% from D-glucose and D-galactose, respectively 227), The... 

Osotriazoles of diketones previously had been described by von Pech-mann 2 0) who obtained them by the oxidation of the corresponding di-hydrazones. The corresponding osotriazoles of the sugars are formed directly by the action of copper sulfate. The formation of the phenyl-D-glucoso-triazole (II) from glucose phenylosazone (I) is illustrated. Its structure is demonstrated by oxidation with periodic acid to the 2-phenyl-4-formyl-osotriazole (III) which is identical with the product obtained previously by von Pechmann from mono-0-acetyldinitrosoacetone phenylhydrazone (IV). 

A chemical method (41) of degrading glucose was developed to distinguish between carbon atoms 3 and 6. D-Glucose was converted to the methyl D-glucopyranoside which was then oxidized with periodic acid at room temperature to convert carbon atom 3 to formic acid. A second periodic acid oxidation of the hydrolyzed dialdehyde, which was also produced, gave carbon atom 6 as formaldehyde. 

FIGURE 22.42 Formation of methyl D-glucopyranoside and further oxidation with periodic acid gives the observed dialdehyde product, which is evidence that the cyclic form of glucose is (mainly) a pyranose. A furanose would give a different oxidation product. 

Sucrose derivatives with substituents at the primary positions undergo selection oxidation with periodate in the glucose ring, the 6,l, 6 -tri-0-trilyl derivative reacting at the 2,3-diol, and the TBDMS analogue at the 3,4-position. Products of oxidation were... 

Cytochemical staining, by a method involving oxidation with periodate and reaction with thiosemicarbazide and osmium tetroxide, has revealed the presence of polysaccharide lamellae on the surface of the cell membrane of Claviceps purpurea.The membranous clusters in vacuolar bodies of the endoplasmic reticulum membranes, tonoplasts, and cytoplasmic membranes are covered with these lamellae. Somatic and metabolic polysaccharides composed of D-mannose and L-rhamnose have been isolated from Certocystic stenoceras and Sporotrichum schenckii , chemical and immunological analyses indicated close similarities in their structures. When pseudoplasmodia of Dictyostelium discoideum were incubated with 2-acetamido-2-deoxy-D-[ H]glucose, the label was incorporated into a polysaccharide in the slime sheath. The incorporated label disappeared... 

D-Glucose Oxidase.— The carbohydrate moieties of D-glucose oxidase from Aspergillus niger have been modified by oxidation with periodate ion. Although ca. 60% of the carbohydrate residues were oxidized at pH 5.6, none of the amino-acid residues was oxidized. The oxidized enzyme retained its full activity and was converted into an immobilized form. 

In a study of the oxidation of 2-amino-2-deoxy-D-glucose (D-glucosamine) derivatives, Neuberger12 obtained better results using sodium metaperiodate (at its accompanying pH of 3 to 4) than with periodic acid at lower pH values and a pH of 4.5 was found by Jeanloz and Forchielli78a to be optimal for these derivatives. 

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