Polysaccharide periodate

Launer, H. and Tomimatsu, Y. 1961. Alkali sensitivity of polysaccharides periodate starches, periodate dextran and a polygalacturonide, J. Org. Chem., 26 541-545. 

However, when applied to polysaccharides, periodate oxidation seems in many cases to be accompanied by depolymerization, such as the case of alginates and chitosans [18, 19]. In turn, the exposed reducing ends consume additional periodate, thereby leading to over oxidation [20, 21]. 

There are two general methods for the determination of the character of the linkage of polysaccharides periodic acid oxidation (1,2) and methylation analysis (3). The present paper gives details of the possibilities for the utilization of the periodate oxidation. 

Information about irregularities in the polymer chain was gained by studying the total periodate oxidation of the polysaccharide. Periodic acid or its salts react with a-diols to give rise to two carbonyl groups and iodate. In case of three adjacent hydroxyl groups the initially formed a-hydroxy aldehyde undergoes further oxidation with formation of one equivalent of formic acid ... 

Oxidation of polysaccharides is a far more attractive route to polycarboxylates, potentially cleaner and less cosdy than esterification. Selectivity at the 2,3-secondary hydroxyls and the 6-primary is possible. Total biodegradation with acceptable property balance has not yet been achieved. For the most part, oxidations have been with hypochlorite—periodate under alkaline conditions. In the 1990s, catalytic oxidation has appeared as a possibiUty, and chemical oxidations have also been developed that are specific for the 6-hydroxyl oxidation. 

Two helices are packed antiparallel in the orthorhombic unit cell. Association of the helices occurs through a series of periodic carboxylate potassium water - carboxylate interactions. An axial projection of the unit-cell contents (Fig. 23b) shows that the helices and guest molecules are closely packed. This is the first crystal structure of a polysaccharide in which all the guest molecules in the unit cell, consistent with the measured fiber density, have been experimentally located from difference electron-density maps. The final / -value is 0.26 for 54 reflections, of which 43 are observed, and it is based on normal scattering factors.15... 

Investigations on biocompatible hydrogels based exclusively on polysaccharide chains were reported chitosan was linked with dialdehyde obtained from scleroglucan by controlled periodate oxidation [218]. The reaction took... 

With endogeneous pectic polysaccharides as substrates, the pectin methyhransferase activity was measured as radioactivity linked to oxalate-soluble polys x harides after extensive washing of microsomes with IM ethanolic NaCL Figure 2 shows that the rate of methylesterification of pectic substances was maximal on days 4 and 6 these maximum activities were observed within this period in at least five independent ejqjeriments. On the other hand, little activity was noted in young cells before day 2, and in old cells after day 9. In other words during the stationary phase the newly synthesised pectins remained unesterified because of the lack of pectin methyltransferase activity. 

Isolation of polysaccharide fractions After a growth period of 8 days the cell biomass was separated by filtration and the spent culture medium was used for the isolation of polysaccharides. The following procedures were examined ... 

The oxidative cleavage of v/c-diols to give two carbonyl functions (Eq. 5.3) by periodates was first observed by Malaprade and has since been widely applied to the carbohydrate area.50 Since both the reagent sodium periodate and the carbohydrate substrate are water soluble, the reaction is usually carried out in aqueous media.51 The reaction has been applied to polysaccharides such as starch.52 The periodate oxidations of sodium alginate in water as well as a dispersion in 1 1 ethanol-water mixture have been compared.53 Because sodium alginate forms a highly viscous solution, the oxidation was observed to be more extensive in ethanol-water. 

Selective staining of polysaccharide in the cell is said to depend upon the oxidizing action of periodate on such chemical configurations as a, p glycols and a-hydroxyketones. Polyaldehydes generated by this selective oxidation react with sulfite-decolorized fuchsin. Polysaccharide areas in the cell are colored red by the stain. 

In this group we place mainly the neutral bacterial slimes and reserve carbohydrates. They are better defined products than those previously dealt with and as such may of course be regarded as true polysaccharides. Invariably, however, saponification methods are required to rid them of protein residues and to make them water-soluble. The more soluble mold polysaccharides appear to lose their protein constituents by autolytic processes during the longer periods required for mold metabolism. Mold slime production can, however, readily be demonstrated on a solid medium. It is proposed here to give briefly some of the types of structure known in the group. 

In some instances, reducing sugars are present that can be reductively aminated without prior periodate treatment. A reducing end of a monosaccharide, a disaccharide, or a polysaccharide chain may be coupled to a diamine by reductive amination to yield an aminoalkyl derivative bound by a secondary amine linkage (Figure 1.96). Also see Section 4.6, this chapter, for an extensive discussion on carbohydrate modification techniques. 

This simple strategy can be used to add amine residues to polysaccharide molecules after formation of aldehydes by periodate or enzymatic oxidation (Section 4.4, this chapter). Thus, glycoconjugates or carbohydrate polymers such as dextran may be derivatized to contain amines for further conjugation reactions. 

Oxidation of polysaccharides using 10 mM or greater concentrations of sodium periodate at room temperature results in the cleavage of adjacent hydroxyl-containing carbon-carbon bonds on other sugars besides just sialic acid residues (Lotan et al., 1975). High concentrations... 

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