Oxidation amylopectin

An alternative approach has been described by Hirst and coworkers,86 in which periodate-oxidized amylopectin is hydrolyzed and the percentage of D-glucose in the hydrolyzate estimated chromatographically. (If a cross... 

Hydroxyethylstarch (HES) is prepared from the amylopectin of waxy maize starch by hydrolysis and subsequent treatment with ethylene oxide. Amylopectin is a branched polyglucose composed of chains of a 1-4 linked glucose residues, to which a number of branches are attached by a 1-6 linkages (Aspinall 1970). When soluble amylopectin is intravenously injected into animals, it is rapidly degraded by a-amylase and is therefore unsuitable as a plasma substitute. For this reason Wiedersheim (1957) suggested substitution of amylopectin with hydroxyethyl groups to slow down the action of amylase and so extend its persistence in the circulation. He showed that such HES preparations had useful properties as plasma expanders and were relatively nontoxic. These results were subsequently confirmed and extended (Thompson et al. 1962, 1964, 1970). 

Com and rice starches have been oxidized and subsequently cyanoethylated (97). As molecular size decreases due to degradation during oxidation, the degree of cyanoethylation increases. The derivatized starch shows pseudoplastic flow in water dispersion at higher levels of cyanoethylation the flow is thixotropic. Com and rice starches have been oxidized and subsequently carboxymethylated (98). Such derivatives are superior in the production of textile sizes. Potato starch has been oxidized with neutral aqueous bromine and fully chemically (99) and physically (100) characterized. Amylose is more sensitive to bromine oxidation than amylopectin and oxidation causes a decrease in both gelatinization temperature range and gelatinization enthalpy. 

Table I shows the results of periodate oxidation and methylation applied to amylopectins from various sources. If the percentage of amylose in a whole starch is known, the length of unit chain of the amylopectin component can be calculated from the results of periodate oxidation of the whole starch (see Table II). The length of unit chain appears to depend on the botanical species, but not the variety, from which the starch wras isolated. In the case of tapioca and corn amylopectins, sub-fractionation of these by precipitation with methanol, followed by periodate oxidation, showed the sub-fractions had the same degree of branching as the original amylopectins.71 The action of periodate on whole starches and amylopectins is now so well established and accurate, that it may well completely supersede the methylation technique for pure starches, in view of its many advantages.

Starch source Amylose, % Average (a) by metky-lation length of t b) by Periodate oxidation tnit chain (c) calc, for amylopectin from (6) References... 

Fig. 7 Maltotetraose hybrids with various carriers resulting in different chain architectures A poly(ethylene oxide) Ba and Bb poly(acrylic acid), amylose, cellulose, and other polysaccharides Ca cyclodextrin and multifunctional acids Cb amylopectin D crosslinked poly(acryl amide) [156] - Reproduced by permission of Wiley...

Structural analysis of isolated amylose and amylopectin components has been carried out by standard methods based on methylation, periodate oxidation, and partial acid hydrolysis studies. Methylation and periodate oxidation studies established the linkage types and frequency of... 

Starch (amylose and amylopectin) hydrolysis along with ester-fication, etherification or oxidation have been previously discussed as available methods for producing starch derivatives with improved water dispersibilities and reduced retrogradation potential (, ). Since oxidative and hydrolytic reactions are simple, easily controlled chemical modifications, starch-derived polymers made by hydrolysis alone or oxidative and hydrolytic processes were developed and tested. 

Nitrotoluenes, Van No strand, NY(1918) 2)M.Kostevitch, "Tarry Matter of Alpha Trinitrotoluene, Part II, Imprd Art Vol-taire,P aris( 1927), 8 3)Sidgwick( 19 37), 259 et seq 4)Davis(1943), 136-7, 147, 149-51 170-1 5>negering( 1950), 139 seq 6) Dept of the Army TM 9-1910( 1955), 146 Alkalies, Action on Nitric Esters. Organic nitrates in general are readily saponified by alkaline solns. A simple metathetical reaction to yield the alkali nitrate and alcohol does not take place instead, as a result of simultaneous oxidation and reduction, alkali nitrite and a variety of products are formed depending on the conditions of the reaction. The resistance of different nitric esters to alkalies varies considerably. Thus, starch nitrate is decomposed much more slowly than cellulose nitrate and amylopectin nitrate still more alowly... 

R. L. Whistler and R. Schweiger, Oxidation of amylopectin with hydrogen peroxide at different hydrogen ion concentrations, J. Am. Chem. Soc., 81 (1959) 3136-3139. 

Volatile compounds generated by model systems of zeln, corn amylopectin and corn oil extruded at barrel temepratures of 120°C and 165°C were analyzed by GC and GC/MS. The largest quantities of lipid oxidation products were detected in systems containing all three components. In each system, the quantity of 2,4-deca-dienal was low relative to the quantities of hexanal, heptanal and benzaldehyde. Identification of the Maillard reaction products, 2-methyl-3(or 6)-pentyl-pyrazine, 2-methyl-3(or 6)-hexylpyrazine and 2,5-di-methyl-3-pentylpyrazine, suggested that lipid-derived aldehydes might be involved in the formation of substituted pyrazines. 4-Methylthiazole was identified as a major decomposition product of thiamin when corn meal containing 0.5% thiamin was extruded at a final temperature of 180°C. 

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