Starch esters hydrolysis

Common starch esters include the acetates. High d.s. starch acetates have been formed by using acetic anhydride with either sodium acetate or pyridine catalysts at 90-100 °C [158,159,160]. The major use of starch acetates have been in the study of the stmctures of amylose and amylopectin after acid hydrolysis. Acetylation of granular starch in aqueous suspension by acetic anhydride at pH 10-11 is used to produce low d.s. starch acetates that are primarily used for the stabilization of their viscosity and for their water-soluble clarity. The acetylation decreases the hydrophilic character and increases the hydrophobic character of starch. The major uses of starch acetates is in the paper industry for surface sizing to give improved print quality, uniform porosity, surface strength, and resistance to various solvents [161]. 

In other reactions of starch esters, for example, 2,3-di-O-acetylamylose reacted with A-iodosuccinimide in the presence of triphenylphosphine to give 2,3-di-0-acetyl-6-deoxy-6-iodoamylose.2019 The ester bonds are fairly stable to acid-catalyzed hydrolysis. Starch esterified with acetylsalicylic acid administered to dogs did not increase the acetylsalicylic acid level to any significant extent in the animal s blood serum.2020 The slow release of herbicides from their esters with starch was analyzed.2021,2022 Alkaline hydrolysis of starch esters is easier than acid hydrolysis.2023 The enthalpy of starch acetate formation was 143.5kJ/mole, and acetylation decreased the susceptibility of the starch backbone to enzymatic hydrolysis and iodine uptake.2024 The hydrolysis of starch and starch acetate in alkaline solutions obeys second-order kinetics.1988... 

In context with RR, the following w. should be mentioned alginates (- sodium alginate) ->car-boxymethyl cellulose - carrageenan - guar gum - locust gum gum arabic - hydroxyethyl cellulose - hydroxypropyl cellulose - methyl-cellulose - mixed ethers of cellulose ->pectin, - starches, starch esters, - starch ethers, - oxidized starches, -+dextrins, - starch hydrolysis products, - maltodextrins and their derivatives, - dextran, - scleroglucan, - maltodextrins and - xanthan. 

General protease, a-amylase, and exoglucanase activities were estimated using hide powder-, amylose-, and celliilose-azure substrates, respectively, as described earlier (49). Here, standard curves were developed for the hydrolysis of each azure-linked substrate by standard enzymes of known activity. By this method, one cellulose-azure hydrolysis unit corresponds to one filter paper unit, one unit of hide powder-azure activity corresponds to the hydrolysis of 1.0 nmole of iV-benzoyl-L-tyrosine ethyl ester (BTEE) per min, and one amylose-azure unit of activity corresponds to the hydrolysis of 1.0 nmole of maltose from starch per 30 min. 

The first step in glycolysis is the phosphorylation of glucose to give the ester glucose 6-phosphate. The glucose starting material may well have come from hydrolysis of starch obtained in the diet, or by utilization of glycogen reserves. 

Potato starch usually contains 0.01-0.6% (w/w) phosphorus. Although phosphorus is present at very low levels, it has a significant effect on the physicochemical properties of starch. Phosphorus is in part responsible for the high swelling power, paste stability, and resistance to enzyme hydrolysis of potato starch. Potato starches contain significant amounts of monophosphate esters... 

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. 

The structures of the disaccharides and higher saccharides (obtained by partial hydrolysis of polysaccharides) can be examined by periodate or lead tetraacetate oxidation. Ahlborg studied the periodate oxidation of disaccharides and starch dextrins in 0.5 N sulfuric acid. Since the intermediate formate esters were hydrolyzed, these conditions were favorable for overoxidation. The (1 — 4)- and (1 —> 6)-linkages in the starch dextrins were each found to be associated with a characteristic consumption of oxidant. Neumtiller and Vasseur studied periodate oxidation in solutions of various acidities, from strongly acid to neutral, and showed that there were differences between different types of disaccharides. 

In this connection it may be mentioned that many ordinary yeasts ferment, generally very slowly, isomaltose and trisaccharides (limit dextrins) with one maltose and one isomaltose linkage. - Dried yeasts ferment starch and limit dextrins mth a fairly high velocity. This fermentation is probably not due to a hydrolysis of the saccharides to D-glucose or maltose, but to a phosphorolysis to the Cori ester (a-D-glucopyranose 1-phosphate). 

Amylopectin of potato starch and probably amylopectin of other tuber starches occurs as a natural ester of phosphoric acid. Potato amylopectin" contains approximately 0.07-0.09% phosphorus, " or one phosphate group for every 212 to 273 anhydroglucose units. The phosphate appears to be attached mainly to the primary alcohol group since, on hydrolysis, potato amylopectin (separated by electrodialysis)... 

Chromatographic batch reactors are employed to prepare instable reagents on the laboratory scale (Coca et al., 1993) and for the production of fine chemicals. These applications include the racemic resolution of amino acid esters (Kalbe et al., 1989), acid-catalyzed sucrose inversion (Lauer, 1980), production of dextran (Zafar and Barker, 1988) and saccharification of starch to maltose (Sarmidi and Barker, 1993a). Sardin et al. (1993) employed batch chromatographic reactors for different esterification reactions such as the esterification of acetic acid with ethanol and the transesterification of methylacetate. Falk and Seidel-Morgenstern (2002) have investigated the hydrolysis of methyl formate. 

The concept that a catalyst provides an alternate mechanism for accomplishing a reaction, and that this alternate path is a more rapid one, has been developed in many individual cases. The basis of this idea is that the catalyst and one or more of the reactants form an intermediate complex, a loosely bound compound which is unstable, and that this complex then takes part in subsequent reactions which result in the final products and. the regenerated catalyst. Homogeneous catalysis can frequently be explained in terms of this concept. For example, consider catalysis by acids and bases.. In aqueous solutions acids and bases can increase the rate of hydrolysis of sugars, starches, and esters. The kinetics of the hydrolysis of ethyl acetate catalyzed by hydrochloric acid can be explained by the following mechanism ... 

Several types of enzymes have found uses in LADD compositions [4,48], Most common are proteases, amylases, and lipases, which attack proteinaceous, starchy, and fatty soils, respectively. Proteases work by hydrolyzing peptide bonds in proteins. Proteases differ in their specificity toward peptide bonds. The typical protease used in LADD formulations, bacterial alkaline protease (subtilisin), is very nonspecific. That is, it will attack all types of peptide bonds in proteins. In contrast to proteases, amylases catalyze the hydrolysis of starch. They attack the internal ether bonds between glucose units, yielding shorter, water-soluble chains called dextrins. Lipases work by hydrolyzing the ester bonds in fats and oils. Often, combinations are used because of the specificity of each kind to one type of soil. The commercially available enzymes are listed in Table 9.6. 

A membrane cell recycle reactor with continuous ethanol extraction by dibutyl phthalate increased the productivity fourfold with increased conversion of glucose from 45 to 91%.249 The ethanol was then removed from the dibutyl phthalate with water. It would be better to do this second step with a membrane. In another process, microencapsulated yeast converted glucose to ethanol, which was removed by an oleic acid phase containing a lipase that formed ethyl oleate.250 This could be used as biodiesel fuel. Continuous ultrafiltration has been used to separate the propionic acid produced from glycerol by a Propionibacterium.251 Whey proteins have been hydrolyzed enzymatically and continuously in an ultrafiltration reactor, with improved yields, productivity, and elimination of peptide coproducts.252 Continuous hydrolysis of a starch slurry has been carried out with a-amylase immobilized in a hollow fiber reactor.253 Oils have been hydrolyzed by a lipase immobilized on an aromatic polyamide ultrafiltration membrane with continuous separation of one product through the membrane to shift the equilibrium toward the desired products.254 Such a process could supplant the current energy-intensive industrial one that takes 3-24 h at 150-260X. Lipases have also been used to prepare esters. A lipase-surfactant complex in hexane was used to prepare a wax ester found in whale oil, by the esterification of 1 hexadecanol with palmitic acid in a membrane reactor.255 After 1 h, the yield was 96%. The current industrial process runs at 250°C for up to 20 h. 

Starch derivatives may also undergo hydrolysis and degradation under alkaline conditions. The hydrolysis of the nitriles, amides, and esters resulting from the reaction of starch with corresponding vinyl monomers is obvious. Considerable attention has been paid to the alkaline degradation of starch dialdehyde. It de-polymerized readily supposedly as a result of -elimination at C-5, although such a questionable -elimination should not be facile).70... 

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