Amylose esters

Figure 5.9. (a) A cellulose ester. The scale of the side chains is reduced for convenience. (b) An amylose ester. The vertical scale is again reduced. 

Figure I. Effect of the reaction time and NaOH catalyst concentration on die (a) degree of substitution and (b) recuperation yield of amylose ester obtained from reaction between amylose and octanoic acid at 195°C. XI (Time) 2 to 6 h X2 ([Catalyst]) 1.5 to 23 meq/eq OH...

The ethanol concentration in the emulsions was fixed at 2.S eq/eq OH. The response surface analysis showed that it is necessary to set the reaction conditions at [NaOH] = 23 meq/eqOH and time = 6 hr to synthesize an amylose ester with a high DS and RR, that is DSg = 0.50 and RR = 70%. These conditions were used to study the effect of the catalyst (Table 1) and biopolymer type (Table 2) on the DS and RR at the fatty esters. 

R may be aliphatic, aromatic or substituted aromatic. The second type, the amylose esters are similar in form. 

Molecular Interactions. Various polysaccharides readily associate with other substances, including bile acids and cholesterol, proteins, small organic molecules, inorganic salts, and ions. Anionic polysaccharides form salts and chelate complexes with cations some neutral polysaccharides form complexes with inorganic salts and some interactions are stmcture specific. Starch amylose and the linear branches of amylopectin form inclusion complexes with several classes of polar molecules, including fatty acids, glycerides, alcohols, esters, ketones, and iodine/iodide. The absorbed molecule occupies the cavity of the amylose helix, which has the capacity to expand somewhat to accommodate larger molecules. The starch—Hpid complex is important in food systems. Whether similar inclusion complexes can form with any of the dietary fiber components is not known. 

Values of /c2 and Kd for the reactions of the cycloamyloses with a variety of phenyl acetates are presented in Table IV. The rate constants are normalized in the fourth column of this table to show the maximum accelerations imposed by the cycloamyloses. These accelerations vary from 10% for p-f-butylphenyl acetate to 260-fold for m-f-butylphenyl acetate, again showing the clear specificity of the cycloamyloses for meta-substituted esters. Moreover, these data reveal that the rate accelerations and consequent specificity are unrelated to the strength of binding. For example, although p-nitrophenyl acetate forms a more stable complex with cyclohexa-amylose than does m-nitrophenyl acetate, the maximal rate acceleration, h/kan, is much greater for the meta isomer. 

Among optically active polymers, polysaccharide derivatives are particularly valuable. Polysaccharides such as cellulose and amylose are the most readily available optically active polymers and have stereoregular sequences. Although the chiral recognition abilities of native polysaccharides are not remarkable, they can be readily converted to the esters and carbamates with high chiral recognition abilities. The chiral recognition mechanism of these derivatives has been clarified to some extent. 

The anions of CDs may also function as simple basic catalysts towards acidic substrates included in their cavities. Such was observed by Daffe and Fastrez (1983) who studied the deprotonation and hydrolysis of oxazolones in basic media containing CDs. Also, in a paper dealing mainly with catalysis by amylose, it was noted that CDs catalyse the deprotonation of long chain /3-keto esters in basic aqueous DMSO (Cheng et al., 1985) no saturation kinetics were found for CDs, indicating weak substrate binding under the conditions used. 

Ester derivatives of cellulose, chitin, dextran, amylose, and amylopectin were prepared utilizing the acid chloride derivatives described in Part B of the Experimental Section. 

Table I lists physical data for a number of the carbamate and ester derivatives of cellulose, chitin, amylose, amylopectin, and dextran synthesized as described in the Experimental Section. The solubility of the polysaccharide starting materials as well as that of the produced derivatives allows for macromolecular characterization through techniques including UV, NMR, IR, high pressure liquid chromatography, etc.

Hammett substituent constant, effect of cyclo-amyloses on, in hydrolysis of phenyl esters, 23 222... 

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. 

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