Starch, complexes fractionation

Starch complexation with thymol was proposed for the fractionation of starch,704 but the procedure is not as efficient as that with 1-butanol. Fractionation with thymol followed by the use of 1-butanol is used to produce high-purity components. Complexation with naphthols revealed that 1-naphthol forms complexes with starch more readily than does its 2-isomer.673 1-Naphthol complexes in two modes, as suggested by the Scatch-ard plot, and the binding is rather weak.717 Complexes between a formalde-hyde-hydroquinone polymer and starch have also been detected.718... 

The formation of starch complexes with other polysaccharides is perhaps best evidenced by the sorption of starch on cellulose and its derivatives. This sorption is selective with respect to amylose and amylopectin.1065 1066 Cotton fibers selectively adsorb amylose and not amylopectin.1667-1071 However, this method cannot be used for starch fractionation because cotton was considered to induce degradation (hydrolysis).1067 On the other hand, a method of purifying amylopectin that involves sorption of amylose on defatted cellulose has been published.1072 Reversible adsorption of amylopectin on cellulose occurs when starch is equilibrated with urea in 32-35% ethanol. There are also published attempts to separate starch components on filter paper.1073-1076 The reverse idea is applied in the stabilization of nitrocellulose by its sorption on starch.1077... 

At 20 , at a constant concentration, of starch, of 2.5 g. per 100 ml. Percentage of total starch A. Measured by potentiometric titration B. AB/3.75. Blank determination of total available amylose, by complex-fractionation with amyl alcohol at its critical concentration. ... 

It will be noted that this type of complex-formation is entirely different from that in which complexes are formed between amylose and certain polar, organic compounds. In contrast to the precipitates of the latter complexes (which are of a distinct, crystalline appearance), the starch-alkaline-earth hydroxide complexes are amorphous, curdlike flocculates. These complexes di,s.sociate on diluting them with water, and the starch redissolves. According to the patent description, the amylose complexes dissolve much more easily than the amylopectin complexes hence, fractionation must occur if water is added stepwise. Likewise, fractionation will take place if the starch complexes are partially neutralized, by the gradual addition of an acid. For obvious reasons, such acids as carbonic acid and sulfuric acid (which give insoluble calcium salts) are preferred. Furthermore, it is claimed that gradual addition of caustic alkali to a starch solu-... 

When starch is fractionated into its two components, usually by precipitating the amylose from solution by means of an organic solvent (such as an alcohol), a third type of structure is found this survives drying, and ultimately reverts to the B structure upon rehydration. This structure has been termed the V form, and it yields an x-ray pattern that is distinctly different from the other two types. Essentially the same pattern was observed for the amylose-iodine complex. Bundle and coworkers studied the various V amyloses obtained by complexing with alcohols or iodine, and, on the basis of powder diagrams, suggested unit-cell parameters for both the wet and dry (hydrated and anhydrous) states, as shown in Table I (seep. 422). From these data, Bear had suggested earlier that the "V structure of amylose is helical. (Historically, it is of... 

The molecular uniformity of constituting components of a nb/lcb glucan fraction of potato starch was investigated with Sepharose CL 2B (Fig. 16.16) as well as with Sephacryl S-1000 (Fig. 16.17). Therefore, each of the subsequently eluted 3-ml fractions was analyzed on their potential to form inclusion complexes with iodine, a sensitive test for the presence of nb/lcb glucans. Results are shown in Fig. 16.17 in terms of branching index, the ratio of extinction of pure iodine solution and of nb/lcb glucan/iodine complex the higher the index, the more pronounced the nb/lcb characteristics. 

FIGURE 16.17 Nonbranched/long chain branched glucans of potato starch dissolved in hot water-steam and 0.1 M NaOH 1.2 ml of the 18-mg/ml solution was separated on Sephacryl S-1000 (95 X 1.6 cm) 3-ml fractions were collected for further analysis normalized (area = 1.0) eluogram profiles (ev) constructed from an off-line determined mass of carbohydrates for each of the fractions branching index ( ) determined from iodine-complexing potential of individual 3-ml fractions flow rate 0.40 ml/ min V ,i = 75 ml, Vtot = 162 ml eluent 0.005 tA NaOH. 

The most widely used complexing agents are alcohols (butanol, n-propyl alcohol and n-pentyl alcohol1). Schoch33 now recommends the use of Pen-tasol, a commercial mixture of pentyl alcohols, for the first precipitation, and 1-butanol for recrystallizations. For com (maize) starch, this avoids contamination of the amylopectin with an intermediate fraction which is sufficiently linear to be precipitated with Pentasol and yet has a degree of branching which prevents complex formation with butanol. 

The reactions of potassium iodide in aqueous solutions are those of iodide ion, r. In iodometric titration I combines with iodine to form triiodide ion, I3. The latter adds to (i-amylose fraction of the starch to form a blue complex. 

To determine the amylose content of starch, the iodine reaction has been most commonly used because amylose and amylopectin have different abilities to bind iodine. The methods such as blue value (absorbance at 680 nm for starch-iodine complex using amylose and amylopectin standards), and potentiometric and amperometric titration have been used for more than 50 years. These procedures are based on the capacity of amylose to form helical inclusion complexes with iodine, which display a blue color characterized by a maximum absorption wavelength (kmax) above 620 nm. During the titration of starch with iodine solution, the amount (mg) of iodine bound to 100 mg of starch is determined. The value is defined as iodine-binding capacity or iodine affinity (lA). The amylose content is based on the iodine affinity of starch vs. purified linear fraction from the standard 100 mg pure linear amylose fraction has an iodine affinity of 19.5-21.0mg depending on amylose source. Amylopectin binds 0-1.2mg iodine per 100mg (Banks and Greenwood, 1975). The amylose content determined by potentiometric titration is considered an absolute amylose content if the sample is defatted before analysis. 

Starch is used as an indicator in the reaction. The end point is marked by the appearance of a deep blue starch-iodine complex when the first fraction of a drop of unreacted If remains in the solution. 

Starch is composed of macromolecular components, a-amylose and (i-aim -lose. The former reacts irreversibly with iodine to form a red adduct. (i-Aim losc. on the other hand, reacts with iodine forming a deep blue complex. Because this reaction is reversible, [3-amyl0sc is an excellent choice for the indicator. The undesired alpha fraction should be removed from the starch. The soluble starch that is commercially available, principally consists of (3-amylose. (3-Amylose is a polymer of thousands of glucose molecules. It has a helical structure into which iodine is incorporated as I5. ... 

Other WAXD starch patterns, known as V-types, are associated with the amylose fraction. In V-amylose, the chain conformation is a left-handed single helix with six residues per turn (V6) for complexes with aliphatic alcohols and monoacyl lipids with ligands bulkier than a hydrocarbon chain, helices of seven or eight glucose residues per turn are feasible.31 Aliphatic chains within amylose helices are rather locked... 

Amyloses of five commercially important starches (wheat, corn, rice, tapioca and potato) were purified by fractional crystallization of their amylose-alcohol complexes and shown to be free of amylopectin.111,205 All five amyloses showed comparable iodine affinity, blue value and max of their polyiodide complexes (Table 10.5), which is consistent with their being (1 —4)-linked a-glucans with an average DPn of —500 or above.206 The average size of amylose molecules in cereal starches is smaller than... 

In an alternative route, starch is complexed with a polyamine, poly(vinyl amine), polyethylene imine) or chitosan to render it cationic. Although stronger, these complexes may also separate with time and lead to an undesirable accumulation of a low molecular weight, high-charge polyamine fraction and interference in the retention process. 

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