Amylopectin complexes

Mokhnach and Rusakova11 have shown that amylose-iodine and also starch-iodine complexes absorb at 226, 288-290, 344-360, and 585-620 nm. The first band appears only when iodine is added to the solution simultaneously with KI, and it is absent when only iodine is added. The longest-wavelength absorption may be indicative of the molecular size of the carbohydrate portion of the complex, as demonstrated106 in Table VIII. Spectra of iodine-amylopectin complexes were measured by Archibald et al.146 The UV absorption spectrum of the starch-iodine complex is shown... 

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-... 

Off-line iodine complexing is a frequently used method to characterize the SEC fractions. Amylose-iodine and iodine-amylopectin complex have a maximum absorbance at about 658 and 546 nm, respectively. Recently, Suortti and Pessa (63) demonstrated that is is possible to do iodine complexing detection on-line, such as that shown in Figure 4. Photodiode array (PDA) ultraviolet (UV) detectors are readily available now. PDA can take the UV spectrum of the eluant on the fly. The information is stored in the computer. After the run, a contour plot or three-dimensional plot can be shown on the screen or printed out. Iodine complexing with PDA detection can be a very useful technique for characterizing starch samples. 

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. 

Amylose [9005-82-7] (C Hio05) (/br use in iodine complex formation). Amylopectin was removed from impure amylose by dispersing in aqueous 15% pyridine at 80-90 (concn 0.6-0.7%) and leaving the soln stand at 44-45° for 7 days. The ppte was re-dispersed and recrystd during 5 days. After a further dispersion in 15% pyridine, it was cooled to 45°, allowed to stand at this temperature for 12hours, then eooled... 

Amylopectin accounts for the remaining 80% of starch and is more complex in structure than amylo.se. Unlike cellulose and amvlose, which are linear polymers, amylopectin contains 1- 6-cr-glycoside branches approximately every 25 glucose units. 

There are two types of glucose chains in starch. One is a simple chain called amylose, and the other is a complex branched form called amylopectin. In the starch grains in a plant, amylopectin makes up the bulk of the material, from 50 to 80 percent by weight, made up of several million amylopectin molecules per starch grain. The rest is a much larger number of the smaller amylose chains, made up of 500 to 20,000 glucose units in each chain. Amylopectin molecules are made of several million glucose units. 

Successful methods entail precipitation of the amylose from solution as an insoluble complex, which is removed by high-speed centrifuging the amylopectin is isolated from the supernatant liquor by precipitation with alcohol or, more satisfactorily, by freeze-drying. (Precipitation with alcohol does not always appear to be quantitative, and the physical form of the product obtained by freeze-drying is more satisfactory for subsequent dissolution and esterification.) The amylose can then be further purified by reprecipitation with the same or, preferably, a different complexing agent. 

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. 

Tapioca and maize amylopectins have been sub-fractionated by fractional precipitation from aqueous solution with increasing amounts of methanol,64 71 and potato amylopectin by preferential precipitation on electrodialysis of the iodine complex.72 When these three amylopectins were subjected to chromatography, and eluted with a neutral buffer, all were found to consist of several sub-fractions.70... 

The physical form of the component is extremely important for ease of esterification for amylose, the order of reactivity is amylose complex > freeze-dried or freshly precipitated amylose > alcohol-precipitated, ether-dried amylose, whereas freeze-dried amylopectin is more reactive than... 

Fig. 7. 134C-N.m.r. Spectrum ofDiphenylborinate Complex of Potato Amylopectin in...

More complex starches are termed amylopectins and contain branched chains. Starches can be very large molecules indeed, with molecular masses ranging up into the millions. 

Amylopectin Amylopectin is similar to amylose except that the glucose chain has branches. These branches involve linkages at the -CH2OH position ( 6), which makes them a 1 —> 6 linkages. Amylopectin is water-soluble it also interacts with iodine to form a reddish-purple complex. Typically, amylopectin is ten times the size of an amylose molecule. Digestion requires (3-amylase (1 4 linkages) and a second... 

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 consists of two main components amylose (insoluble in cold water) and amylopectin (soluble in cold water). Amylose, which accounts for about 20 per cent by weight of starch, has an average molecular weight of over 10. It is a polymer of glucopyranose units linked together through a l,4 -linkages in a linear chain. Hydrolysis of amylose produces maltose. Amylose and iodine form a colour complex, which is blue/black. This is the colour reaction of iodine in starch, a confirmatory test for the presence of starch. 

Starch granules are composed of two different polysaccharides, amylopectin and amylose the former constitutes about 80 % of the most common starches. Separation of the two components can be achieved by selective precipitation involving the formation of an insoluble complex of amylose with polar organic substances. 

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