Starch complexes with organic molecules

In its primary structure, the AGU are existing in the conformation c (chair conformation). The valence angles between the AGU are favoring a helical conformation, formed by 6-8 AGU, as the energetically most suitable state. The normal state in solution is that of a disturbed helix. An ideal stable helix conformation is formed and stabilized when hydrophobic molecules (iodine, aliphatic alcohols and acids) are allowed to penetrate into the molecular channel. The formation of such inclusion complexes is a typical property of a. and may be compared best with the inclusion behavior of - cyclodextrin. Insoluble complexes with organic solvents are used to precipitate amylose from starch solutions during fractionation. 

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. 

Cyclodextrins, products of the degradation of starch by an amylase of Bacillus macerans(1), have been studied in terms of chemical modifications, mainly for the purpose of developing efficient enzyme mimics(2). Not only their unique cyclic structures, but also their ability to form Inclusion complexes with suitable organic molecules, led us to Investigate the total synthesis of this class of molecules(3) We describe here an approach to a total synthesis of alpha(l), gamma(2), and "iso-alpha" cyclodextrin (3). 

Structural studies of amylose have, in turn, revealed a wide range of crystalline polymorphy, both in chain conformation and in crystalline packing. An example is the group of V-amyloses that exist as complexes with small organic molecules, water, or iodine. The latter complex is particularly interesting because it displays an intense blue color. The V-amyloses can be prepared by precipitation or drying from solution, and they crystallize readily. Consequently, their crystal structures are of interest in connection with any regenerated form of starch material. 

It has been almost two centuries since the first reports on the interaction between iodine and starch to produce a blue color, and more than fifty years since the discovery of the complexation between aliphatic alcohols and starch that revealed this polysaccharide to have a linear and a branched component. A large and diffuse body of published work exists on the interaction of starch and its components with other molecules and with ionic substances. Two closely related chapters in this volume, by Tomasik (Cracow, Poland) and Schilling (Ames, Iowa), provide comprehensive accounts of the extensive literature on complexes of starch with inorganic and with organic guests. 

The cyciomaitodextrins (a-CD, -CD, and y-CD) can be selectively obtained from a fermentation culture or an enzyme digest of cyclomaltodextrin glucanotransferase reaction with solubilized starch. The majority of the cyclomaltohexaose (a-CD) can be separated from cycloma-Itoheptaose (/3-CD) and y-CD by their selective precipitation with p-cymene from the culture supernatant or from an enzyme digest [168]. The a-CD can then be precipitated from the supernatant with cyclohexene, which is extracted with acetone to remove the cyclohexene and the a-CD can be crystallized from water or a propanol-1/water solution [169]. The p-cymene precipitates of /3-CD and y-CD are put into a water solution and /3-CD selectively precipitated from y-CD with fluorobenzene. The y-CD is then precipitated with anthracene saturated in diethyl ether. After the removal of the fluorobenzene from /3-CD with acetone or ethanol extraction, /3-CD can be crystallized from water, and after the removal of anthracene with acetone or ethanol extraction from y-CD, it can also be crystallized from water [170,171]. The selective precipitations of the cyciomaitodextrins with various organic molecules is based on the selective formation of complexes of the organic molecules with the specific sizes of the cyciomaitodextrins and the relatively hydrophobic interior cavities of the cyciomaitodextrins [166,167,168]. 

These basic organic molecules can react with each other to form larger, more complex macromolecules. Amino acids can combine to form larger peptide chains, which in turn can combine to form protein molecules. Likewise, simple sugar molecules can combine to form polysaccharide molecules that combine to form starches and cellulose. 

The limited solubility of starch and its modified products may affect the reversibility of many reactions. This may explain several, apparently unusual, reactions reported in starch chemistry. There are, for example, reports of starch esterification with sodium hydrogenphosphates, acylation of starch with acyl amides (which is equivalent to the transformation of an amide into an ester), and the formation of alkali-metal starchates upon treatment of starch with alkali (a reaction which fails for simple alcohols). A specific property of starch is its ability to form surface sorption and helical inclusion-complexes with many inorganic and organic guest molecules.4... 

Common adsorbents are oxides such as silica, alumina, alumino-silicates, and clays, among others. Rarer studies were also presented for cellulose and cellulose derivatives or starch [2a]. Cyclodextrins and calixarenes are good examples of organic host molecules, which can form inclusion complexes with many guest molecules. 

Similarly, the biodegradation process affects more complex organic molecules such as natural polymers (starch, cellulose and so on) and some man-made polymers. This is indeed the case of biodegradable polymers used for the production of plastic articles that have been designed with the aim of being biodegraded in the soil or in composting plants. 

---