The Principles of Starch Gelatinization and Retrogradation

The polysaccharides, such as κ-carrageenan, ι-carrageenan, agarose (agar), gellan gum, amylose, curdlan, alginate, and deacetylated rhamsan gum, in water changed into an ice-like structure with hydrogen bonding between polymer and water molecules, and between water-water molecules even at a concentration range of 0.1% - 1.0% (W/V) at room temperature, resulting in gelation. Such dramatic changes from liquid into gels have been understood at the molecular level in principles. In this review, we describe the structure-function relationship of starch on the view point of rheological aspects and discuss gelatinization and retrogradation mechanism including water molecules at molecular level. The starch molecules (amylose and amylopectin) play a dominant role in the center of the tetrahedral cavities occupied by water molecules, and the arrangement is partially similar to a tetrahedral structure in a gelatinization process. The arrangement should lead to a cooperative effect stabilizing extended regions of ice-like water with hydrogen bonding on the surface of the polymer molecules, where hemiacetal oxygen and hydroxyl groups might participate in hydrogen bonding with water molecules. Thus, a more extended ice-like hydrogen bonding within water molecules might be achieved in a retrogradation process. Though many investigations not only include starch gelatinization and retrogradaion, but also the gelling properties of the polysaccharides have been undertaken to elucidate the structure-function relationship, no other researchers have established mechanism at the molecular level. There is reasonable consistency in our investigations.