Recent studies of the mechanisms determining the rate and extent of starch digestion by α-amylase are reviewed in the light of current widely-used classifications for (a) the proportions of rapidly-digestible (RDS), slowly-digestible (SDS), and resistant starch (RS) based on in vitro digestibility, and (b) the types of resistant starch (RS 1,2,3,4…) based on physical and/or chemical form. Based on methodological advances and new mechanistic insights, it is proposed that both classification systems should be modified. Kinetic analysis of digestion profiles provides a robust set of parameters that should replace the classification of starch as a combination of RDS, SDS, and RS from a single enzyme digestion experiment. This should involve determination of the minimum number of kinetic processes needed to describe the full digestion profile, together with the proportion of starch involved in each process, and the kinetic properties of each process. The current classification of resistant starch types as RS1,2,3,4 should be replaced by one which recognizes the essential kinetic nature of RS (enzyme digestion rate vs. small intestinal passage rate), and that there are two fundamental origins for resistance based on (i) rate-determining access/binding of enzyme to substrate and (ii) rate-determining conversion of substrate to product once bound.

Although high‐amylose starches are not a recent innovation, their popularity in recent years has been increasing due to their unique functional properties and enhanced nutritional values in food applications. While high‐amylose maize, barley, and potato are commercially available, high‐amylose variants of other main crops such as wheat and rice have once been developed more recently and will be available commercially in the near future. This review summarizes the development, structure, and nutritional functionality of high‐amylose starches developed and reported so far. The range of biotechnological strategies utilized are reviewed, as are the consequent effects on structural properties at different length scales, as well as sensory aspects of foods containing high‐amylose starch (HAS). This review identifies the molecular and microstructural features contributing to digestive enzyme resistance not only in native HAS but also in forms of relevance to food processing. During heat treatment, HAS tends to retain or form dense molecular structures that resist amylase degradation through the retention of the granular structure as well as helices (type‐2 resistant starch [RS]), reassociation of glucan chains (type‐3 RS), and formation of lipid–amylose complexes (type‐5 RS). The review also identifies opportunities for food manufacturers and consumers to incorporate HAS in food products and diets for better nutritional outcomes.

Increasing the level of starch that is not digested by the end of the small intestine and therefore enters the colon (‘resistant starch’) is a major opportunity for improving the nutritional profile of foods.