Recent developments in methods and instrumentation have contributed to major advances in our understanding of the fine structure of amylose and amylopectin. The structure of the starch granule slowly unravels with new insight into key structural features. Following a brief presentation of the structural features common to all starches, the most recent findings for the structure of amylose and amylopectin are reported. The organization of different types of chains in amylopectin is discussed with a critical review of the ‘cluster’ model leading to the presentation of alternative models. The locations of molecular components in the starch granule are described according to a progress structural order. The description of the crystalline components is followed by a presentation of their supramolecular arrangements. The crystalline components comprise platelet nanocrystals which have already been identified and characterized, and other less well characterized ‘blocklet components’. The location and state of amylose within the granule is also presented. This comprehensive review aims at distinguishing between those structural features that have received widespread acceptance and those that are still under debate, with the ambition of being educational and to provide stimulation for further fundamental investigation into the starch granule as a macromolecular assembly.

Starch is a major food supply for humanity. It is produced in seeds, rhizomes, roots and tubers in the form of semi-crystalline granules with unique properties for each plant. Though the size and morphology of the granules is specific for each plant species, their internal structures have remarkably similar architecture, consisting of growth rings, blocklets, and crystalline and amorphous lamellae. The basic components of starch granules are two polyglucans, namely amylose and amylopectin. The molecular structure of amylose is comparatively simple as it consists of glucose residues connected through α-(1,4)-linkages to long chains with a few α-(1,6)-branches. Amylopectin, which is the major component, has the same basic structure, but it has considerably shorter chains and a lot of α-(1,6)-branches. This results in a very complex, three-dimensional structure, the nature of which remains uncertain. Several models of the amylopectin structure have been suggested through the years, and in this review two models are described, namely the "cluster model" and the "building block backbone model". The structure of the starch granules is discussed in light of both models.

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Starch continues to be an important renewable biopolymer in both the food and non-food industries. Its properties, which vary depending on the plant source, stem directly from its structure. The recent substantial increase in knowledge of the molecular structure of starch components and the architecture of starch granules has contributed significantly to an enhanced understanding of the structural base of starch functionality. This résumé provides an overview of the present views of the starch structure-function relationships with an emphasis on industrially important starch sources.

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