Amylopectin from two double maize mutant starches of A-crystalline (wxdu) and B-crystalline type (aewx) was subjected successively to hydrolysis involving alpha and beta amylases, which isolated clusters and all branching zones of clusters (BZC), Enzymatic analysis together with ionic and size-exclusion chromatography revealed the structural features of the clusters and BZC and their role hi starch crystallization. A-type clusters were larger (<(dp(n))over bar> > 80) and contained more (but shorter) chains than B-type clusters. The BZC of A-type starch was also larger, but with a shorter distance between the branching points than in B-type BZC. A-type clusters had a densely packed structure and B-type a poorly branched structure. Models for the structure of A- and B-type clusters are presented, and a hypothesis for the influence of cluster geometry on crystallization is proposed. (C) 2000 Elsevier Science Ltd. All rights reserved.