Amylose fractions of different peak Degree of Polymerisation (DP) (DP20, DP60, DP400, DP950) were complexed with docosanoic acid (C22) and glyceryl monostearate (GMS) at 60 and 90degreesC. Complexation yields, relative crystallinities, dissociation temperatures and enthalpies increased with amylose chain lengths (DP20-DP60-DP400). Relative crystallinities and thermal stabilities of the DP950-complexes were slightly lower than those of the other amylose fractions, probably due to increased conformational disorders, resulting in crystal defaults. Molecular weight distributions of the complexes revealed that, irrespective to the complexation temperature, the critical DP for complex formation and precipitation was 35 and 40 for complexes with GMS and C22, respectively, corresponding to the length needed to accommodate two GMS- or C22-molecules within an amylose helix. Complexation of dextrins with a well-chosen lipid, allows to separate starch derived dextrins with a predictable critical chain length as border. Dextrins, of sufficient DP will complex and precipitate, while the shorter dextrins will remain in solution. (C) 2004 Elsevier Ltd. All rights reserved.