Crystal Polymorphism of Curdlan Propionate: 6-Fold versus 5-Fold Helices

The molecular and crystal structures of curdlan propionate (CDPr) were examined by the X-ray fiber diffraction methods combined with energy calculations. CDPr forms two different crystal structures (CDPr forms I and II) depending on annealing conditions: solvent-annealing yields CDPr form I, whereas thermal-annealing gives CDPr form II. In CDPr form I, the 6/1 helix is packed in the hexagonal unit cell with a = b = 1.154 nm, and c (fiber axis) = 2.287 nm. In the case of CDPr form II, the 5/1 helix is packed in the pseudohexagonal cell with a = b = 1.175 nm, and c (fiber axis) = 1.859 nm. The crystal transition from CDPr forms I to II occurs by thermal-annealing at temperatures ≥ 160 °C.