The influence of high supersaturation on kinetic control and the impor
tance of the polypeptide structure in the crystallization of calcium c
arbonate polymorphs were studied in crosslinked gelatin films containi
ng high concentrations of the polypeptides poly-L-aspartate and poly-L
-glutamate. Oriented crystallization of vaterite occurs in uniaxially
deformed gelatin films containing poly-L-aspartate at concentations gr
eater than 100 mg per gram of gelatin. The fact that no orientation of
the mineral phase was observed with entrapped poly-L-glutamate at the
same concentrations suggests that the oriented crystallization is con
trolled by the beta sheet structure assumed by poly-L-aspartate in the
presence of calcium ions. These results indicate that local supersatu
ration in the microenvironment in which nucleation and growth occur pl
ays an important role in controlling the deposition of vaterite in cro
ss-linked gelatin films. However, collagen bundles se and the ordered
and oriented polypeptide chains of poly-L-aspartate can contribute to
the control of polymorphism by inducing the formation of a specific ph
ase by epitaxial crystallization, as suggested by the preferentially o
riented deposition of vaterite and aragonite. This is of potential sig
nificance in biomineralization processes and in materials science.