Random and Sequential Copolypeptides Containing O‐Phospho‐ L ‐Threonine and L ‐Aspartic Acid; Roles in CaCO3 Biomineralization

The present study describes the synthesis of novel polypeptides containing O-phospho-L-threonine [Thr(PO(3)H(2))] and L-aspartic acid. Random copolypeptides copoly[Thr(PO(3)H(2))(X)Asp(Y)] (X:Y = 25:75, 50:50, 75:25), were conventionally prepared by copolymerization of Thr(PO(3)Ph(2)) N-carboxyanhydride (NCA) and Asp(OBzl) NCA followed by deprotection of the phenyl and benzyl groups by catalytic hydrogenolysis over PtO(2). Polycondensation of the protected peptide p-nitrophenyl esters [Thr(PO(3)Ph(2))](Z)-Asp(OBzl)-ONp and subsequent deprotection yielded the sequential polypeptides poly[Thr(PO(3)H(2))(Z)-Asp] (Z = 1-4). By using the synthetic polypeptides, their effects on the growth of CaCO(3) crystals were examined. In the poly[Thr(PO(3)H(2))(Z)-Asp]/CaCO(3) systems, brushlike calcite and spherical vaterite were formed, with the former being found at [Ca(2+)]/[Res] ratios of > or =180, > or =140, > or =120, and > or =100 for Z = 1, 2, 3, and 4, respectively. These results indicate that an increase of Thr(PO(3)H(2)) residues in the repetitive unit induces the characteristic brushlike calcite, a fact indicating that Thr(PO(3)H(2)) residues can modify the CaCO(3) crystal morphology.