Communications polyelectrolytes including poly-L-glutamate, can be explained on the basis of the model proposed by Addadi et al.L4I These authors demonstrated that the P-sheet structure of the polyaspartate adsorbed on solid substrate is essential in order to induce (001)-oriented calcite nucleation by matching the charged groups of the polymer and the intercationic distances in the crystal lattice of the salt. It follows that the [3-sheet structure should be assumed by the exposed stretches of poly-L-aspartate on the surface of the gelatin films, while for the other polyelectrolytes considered the electrostatic interactions do not seem to be dictated by structural factors.Gelatin containing polyelectrolytes can be considered a versatile system for the planning of new films with tailor made surfaces. In fact, this system overcomes the compatibility problem between inert matrix and water-soluble polyelectrolytes or protein generally associated with biological mineralization. Furthermore, the nature, density and structural disposition of the charged groups on the surface can be regulated in a simple way by changing the kind and the amount of the polyelectrolytes in the film.
ExperimentalType A gelatin from porcine skin was used (G-2500). The sodium salts of poly-L-aspartic acid (P-5387, average M.w. = 9900), poly-L-glutamic acid (P-4636, average M.Iv. = 6100). sulfate chondroitine A (C-8529) and C (C-4384) and carrageenan K (C-1263) were supplied by Sigma Co.3.0mlofa2% aqueousgelatinsolutioncontainingfrom5x 10-'to5 x lo-' weight percent (relative to gelatin) of polyelectrolyte was used to fill a Petri dish (diameter = 5 cm) on the bottom of which the film was obtained after water evaporation at room temperature. 5.0 ml of a 5 % glutaraldehyde solution in phosphate buffer (pH = 7.5) were placed on the film for 24 h. The films kept on the bottom of the dishes were thoroughly washed three times with water, dialyzed for 24 h against 3.0 ml of a l mM CaC1, solution to obtain calcium salts, and then washed again with water and dried. The air-dried films were 22 pm thick.Calcite crystals were grown, as reported by Addadi et a1.[4], at a temperature of 18 _+2 "C by very slow diffusion of (NH,),CO, vapor in the dishes, containing 2.9 ml of a 7.5 mM CaCI, solution. The crystals obtained after different times, up to four days, were examined by optical and scanning electron microscopy and X-ray powder diffraction. Crystals were counted under a microscope ( x 40) and nucleation density (crystals per cm2) was averaged over the total surface of the film (19.6 cm'). The (001) oriented crystals were identified by the hexagonal symmetry in two dimensional projection down the c axis.