Calcium Phosphate with a Channel-like Morphology by Polymer Templating

Calcium phosphate mineralization from aqueous solution in the presence of organic growth modifiers has been intensely studied in the recent past. This is mostly due to potential applications of the resulting composites in the biomaterials field. Polymers in particular are efficient growth modifiers. As a result, there has been a large amount of work on polymeric growth modifiers. Interestingly, however, relatively little work has been done on polycationic additives. The current paper shows that poly(ethylene oxide)b-poly(L-lysine) block copolymers lead to an interesting morphology of calcium phosphate precipitated at room temperature and subjected to a mild heat treatment at 85 degrees C. Electron microscopy, synchrotron X-ray diffraction, and porosity analysis show that a (somewhat) porous material with channel-like features forms. Closer inspection using transmission electron microscopy shows that the channels are probably not real channels. Much rather the morphology is the result of the aggregation of ca. 100-nm-sized rodlike primary particles, which changes upon drying to exhibit the observed channel-like features. Comparison experiments conducted in the absence of polymer and with poly(ethylene oxide)-b-poly(L-glutamate) show that these features only form in the presence of the polycationic poly(L-lysine) block, suggesting a distinct interaction of the polycation with either the crystal or the phosphate ions prior to mineralization.