Formation of hydrated calcium oxalates in the presence of poly-L-aspartic acid.

Abstract

The effect of poly-L-aspartic acid (PA) on the crystal structure of calcium oxalate crystals grown after spontaneous nucleation was evaluated as a function of relative supersaturation and calcium:oxalate ratio in a buffered salt solution, with pH and ionic strength in the range of normal human urine. PA was used as a model for naturally occurring acidic urine proteins that have been shown to inhibit nucleation and growth of calcium oxalate crystals. The crystals grown were characterized by optical microscopy and X-ray powder diffraction. It was observed that calcium oxalate monohydrate was the preferred crystalline form in the absence of added PA, and it was the only crystalline form obtained at most conditions tested without PA. However, the presence of PA favored the formation of calcium oxalate dihydrate crystals, when present in adequate quantities. The quantity of PA required to affect this change in preferred crystal structure was increased at higher supersaturations and at lower calcium:oxalate ratios, exhibiting a non-linear dependence on both variables. PA was also shown to be a kinetic inhibitor of calcium oxalate dihydrate crystallization. Aspartic acid monomer was found to cause no change in the preferred structure of calcium oxalate monohydrate at mass concentrations well beyond those required with PA to obtain 100% calcium oxalate dihydrate, indicating the critical importance of the polymeric nature of PA for this effect on crystal structure.