This study investigated the effect of colloidal selenium nanoparticles modified with bovine serum albumin (nanoSe0–BSA) on the crystal phase and morphology of CaC2O4 and explained the cooperative inhibition mechanism of nanoSe0 and BSA on the crystallization of CaC2O4. The results were compared with those for nanoSe0 and BSA individually. NanoSe0 could induce the formation of oval or spherical calcium oxalate monohydrate (COM) crystals at high concentrations. BSA could induce the formation of hexagonal plate-shaped COM crystals at low concentrations and the formation of thin diamond-shaped COM crystals and mixed hydrates with cracks at high concentrations. NanoSe0–BSA showed additive effects on CaC2O4 crystal growth. NanoSe0–BSA could induce the formation of mixed hydrates with more surface cracks and obvious voids at relatively low BSA concentrations. These mixed hydrates were considered to be calcium oxalate trihydrate (COT) or calcium oxalate dihydrate (COD) crystals containing BSA or nanoSe0–BSA. These results were a consequence of the interaction of nanoSe0 with BSA. UV–vis, circular dichroism, and FT-IR spectra indicated that the binding of nanoSe0 to BSA induces a change in the secondary structure of BSA and forms the complex. The nanoSe0–BSA binding constant (2.257 × 104 L mol–1) and number of binding sites (1.13) were calculated from the data of fluorescence spectra.
The nanoSe0-polyphenol complexes with a 3:1 polyphenol/nanoSe0 molar ratio were prepared by colloidal selenium nanoparticles (nanoSe0) modified with gallic acid (GA), propyl gallate (PG), and pyrogallic acid (PA), which were spherical with average diameter about 38–77 nm. On this basis, we studied the effect of nanoSe0-polyphenol on the CaC2O4 crystallization and also elaborated the modulation mechanism, which were compared with those for each polyphenol individually. NanoSe0-GA and nanoSe0-PA were easy to induce the formation of calcium oxalate dihydrate (COD) crystals, while nanoSe0-PG induced the formation of quasi-rectangular calcium oxalate monohydrate (COM), multilayered calcium oxalate trihydrate (COT) crystals, and an amount of COD crystals in a dose-dependent fashion by nanoSe0-PG. The strong effect of nanoSe0-polyphenol on the formation of COD and COT crystals could be attributed to electrostatic interaction between nanoSe0-polyphenol and CaC2O4 crystals. The results obtained in the polyphenol system were similar to, as well as different from, nanoSe0-polyphenol because the effect of the polyphenol on the CaC2O4 crystallization could result from not only electrostatic interaction between polyphenols and Ca2+ ions, but also hydrogen bonding interaction between the polyphenols and C2O4 2– groups. All the obtained COD crystals were thermostable even at 70 °C, while COT crystals were temperature dependent.
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