Understanding the effect that specific amino acids (AA) exert on calcium phosphate (CaPs) formation is proposed as a way of providing deeper insight into CaPs’ biomineralization and enabling the design of tailored-made additives for the synthesis of functional materials. Despite a number of investigations, the role of specific AA is still unclear, mostly because markedly different experimental conditions have been employed in different studies. The aim of this paper was to compare the influence of different classes of amino acids, charged (aspartic acid, Asp and lysine, Lys), polar (asparagine, Asn and serine, Ser) and non-polar (phenylalanine, Phe) on CaPs formation and transformation in conditions similar to physiological conditions. The precipitation process was followed potentiometrically, while Fourier transform infrared spectroscopy, powder X-ray diffraction, electron paramagnetic spectroscopy (EPR), scanning and transmission electron microscopy were used for the characterization of precipitates. Except for Phe, all investigated AAs inhibited amorphous calcium phosphate (ACP) transformation, with Ser being the most efficient inhibitor. In all systems, ACP transformed in calcium-deficient hydroxyapatite (CaDHA). However, the size of crystalline domains was affected, as well as CaDHA morphology. In EPR spectra, the contribution of different radical species with different proportions in diverse surroundings, depending on the type of AA present, was observed. The obtained results are of interest for the preparation of functionalized CaPs’, as well as for the understanding of their formation in vivo.
CaCO3 precipitation is physical-chemical basis of biomineral formation of hard tissue (shells, skeletons) in marine calcifying organisms (=biomineralization). Processes controlling biomineralization are still not fully clarified, so the study of influence of pH on basic processes of CaCO3 precipitation should contribute to better understanding of biomineralization under climate change. This paper reports on the effect of initial pH (pH0) and type of stirring (mechanical and magnetical) on spontaneous precipitation and phase composition, size and morphology of spontaneously precipitated CaCO3 formed at the identical initial supersaturation, ionic strength and a(Ca2+)/a(CO32−) ratio. The initial pH varied in a range 8.50 ≤ pH0 ≤ 10.50 and included values relevant for mimicking the conditions related to biomineralization in marine organisms. In all systems two CaCO3 polymorphs were found: calcite and/or vaterite. The increase of pH0 favoured the formation of rhombohedral calcite no matter the type of stirring. This was exclusively influenced by the systems’ pH0 (other relevant initial parameters were identical). Furthermore, increase of pH0 caused change of vaterite morphology from cauliflower-like spheroids to regular spherulites. The mechanically stirred systems produced larger calcite and vaterite particles and higher content of calcite.
Plate-like calcite crystals with expressed unstable {001} planes are interesting research model for investigations of interfacial interactions of different additive molecules, but also the crystal growth mechanisms. The aim of this study is to reproducibly prepare a significant amount of well-defined plate-like calcite crystals and to investigate the critical experimental parameters. Thus, in precipitation system c(NaHCO3) = c(CaCl2) = 0.1 mol dm−3, the influence of hydrodynamic parameters (mode of mixing of the reaction components) and a presence of lithium ions Li+ within a wide range of concentrations, 0.0 mol dm−3 < c(Li+) < 1.0 mol dm−3, have been studied. In addition, the kinetics of the solution mediated transformation of the initially formed metastable polymorph, vaterite, were followed in order to reproducibly describe the formation of stable calcite with expressed unstable morphology. The results indicate that the plate-like calcite is formed predominantly when the ultrasound irradiation is applied at c(Li+) ≥ 0.3 mol dm−3. On the other hand, when the magnetic and mechanical stirring are applied at higher Li+ concentrations, truncated rhombohedral crystals in a mixture with plate-like crystals are obtained. It was also found that the Li+ addition significantly prolonged the transformation, mainly by inhibiting the crystal growth of calcite.
Liposomes (lipid vesicles) are often considered to be a versatile tool for the synthesis of advanced materials, as they allow various control mechanisms to tune the materials’ properties. Among diverse materials, the synthesis of calcium phosphates (CaPs) and calcium carbonates (CaCO3) using liposomes has attracted particular attention in the development of novel (bio)materials and biomineralization research. However, the preparation of materials using liposomes has not yet been fully exploited. Most of the liposomes used have been anionic and/or zwitterionic, while data on the influence of cationic liposomes are limited. Therefore, the aim of this study was to investigate and compare the influence of differently charged liposomes on CaPs and CaCO3 formation. Zwitterionic 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC), negatively charged 1,2-dimyristoyl-sn-glycero-3-phospho-L-serine (DMPS), and positively charged 1,2-dioleoyl-sn-glycero-3-ethylphosphocholine (EPC) lipids were used to prepare the respective liposomes. The presence of liposomes during the spontaneous precipitation of CaPs and CaCO3 affected both the precipitation and transformation kinetics, as well as the morphology of the precipitates formed. The most prominent effect was noted for both materials in the presence of DMPS liposomes, as (nano) shell structures were formed in both cases. The obtained results indicate possible strategies to fine-tune the precipitation process of CaPs and CaCO3, which may be of interest for the production of novel materials.
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