A key feature of biomineralization processes is that they take place within confined volumes, in which the local environment can have significant effects on mineral formation. Herein, we investigate the influence of confinement on the formation mechanism and structure of calcium phosphate (CaP). This is of particular relevance to the formation of dentine and bone, structures of which are based on highly mineralized collagen fibrils. CaP was precipitated within 25–300 nm diameter, cylindrical pores of track etched and anodised alumina membranes under physiological conditions, in which this system enables systematic study of the effects of the pore size in the absence of a structural match between the matrix and the growing crystals. Our results show that the main products were polycrystalline hydroxapatite (HAP) rods, together with some single crystal octacalcium phosphate (OCP) rods. Notably, we demonstrate that these were generated though an intermediate amorphous calcium phosphate (ACP) phase, and that ACP is significantly stabilised in confinement. This effect may have significance to the mineralization of bone, which can occur through a transient ACP phase. We also show that orientation of the HAP comparable, or even superior to that seen in bone can be achieved through confinement effects alone. Although this simple experimental system cannot be considered, a direct mimic of the in vivo formation of ultrathin HAP platelets within collagen fibrils, our results show that the effects of physical confinement should not be neglected when considering the mechanisms of formation of structures, such as bones and teeth. 相似文献
Although the polymorphism of calcium carbonate is well known, and its polymorphs—calcite, aragonite, and vaterite—have been highly studied in the context of biomineralization, polyamorphism is a much more recently discovered phenomenon, and the existence of more than one amorphous phase of calcium carbonate in biominerals has only very recently been understood. Here we summarize what is known about polyamorphism in calcium carbonate as well as what is understood about the role of amorphous calcium carbonate in biominerals. We show that consideration of the amorphous forms of calcium carbonate within the physical notion of polyamorphism leads to new insights when it comes to the mechanisms by which polymorphic structures can evolve in the first place. This not only has implications for our understanding of biomineralization, but also of the means by which crystallization may be controlled in medical, pharmaceutical, and industrial contexts. 相似文献
The effect of concentration of structurally-different carboxylic acids such as ethylene diamine tetraacetic acid (H4edta), citric acid (H3cit), tartaric acid (H2tart), and acetic acid (HOAc) on growth and aggregation of calcium oxalate (CaOxa) in gel systems was comparatively investigated. H2tart and H3cit could change the morphology of cal- cium oxalate monohydrate (COM) and induce the formation of calcium oxalate dihydrate (COD). H4edta could induce the formation of COD at a lower concentration of 0.33 mmol/L and have the strongest ability to inhibit aggregation of COM. HOAc inhibited COM aggregation only at a higher concentration than 500 mmol/L. With increasing the number of carboxylic groups in an acid or increasing the concentration of carboxylic acid, the capacity of this acid to induce COD formation and to inhibit growth and aggregation of COM crystals increased. That is, this capacity followed the order: H4edta〉H3cit〉H2tart〉 〉HOAc. The result in this work suggested that the presence of H3cit and H2tart in urine played a role in the natural defense against stone formation. 相似文献
Biomineralization is believed to be achieved by the intimate cooperation of soluble macromolecules and an insoluble matrix at the specific inorganic–organic interface. It has been reported that positively charged matrices play an important role in controlling the structure of CaCO3 at surfaces, although detailed mechanisms remain unclear. In this work, we studied the transformation from amorphous CaCO3 to calcite crystals on surfaces by using thin films of poly(2‐(dimethylamino)ethyl methacrylate) (PDMAEMA) and its quaternized form. The positively charged PDMAEMA film was found to possess unique properties for CaCO3 crystallization: individually separated, single calcite crystals were formed on the PDMAEMA film in the absence of poly(acrylic acid) (PAA), while circularly fused calcite crystals were formed in the presence of PAA. The circularly fused (rosette‐shaped) calcite crystals could be changed from a completely packed rosette to a ring‐shaped, hollow structure by tuning the crystallization conditions. A number of factors, such as reaction time, amount of (NH4)2CO3, concentration of PAA, and charge of matrix‐films, were varied systematically, and we now propose a mechanism based on these observations. 相似文献
Phytate has been classified as an anti-nutrient, but there are no adverse effects from the consumption of a balanced diet with 1 to 2 g of daily phytate (inositol-hexaphosphate, InsP6) as a calcium magnesium salt, the form naturally present in grains. Furthermore, recent research has shown that phytate consumption may prevent pathological calcifications, such as kidney stones and cardiovascular calcifications. However, many endogenous and exogenous enzymes can hydrolyze phytate to lower inositol phosphates (InsPs) that also have biological activity. We performed a controlled hydrolysis of phytate and identified the products (InsPs) using tandem mass spectrometry (MS/MS). The total level of all InsPs was measured using a non-specific methodology. In addition, we evaluated the effects of the InsP6 hydrolysates on calcium oxalate crystallization using scanning electron microscopy and measuring the time needed for the induction of crystallization. Our results indicate that InsP6 and its hydrolysis products functioned as effective inhibitors of calcium oxalate crystallization. Thus, even though InsP6 is hydrolyzed after consumption, the enzymatic products also have the potential to reduce pathological calcifications. Finally, although it is useful to measure the overall level of InsPs in biological fluids, such as urine, there is a need to develop simple analytical methods to quantify the level of individual InsPs. 相似文献
Summary: Crystallization, melting and annealing of nanoparticles of tetracontane were simulated via a Monte Carlo method on the second nearest neighbor diamond (2nnd) lattice by including short‐ and long‐range interactions. Nanoparticles can be obtained from an equilibrated tetracontane melt by increasing three periodic lengths to values that are effectively infinite. Nanoparticles, which contain 155 chains of C40H82, have been produced. After a deep quench from 473 K to 298 K, the crystallization process was investigated by the evolution of the density profile, fraction of bonds in the trans state, and the orientational order parameter. The vicinity of the center is less dense and less well ordered than portions of the nanoparticle located further from the center. The crystals form first in the region close to the surface. Each nanoparticle usually contains multiple crystalline domains. A melting phenomenon was observed at a temperature about 365 K when the nanoparticle crystal was heated. Annealing of the multiple domain crystal at 360 K can transform the structure to a more regular one without a grain boundary.
Snapshot of the final structure containing a single domain crystal after 20 million MCS. 相似文献
Calcium phosphates stand among the most promising nanobiomaterials in key biomedical applications, such as bone repairment, signalling or drug/gene delivery. Their intrinsic properties as crystalline structure, composition, particle shape and size define their successful use. Among these compounds, metastable amorphous calcium phosphate (ACP) is currently gaining particular attention due to its inherently high reactivity in solution, which is crucial in bone development mechanisms. However, the preparation of this highly desired (bio)material with control over its shape, size and phase purity remains as a synthetic challenge. In this work, the epoxide route was adapted for the synthesis of pure and stable ACP colloids. By using biocompatible solvents, such as ethylene glycol and/or glycerine, it was possible to avoid the natural tendency of ACP to maturate into more stable and crystalline apatites. Moreover, this procedure offers size control, ranging from small nanoparticles (60 nm) to micrometric spheroids (>500 nm). The eventual fractalization of the internal mesostructured can be tuned, by simply adjusting the composition of the ethylene glycol:glycerine solvent mixture. These findings introduce the use of green solvents as a new tool to control crystallinity and/or particle size in the synthesis of nanomaterials, avoiding the use of capping agents and preserving the natural chemical reactivity of the pristine surface. 相似文献
Stable silver nanoparticles was successfully synthesized by chemical reduction of silver nitrate in an ionic liquid,1-n-butyl-3-methylimidazolium tetrafluoroborate([BMIM]·BF4) at room temperature.Results of UV-Vis diffuse reflectance spectroscopy show as-prepared Ag nanoparticles exhibit a typical emission peak at 400―430 nm.By varying the reaction temperature and the precursor concentration,the size and the shape of the silver nanoparticles could be easily controlled under mild conditions.Analyses of trans... 相似文献
Skeletal Ni catalysts were prepared from an amorphous Ni40Zr60 alloy (a‐NiZr) by heating at various temperatures under vacuum, followed by the selective extraction of Zr moieties by an HF treatment. Each sample was characterized by various spectroscopic methods, and the catalytic performance was tested in the hydrogenation of 1‐octene. The differences in preparation temperatures of a‐NiZr strongly affected the catalytic performance of the obtained catalysts, whereby those prepared from heated a‐NiZr in the pre‐crystallization state exhibited higher catalytic activity. Especially, moderate thermal treatment of a‐NiZr at a temperature slightly lower than that for its crystallization, that is, ~573 K, resulted in a significant enhancement of the catalytic activity. Such prepared skeletal Ni catalyst can also be used efficiently for hydrogen generation from aqueous hydrazine. 相似文献