Abstract:With their unique ability for substrate recognition and their sequence-specific self-assembly properties, peptides play an important role in controlling the mineralization of inorganic materials in natural systems and in controlling the assembly of soft materials into complex structures required for biological functions. Here we report the use of an engineered heptapeptide that can differentiate between the crystalline anhydrous polymorphs of calcium carbonate. This peptide contains the positively charged amin… Show more
“…However, increasingly sophisticated methods for identifying the macromolecules involved in CaCO 3 biomineralisation suggest a more complex picture in which regulation is achieved using an array of molecules including glycosylated proteins, peptides, metabolites and polysaccharides 18 . Further, binding assays have shown that weakly acidic peptides can associate strongly with CaCO 3 19–21 , and atomic force microscopy (AFM) and molecular dynamics (MD) simulations have demonstrated the strong binding of small hydroxyl-functionalised molecules 22,23 . This suggests potential roles for low-charge and basic molecules in controlling crystal properties.…”
Acidic macromolecules are traditionally considered key to calcium carbonate biomineralisation and have long been first choice in the bio-inspired synthesis of crystalline materials. Here, we challenge this view and demonstrate that low-charge macromolecules can vastly outperform their acidic counterparts in the synthesis of nanocomposites. Using gold nanoparticles functionalised with low charge, hydroxyl-rich proteins and homopolymers as growth additives, we show that extremely high concentrations of nanoparticles can be incorporated within calcite single crystals, while maintaining the continuity of the lattice and the original rhombohedral morphologies of the crystals. The nanoparticles are perfectly dispersed within the host crystal and at high concentrations are so closely apposed that they exhibit plasmon coupling and induce an unexpected contraction of the crystal lattice. The versatility of this strategy is then demonstrated by extension to alternative host crystals. This simple and scalable occlusion approach opens the door to a novel class of single crystal nanocomposites.
“…However, increasingly sophisticated methods for identifying the macromolecules involved in CaCO 3 biomineralisation suggest a more complex picture in which regulation is achieved using an array of molecules including glycosylated proteins, peptides, metabolites and polysaccharides 18 . Further, binding assays have shown that weakly acidic peptides can associate strongly with CaCO 3 19–21 , and atomic force microscopy (AFM) and molecular dynamics (MD) simulations have demonstrated the strong binding of small hydroxyl-functionalised molecules 22,23 . This suggests potential roles for low-charge and basic molecules in controlling crystal properties.…”
Acidic macromolecules are traditionally considered key to calcium carbonate biomineralisation and have long been first choice in the bio-inspired synthesis of crystalline materials. Here, we challenge this view and demonstrate that low-charge macromolecules can vastly outperform their acidic counterparts in the synthesis of nanocomposites. Using gold nanoparticles functionalised with low charge, hydroxyl-rich proteins and homopolymers as growth additives, we show that extremely high concentrations of nanoparticles can be incorporated within calcite single crystals, while maintaining the continuity of the lattice and the original rhombohedral morphologies of the crystals. The nanoparticles are perfectly dispersed within the host crystal and at high concentrations are so closely apposed that they exhibit plasmon coupling and induce an unexpected contraction of the crystal lattice. The versatility of this strategy is then demonstrated by extension to alternative host crystals. This simple and scalable occlusion approach opens the door to a novel class of single crystal nanocomposites.
“…Complexing agents like citrate were suggested to affect early ACP formation 16,17 through the stabilization of ACP clusters whose subsequent aggregation can be promoted by the presence of non-collagenous proteins. 22 Therefore it was tempting to combine the bioactivity and osteoconductivity of vaterite nanoparticles with the flexibility and degradability of a hydrogel in order to develop a new bone grafting material. 18 Amorphous CaCO 3 (ACC) has been considered a potential inorganic precursor to induce the formation of bone minerals.…”
Biomimetic materials have been gaining increasing importance for use as bone biomaterials, because they may provide regenerative alternatives for the use of autologous tissues for bone regeneration. We demonstrate a promising alternative for the use of biomimetic materials based on a biodegradable PEG hydrogel loaded with vaterite nanoparticles as mineral storage. Vaterite, the least stable CaCO 3 polymorph, is stable enough to ensure the presence of a potential ion buffer for bone regeneration, but still has sufficient reactivity for the transformation from CaCO 3 to hydroxyapatite (HA). A combination of powder X-ray diffraction (PXRD), electron microscopy, and Fourier-transform infrared (FT-IR) and Raman spectroscopy showed the transformation of vaterite nanoparticles incorporated in a PEG-acetal-DMA hydrogel to hydroxycarbonate apatite (HCA) crystals upon incubation in simulated body fluid at human body temperature within several hours. The transformation in the PEG-acetal-DMA hydrogel scaffold in simulated body fluid or phosphate saline buffer proceeded significantly faster than for free vaterite. The vaterite-loaded hydrogels were free of endotoxin and did not exhibit an inflammatory effect on endothelial cells. These compounds may have prospects for future applications in the treatment of bone defects and bone degenerative diseases. † Electronic supplementary information (ESI) available: Fig. S1, quantitative phase analysis and determination of the crystallite size based on the XRD data after soaking vaterite nanoparticles in SBF at 37 1C for (a) 24 h (b) 48 h and (c) 72 h. See
“…We have recently developed a method to synthesise nonagglomerated and non-functionalised vaterite nanoparticles (Mugnaioli, Andrusenko, Schüler, et al, 2012;Schüler, Renkel, Hobe, et al, 2014;Schüler & Tremel, 2011). Vaterite, the least stable but most soluble crystalline polymorph of calcium carbonate forms positively charged nanoparticles that react and can be functionalised with carboxylate or phosphonate-bearing ligands (Schüler & Tremel, 2011).…”
We have previously described a promising alternative to conventional synthetic bone biomaterials using vaterite, a metastable CaCO polymorph that increases the local Ca concentration in vitro and leads to an oversaturation of phosphate, the primary bone mineral. This stimulates a natural bone-like mineralisation in a short period of time. In this study, sterile and endotoxin-free vaterite particles were synthesised in a nearly quantitative yield. The 500-1,000 nm vaterite particles did not exhibit any cytotoxic effects as measured by MTS, lactate dehydrogenase, or crystal violet assays on the human osteoblast cell line (MG-63) exposed to concentrations up to 500 μg/ml vaterite up to 72 hr. MG-63, primary human osteoblasts or human umbilical vein endothelial cells in the presence of vaterite up to 500 μg/ml for 7 days exhibited typical growth patterns. Endothelial cells exhibited a normal induction of E-selectin after exposure to LPS and MG-63 cells in osteogenic differentiation medium showed an increased expression of alkaline phosphatase compared with the respective control cells without vaterite. MG-63 cultured on a vaterite-containing degradable poly(ethylene glycol)-hydrogel exhibited strong adhesion and proliferation, similar to cells on cell culture plates. Cells did not attach to gels without vaterite. Our results demonstrate that vaterite particles are biocompatible, do not influence cell gene expression, and that vaterite in hydrogels may be able to serve for adhesion of osteoblasts and as a mineral substrate for natural bone formation by osteoblasts. These characteristics make vaterite particles a highly favourable compound for use in bone regeneration applications.
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