Rod-like Hydroxyapatite Research Articles

The effects of surface modification on the supercapacitive behaviors of novel mesoporous carbon derived from rod-like hydroxyapatite template

Novel mesoporous carbon has been synthesized using rod-like nano-hydroxyapatite (HA) particles as templates, sucrose as carbon precursor by polymerizing, carbonizing and the removal of templates with HCl solution. In the process, HA not only acted as an endotemplate but also an exotemplate producing micropores and mesopores. Subsequently, mesoporous carbon was modified by HNO3 solution with different concentration. The morphology, pore structure, and surface functional groups of the as-obtained samples are analyzed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer–Emmett–Teller method (BET), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The electrochemical performance for electrochemical capacitors is evaluated in a 1M H2SO4 aqueous solution. The results manifest that the structrue of resultant carbon with a high surface area (719.7m2g−1) and large pore volume (1.51cm3g−1) is the replica of HA. After modification, the surface area and pore volume mesoporous carbons slightly decrease, while their electrochemical performance have been significantly improved with the increase of the capacitance from 125.7 to 170.1Fg−1 and a non-decayed cycle life over 5000 cycles for HA-C-0.15N.

Surfactant-Assisted Hydrothermal Synthesis of Hydroxyapatite Nanopowders

Rod-like hydroxyapatite nanoparticles (n-HAp) with a highly ordered nanostructure were prepared by hydrothermal synthesis from calcium chloride, and phosphoric acid, as calcium and phosphorus sources, respectively. Various surfactant families such as cationic (CTAB), anionic (SDS) and nonionic (Triton X-100) were used as regulators of the nucleation and crystal growth. The synthesized nanopowders were characterized using X-ray diffraction (XRD), Fourier transform infrared spectrograph (FTIR) and transmission electron microscopy (TEM). The rod-like morphology was obtained regardless of the surfactant used during the hydrothermal treatment, but the aspect ratio of the crystals was found to be surfactant dependent. The mechanism of crystal growth as well-oriented nanostructure is discussed.

Hydroxyapatite/ovalbumin composite particles as model protein carriers for bone tissue engineering: I. Synthesis and characterization

Hydroxyapatite (HAp) nanoparticles were synthesized from the co-precipitation reaction between calcium oxide from discarded egg shells and phosphoric acid in the absence and the presence of ovalbumin (OVA). 2-Amino-2-hydroxymethyl-propane-1,3-diol (tris-base) was used to control the pH during the co-precipitation (i.e., 7–9). The formation of HAp was confirmed by X-ray diffraction analysis, while both the Fourier-transform infrared spectroscopy and the thermogravimetric analysis confirmed the existence of OVA within the HAp–OVA particles. The crystallite sizes of the individual crystalline entities within the HAp and the HAp–OVA particles were approximated from the (002) reflection peaks by means of the Scherrer's equation. The average particle sizes of the HAp and the HAp–OVA particles were measured by particle size analysis. Transmission electron microscopy revealed that these particles were aggregates of rod-like HAp nanocrystals, whereas scanning electron microscopy revealed that these particles ultimately formed into larger aggregates. Lastly, the decrease in the pH during the precipitation process and the presence of OVA were responsible for the observed increase in the values of pore size, BET specific surface area, and pore volume of the resulting HAp particles.

SYNTHESIS OF MESOPOROUS HYDROXYAPATITE THROUGH A SOFT TEMPLATE ROUTE USING NON-IONIC SURFACTANT

Conventional synthesis of mesoporous hydroxyapatite (HAp) commonly employs coprecipitation method using cationic surfactants such as CTAB. Such surfactants are expensive and create tinier mesopores without an interconnecting pore structure. Using non-ionic surfactants in the synthesis of mesoporous HAp, the pore formation could be induced to tailor desirable pore characteristics. This paper reports on synthesis of mesoporous HAp through soft template route using non-ionic surfactants P123, F127 and P123/F127. Calcination was carried out at 550 °C for 6 hours to reveal pores through the removal of the organic surfactant. The formation of HAp prior and subsequent to the calcination was evaluated through several materials characterization techniques. The X-ray diffraction (XRD) diffractograms revealed characteristic peaks of HAp corresponds to a typical HAp crystal phase, whereby a hexagonal lattice structure was deduced. SEM micrographs revealed rod-like HAp particles with diameter of approximately 24 nm and length ranging from 100 nm. TEM revealed the formation of nanopore channels within the rod-like structure, aligned in a lengthwise direction within the rods. The nanopore channels were consistent with the cavities being generated by the removal of non-ionic surfactant. The pores formed were found to be randomly distributed within the HAp structure.

Single‐step mineralization of woodpile chitosan scaffolds with improved cell compatibility

A facile and efficient single-step mineralization approach was exploited for achieving nanoscopic hydroxyapatite (HAP) crystal layer in chitosan porous matrix, wherein a mixed water-ethanol solvent was used to control the growth of minerals. The crystallographic structure, morphology, and mechanical properties of the scaffold were analyzed with XRD, FTIR, environmental scanning electric microscopy (ESEM), TEM, and compression tests. The behaviors and responses of MC3T3-E1 pre-osteoblast cells on the scaffolds were studied as well. The results showed that the scaffolds kept woodpile structure with predefined and controlled hierarchical structure after mineralization. The inorganic phase in the mineralized chitosan scaffolds was determined as pure rod-like HAP, which settled densely on the matrix. The compression strength and compressive modulus of the scaffolds increased dramatically to 0.54 ± 0.005 MPa and 5.47 ± 0.65 MPa, respectively. During a culture period of 2 and 3 weeks, cell proliferation and in-growth were observed by phase contrast light microscopy and SEM. The alkaline phosphatase (ALP) activity increased after 1 week. Cell viability and cell proliferation index (PI) obtained higher values than that of the chitosan scaffolds. The novel single-step mineralization approach and the porous hybrid scaffolds would be a promising method for designing hybrid bone graft.

Growth mechanism of hydroxyapatite-coatings formed on pure magnesium and corrosion behavior of the coated magnesium

Hydroxyapatite (HAp) coatings were uniformly formed on pure Mg by a hydrothermal treatment using a C 10H 12N 2O 8Na 2Ca (Ca-EDTA) solution. The growth mechanism of the HAp coating was investigated with XRD, SEM and TEM. At the initial stage, dome-shape HAp precipitates were formed on the Mg. Subsequently, the precipitates grew and the coating became a dual-layer consisting of an inner dense HAp layer and outer course layer consisting of rod-like HAp crystals. The protectiveness of the coatings with different treatment times was investigated by a polarization test in a 3.5 wt.% NaCl solution. The corrosion current density decreased with the growth of the HAp coating.

Frabicating hydroxyapatite nanorods using a biomacromolecule template

Rod-like hydroxyapatite (HAp) nanoparticles with various aspect ratios are synthesized by means of low-temperature hydrothermal method in the presence of a N-[(2-hydroxy-3-trimethylammonium) propyl]chitosan chloride (HTCC) template. The synthesized HAps were examined by X-ray diffraction (XRD), Fourier transform infrared spectrophotometer (FTIR) and transmission electron microscopy (TEM) techniques. The results reveal that HAps are rod-like monocrystals, where the size and morphology can be tailored by varying synthesis conditions, such as pH, hydrothermal synthesis temperature and the ratio of PO43− to the quaternary ammonium in HTCC. The mechanism of HTCC template on HAp nanorod preparation is analyzed.

Microstructure of hydroxyapatite- and octacalcium phosphate-coatings formed on magnesium by a hydrothermal treatment at various pH values

Hydroxyapatite (HAp) coatings with and without octacalcium phosphate (OCP) were uniformly formed on pure magnesium by a hydrothermal treatment using a Ca-EDTA solution. The crystal structure, crystallographic orientation and lattice images were investigated using transmission electron microscopy (TEM) and high-resolution TEM. It was demonstrated that the crystal phase and microstructure of the calcium phosphate-coatings can vary with the pH of the treatment solution. In a weak acid treatment solution, a dual-layer structure was formed: an outer coarse layer consisting of plate-like OCP crystals and an inner dense layer consisting primarily of HAp crystals. One piece of the OCP plate corresponded to a single OCP crystal growing parallel to the (1 0 0) OCP. In a weak alkali treatment solution, a dual-layer structure was also formed: an outer coarse layer consisting of rod-like HAp crystals and an inner dense layer consisting of HAp crystals. One piece of the HAp rod corresponded to a single HAp crystal growing along [0 0 2] HAp. In a strong alkali treatment solution, needle-like HAp crystals were formed. No defect was observed in the lattice image of the OCP and HAp. The corrosion current density of pure magnesium in a 3.5 wt.% NaCl solution decreased with the HAp coating more significantly than the OCP + HAp coating. It is revealed that the degree of protection afforded by calcium phosphate-coatings varies with their crystal phase and microstructure.

Poly( d, l-lactide-co-glycolide)/hydroxyapatite core-shell nanospheres. Part 1: A multifunctional system for controlled drug delivery

Biodegradable poly( d, l-lactide-co-glycolide) (PLGA) and bioactive hydroxyapatite (HAp) are selected for the formation of a multifunctional system with the specific core-shell structure to be applied as a carrier of a drug. As a result, both components of PLGA/HAp core-shells are able to capture one part of the drug. Polymeric shells consisting of small nanospheres up to 20 nm in size act as a matrix in which one part of the drug is dispersed. In the same time, ceramic cores are formed of rod-like hydroxyapatite particles at the surface of which another part of the drug is adsorbed onto the interface between the polymer and the ceramics. The content of the loaded drug, as well as the selected solvent/non-solvent system, have a crucial influence on the resulting PLGA/HAp morphology and, finally, unimodal distribution of core-shells is obtained. The redistribution of the drug between the organic and inorganic parts of the material is expected to provide an interesting contribution to the kinetics of the drug release resulting in non-typical two-step drug release.

Synthesis and characterization of hydroxyapatite/β-tricalcium phosphate nanocomposites using microwave irradiation

Microwave assisted synthesis method is a relatively new approach employed to decrease synthesis time and form a more homogenous structure in biphasic calcium phosphate bioceramics. In this study, nanocrystalline HA/β-TCP composites were prepared by microwave assisted synthesis method and, for comparison reason, by conventional wet chemical methods. The chemical and phase composition, morphology and particle size of powders were characterized by FTIR, XRD and SEM, respectively. The use of microwave irradiation resulted in improved crystallinity. The amount of hydroxyapatite phase in BCP ranged from 5% to 17%. The assessment of bioactivity was done by soaking of powder compacts in simulated body fluid (SBF). The decreasing pH of the solution in the presence of β-TCP indicated its biodegradable behavior. Rod-like hydroxyapatite particles were newly formed during the treatment in SBF for microwave assisted substrate synthesis. In contrast, globular particles precipitate under same conditions if BCP substrates were synthesized using conventional wet chemical methods.

Economical and simple fabrication of rod-like hydroxyapatite nanocrystal with good dispersity and crystallinity

The homogeneous hydroxyapatite rod-like nanocrystal was prepared through an economical and simple route under gentle conditions by the aqueous chemical method. The high-resolution transmission electron microscope (HRTEM) displayed that the products were well-dispersed nanorods. The diameter of the nanorods was 4 ± 0.1 nm and the length was 20 ± 0.8 nm. The corresponding selected area electron diffraction (SAED) analysis demonstrated that the products were crystalline. Additionally, both X-ray powder diffraction (XRD) and Fourier transform infrared (FTIR) spectra indicated the characteristic peaks of hydroxyapatite. Moreover, the energy dispersive system (EDS) analysis demonstrated the Ca/P ratio of the product was 1.67, which was in consistent with commercial hydroxyapatite.

Will Fluoride Toughen or Weaken Our Teeth? Understandings Based on Nucleation, Morphology, and Structural Assembly

Fluoride exerts a substantial impact on the biominearlization of hydroxyapatite (HAP). In this study, the effect of fluoride on the nucleation kinetics of HAP was examined quantitatively in a simulated body fluid. It was found for the first time that fluoride promotes the nucleation of HAP. Furthermore, both the concentration of fluoride and the supersaturation of HAP play a key role in the formation of an ordered assembly of rod-like HAP crystallites. At relatively low concentrations of fluoride, an ordered assembly of rod-like crystallites similar to the structure of enamel could be obtained in the simulated body fluid, which could be explained by the self-epitaxial nucleation-mediated assembly. At high concentrations, fluoride may lead to the deterioration of the ordered assembled structure of HAP crystallites. That result is caused by the fast nucleation and growth of HAP crystallites when the supply of nucleation seeds is limited, resulting in the formation of spherulites. Our results illustrate how and why fluoride influences the self-assembled structures of HAP crystallites at low and high concentrations of F(-). Thus, they will substantially advance our understanding on the impact of fluoride ions on the mineralization of HAP and consequently on the dental and bone fluorosis.

High Throughput Methodology for Continuous Preparation of Hydroxyapatite Nanoparticles in a Microporous Tube-in-Tube Microchannel Reactor

A microporous tube-in-tube microchannel reactor (MTMCR) was successfully adopted to prepare hydroxyapatite (HAP) nanoparticles. The rodlike HAP nanoparticles with a mean size of 58 nm, a specific surface area of 49.32 m2/g, and a narrow size distribution were obtained in an MTMCR under a high throughput of 3 L/min. The mean particle size sharply decreased with increasing the continuous phase flow rate, while first decreased and subsequently increased with increasing the dispersed phase flow rate and the reactant concentration. The extension of the mixing distance led to the initial rapid and following slight decrease of the mean particle size. The size of HAP nanoparticles was also strongly dependent on the micropore size on the surface of inner tube. Small micropore size was beneficial for producing small particles. For comparison, HAP nanoparticles were also prepared in a stirred tank reactor (STR) and a T-junction microchannel reactor (TMCR), clearly exhibiting the advantages of the MTMCR over the STR ...

Potential Bioelectroactive Bone Regeneration Polymer Nanocomposites with High Dielectric Permittivity

The frequency dependence of the dielectric permittivity of (barium titanate–hydroxyapatite)/poly(vinylidene fluoride) three-phase nanocomposites is investigated at room temperature and different fractions of barium titanate. The permittivity increases with increasing concentration of barium titanate. A weak decrease in permittivity is also observed for frequencies below 106 Hz. The SEM image inset in a dielectric permittivity vs. frequency curve shows that rod-like hydroxyapatite and sphere-like barium titanate nanoparticles exist in the three-phase nanocomposites.

Interfacial Interactions between Calcined Hydroxyapatite Nanocrystals and Substrates

Interfacial interactions between calcined hydroxyapatite (HAp) nanocrystals and surface-modified substrates were investigated by measuring adsorption behavior and adhesion strength with a quartz crystal microbalance (QCM) and a contact-mode atomic force microscope (AFM), respectively. The goal was to develop better control of HAp-nanocrystal coatings on biomedical materials. HAp nanocrystals with rodlike or spherical morphology were prepared by a wet chemical process followed by calcination at 800 degrees C with an antisintering agent to prevent the formation of sintered polycrystals. The substrate surface was modified by chemical reaction with a low-molecular-weight compound, or graft polymerization with a functional monomer. QCM measurement showed that the rodlike HAp nanocrystals adsorbed preferentially onto anionic COOH-modified substrates compared to cationic NH2- or hydrophobic CH3-modified substrates. On the other hand, the spherical nanocrystals adsorbed onto NH2- and COOH-modified substrates, which indicates that the surface properties of the HAp nanocrystals determined their adsorption behavior. The adhesion strength, which was estimated from the force required to move the nanocrystal in contact-mode AFM, on a COOH-grafted substrate prepared by graft polymerization was almost 9 times larger than that on a COOH-modified substrate prepared by chemical reaction with a low-molecular-weight compound, indicating that the long-chain polymer grafted on the substrate mitigated the surface roughness mismatch between the nanocrystal and the substrate. The adhesion strength of the nanocrystal bonded covalently by the coupling reaction to a Si(OCH3)-grafted substrate prepared by graft polymerization was approximately 1.5 times larger than that when adsorbed on the COOH-grafted substrate.

Effect of silk sericin on assembly of hydroxyapatite nanocrystals into enamel prism-like structure

Taking the inspiration from the biomineral, the silk sericin was selected to modulate the assembly of nanosized hydroxyapatite crystals via a modified co-precipitation method. The effect of silk sericin concentration and mineralization time on the formation of hydroxyapatite nanocrystals, including their nucleation, growth, aggregation, especially assembly dynamics, were investigated using the transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy. The results revealed that both the concentration of silk sericin and the mineralization time could affect the size, morphology and assembly of hydroxyapatite crystals. Higher concentration of silk sericin in the reaction system was apt to form the larger hydroxyapatite crystals and longer mineralization time helped to improve the crystallinity of hydroxyapatite crystals together with an increase of crystal size. More interested thing was that an arrangement of nanocrystals in order was observed when the concentration of silk sericin was kept at 1(w/v)% in the reaction system. The larger rod-like hydroxyapatite crystals of 300–500 nm in length and 50–80 nm in diameter were assembled along the c-axis by the smaller crystals of ca. 20 nm under the control of silk sericin, whose arrangement method was similar to the natural enamel. A proposed formation mechanism of the special structure was elucidated. In addition, the biocompatibility of obtained crystals was evaluated in vitro and their strong ability to promote the cell differentiation and proliferation was proved in the paper, which may be important for the biomedical applications and also for the fundamental studies of cell–matrix interactions.

Electrospun PVA/HAp nanocomposite nanofibers: biomimetics of mineralized hard tissues at a lower level of complexity

Based on the biomimetic approaches the present work describes a straightforward technique to mimic not only the architecture (the morphology) but also the chemistry (the composition) of the lowest level of the hierarchical organization of bone. This technique uses an electrospinning (ES) process with polyvinyl alcohol (PVA) and hydroxyapatite (HAp) nanoparticles. To determine morphology, crystalline structures and thermal properties of the resulting electrospun fibers with the pure PVA and PVA/HAp nanocomposite (NC) before electrospinning various techniques were employed, including transmission electron microscopy (TEM), high-resolution TEM (HR-TEM), scanning electron microscopy (SEM), x-ray diffraction (XRD), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). In addition, FT-IR spectroscopy was carried out to analyze the complex structural changes upon undergoing electrospinning as well as interactions between HAp and PVA. The morphological and crystallographic investigations revealed that the rod-like HAp nanoparticles exhibit a nanoporous morphology and are embedded within the electrospun fibers. A large number of HAp nanorods are preferentially oriented parallel to the longitudinal direction of the electrospun PVA fibers, which closely resemble the naturally mineralized hard tissues of bones. Due to abundant OH groups present in PVA and HAp nanorods, they strongly interact via hydrogen bonding within the electrospun PVA/HAp NC fibers, which results in improved thermal properties. The unique physiochemical features of the electrospun PVA/HAp NC nanofibers prepared by the ES process will open up a wide variety of future applications related to hard tissue replacement and regeneration (bone and dentin), not limited to coating implants.

Histological reaction of sintered nanohydroxyapatite‐coated cuff and its fibroblast‐like cell hybrid for an indwelling catheter

Rapid tissue-ingrowth of a sintered hydroxyapatite(HAp)-coated and cell-hybrid subcutaneous cuff equipped with an indwelling catheter was developed. The rod-like HAp nanoparticles were coated by covalent bonding on the surface of the silk fibroin (SF) fibers for about 100 microm of the length. The fibers were transplanted three-dimensionally on a cuff substrate made of silicone elastomer with an adhesive. The fibroblast-like cells, explanted and proliferated from skin tissue containing the epidermis, dermis, and subcutaneous tissue of Japanese white rabbits, were incubated on the three-dimensional cuff for three days. Three types of cuff--polyester, HAp-coated, and cell-hybrid cuffs--were percutaneously implanted into the backs of the same animals for 3 and 7 days. The subcutaneous tissues around the cuffs were stained with hematoxylin-eosin. Immunohistochemical staining to identify macrophages and alpha-smooth muscle actin (alpha-SMA) was also done and examined by light microscopy. The alpha-SMA-positive area was very limited in the polyester cuff group even after 7 days, although many macrophages infiltrated into the fibers. In the cell-hybrid cuff group, on the other hand, an alpha-SMA-positive area was formed extensively after 3 and 7 days, causing severe inflammation. In the HAp-coated cuff group, an alpha-SMA-positive area was formed among the fibers with little inflammation. The extent order of the alpha-SMA-positive area was cell-hybrid cuff >> HAp-coated cuff >> polyester cuff, while the degree of inflammatory cells order was cell-hybrid cuff >> polyester cuff >> HAp-coated cuff.

Preparation of nano-hydroxyapatite particles with different morphology and their response to highly malignant melanoma cells in vitro

To investigate the effects of nano-hydroxyapatite (HA) particles with different morphology on highly malignant melanoma cells, three kinds of HA particles with different morphology were synthesized and co-cultured with highly malignant melanoma cells using phosphate-buffered saline (PBS) as control. A precipitation method with or without citric acid addition as surfactant was used to produce rod-like hydroxyapatite (HA) particles with nano- and micron size, respectively, and a novel oil-in-water emulsion method was employed to prepare ellipse-like nano-HA particles. Particle morphology and size distribution of the as prepared HA powders were characterized by transmission electron microscope (TEM) and dynamic light scattering technique. The nano- and micron HA particles with different morphology were co-cultured with highly malignant melanoma cells. Immunofluorescence analysis and MTT assay were employed to evaluate morphological change of nucleolus and proliferation of tumour cells, respectively. To compare the effects of HA particles on cell response, the PBS without HA particles was used as control. The experiment results indicated that particle nanoscale effect rather than particle morphology of HA was more effective for the inhibition on highly malignant melanoma cells proliferation.

A Mild and Efficient Biomimetic Synthesis of Rodlike Hydroxyapatite Particles with a High Aspect Ratio Using Polyvinylpyrrolidone As Capping Agent

Rodlike hydroxyapatite (HAp) nanoparticles were synthesized at 60 °C through a biomimetic pathway from Ca(NO3)2·4H2O, H3PO4, and NH4OH. The polymer polyvinylpyrrolidone (PVP) as a capping agent was used to regulate the nucleation and crystal growth of HAp crystal. X-ray diffraction results combined with high-resolution transmission electron microscopy indicated that single phase, nanocrystal HAp powder could be obtained in one-step and the addition of PVP facilitated the preferential growth of nanocrystal HAp along the axis. The formation mechanism of rodlike HAp crystal and the effects of PVP on the crystal nucleation and growth were discussed based on transmission electron microscopy and Fourier transform infrared spectroscopy results.