Preparation of biomedical Ag incorporated hydroxyapatite/titania coatings on Ti6Al4V alloy by plasma electrolytic oxidation

Nano-Ag incorporated hydroxyapatite/titania （HA/TiO2） coatings were deposited on Ti6A14V substrates by the plasma electrolytic oxidation process. Compared with the substrate, the deposited coatings display attractive mechani- cal and biomedical properties. First, the coatings have stronger wear resistance and corrosion resistance. Second, they show a strong antibacterial ability. The mean vitality of the P. gingivalis on the coating surfaces is reduced to about 21%. Third, the coatings have good biocompatibility. The mean viability of the fibroblast cells on the coating surface is increased to about 130%. With these attractive properties, Ag incorporated HA/TiO2 coatings may be useful in the biomedical field.

Sol-gel derived bioactive hydroxyapatite/titania composite films on Ti6Al4V

The composite films consisting of the titania gel impregnated with hydroxyapatite （HAP） submicron particles were prepared on commercial Ti6A14V plates processed by a sol-gel route. HAP powders were synthesized based on wet chemical precipitation method with Ca（NO3）2.4H2O and （NH4）2HPO4 as starting reagents. After being calcined at 900℃, HAP powders were ultrasonically scattered in ethanol to produce HAP sol. The titania sol was prepared using titanium （IV） isopropoxide {Ti[OCH（CH3）2]4} as precursor. Both the titania sol and the HAP/titania mixture were sequentially spin-coated on the substrates and calcined at various temperatures. The characteristics and mechanical adhesion of the composite films were investigated. The results show that the as-prepared films are dense, homogeneous, well-crystallized, and there is a good interfacial adhesion between the film and the substrate. The in vitro bioactivities of these films were discussed based on the analysis of the variations of Ca and P concentrations in the simulated body fluid and their surface morphologies against immersion time.

Bio-inspired Hydroxyapatite/Gelatin Transparent Nanocomposites

Hydroxyapatite(HA)nanoparticles impart outstanding mechanical properties to organicinorganic nanocomposites in bone.Inspired by the composite structure of HA nanoparticles and collagen in bone,a high performance HA/gelatin nanocomposite was first developed.The nanocomposites have much better mechanical properties(elongation at break 29.9%,tensile strength 90.7 MPa,Young’s modulus 5.24 GPa)than pure gelatin films(elongation at break 9.3%,tensile strength 90.8 MPa,Young’s modulus 2.5 GPa).In addition,the composite films keep a high transmittance in visible wavelength range from 0%to 60%of the HA solid content.These differences in properties are attributed to the homogeneous distribution of HA nanoparticles in the gelatin polymer matrix and the strong interaction between the particle surfaces and the gelatin molecules.This protocol should be promising for HA-based nanocomposites with enhanced mechanical properties for biomedical applications.

Effect of Fluoride on the Ion-association of Calcium Phosphate and Crystallization of Hydroxyapatite

Using a titration setup to accurately control the reaction conditions and in situ monitor the reaction,we showed that fluoride exhibited negligible effects on the ion association process of calcium and phosphate and the formation of ACP nanospheres in a buffer solution with constant ionic strength.However,the stability of ACP increased with increasing fluoride concentration,which was ascribed to the inhibitory effect of fluoride on the aggregation of ACP nanospheres and the nucleation of nanocrystals on the surface of ACP nanospheres.Furthermore,fluoride could inhibit the lateral growth of HAP nanosheets and promote the formation of rod-like crystals.These results further improve our understanding of the crystallization pathway of HAP crystals and the regulatory effects of fluoride.

Ionic liquid-assisted preparation of hydroxyapatite and its catalytic performance for decarboxylation of itaconic acid

The synthesis of methacrylic acid from biomass-derived itaconic acid is a green route,for it can get rid of the dependence on fossil resource.In order to solve the problems on this route such as use of a preciousmetal catalyst and a corrosive homogeneous alkali,we prepared a series of hydroxyapatite catalysts by an ionic liquid-assisted hydrothermal method and evaluated their catalytic performance.The results showed that the ionic liquid[Bmim]BF_(4) can affect the crystal growth of hydroxyapatite,provide fluoride ion for fluorination of hydroxyapatite,and adjust the surface acidity and basicity,morphology,textural properties,crystallinity,and composition of hydroxyapatite.The[Bmim]BF4 dosage and hydrothermal temperature can affect the fluoride ion concentration in the hydrothermal system,thus changing the degree of fluoridation of hydroxyapatite.High fluoride-ion concentration can lead to the formation of CaF_(2) and thus significantly decrease the catalytic performance of hydroxyapatite.The hydrothermal time mainly affects the growth of hydroxyapatite crystals on the c axis,leading to different catalytic performance.The suitable conditions for the preparation of this fluoridized hydroxyapatite are as follows:a mass ratio of[Bmim]BF4 to calcium salt=0.2:1,a hydrothermal time of 12 h,and a hydrothermal temperature of 130℃.A maximal methacrylic acid yield of 54.7%was obtained using the fluoridized hydroxyapatite under relatively mild reaction conditions(250℃ and 2 MPa of N_(2))in the absence of a precious-metal catalyst and a corrosive homogeneous alkali.

Characterization of Hydroxyapatite Extracted from Crab Shell Using the Hydrothermal Method with Varying Holding Times

Hydroxyapatite(HA)is a bio ceramic commonly utilized in bone tissue engineering due to its bioactive and osteoconductive properties.Crab shells are usually disregarded as waste material despite their significant CaCO_(3) content,and have not been widely utilized in the synthesis of HA.This study aims to synthesize and analyze HA derived from crab shells using the hydrothermal method with different durations of holding time.This study utilized precipitated calcium carbonate(PCC)derived from crab shells.With a hydrothermal reactor set at 160℃ and varying holding times of 14(HA_14),16(HA_16),and 18(HA_18)h,a PCC and(NH4)2HPO4 mixture was used to synthesize HA.The synthesis results were analyzed using scanning electron microscopy(SEM),fourier transform infrared spectroscopy(FTIR),and X-ray diffraction(XRD)tests.This study has accomplished the synthesis of HA from crab shells.Nonetheless,the final product of synthesis still contained CaCO_(3) as an impurity.The prolonged hydrothermal holding time of 14 to 18 h resulted in a reduction of impurities while increasing the percentage of crystal weight and crystallite size of HA.Specimen CH_18 is the best-quality product generated in this study.This specimen produced HA with the highest percentage of crystal weight and crystallite size compared to the other specimens.Furthermore,specimen CH_18 exhibited the lowest concentration of impurities.The Ca/P ratio in this specimen was also the closest to 1.67.The Ca/P ratio,crystallite size,and crystal weight percentage of this specimen are 1.54,19.06 nm,and 99.1%,respectively.

Post Heat Treatment of Plasma Sprayed Pure and Alumina-Titania Reinforced Hydroxyapatite Coating on SS 304 Steel

It has been reported by previous research work that in plasma spray process hydroxyapatite decomposes into some amorphous phases due to rapid cooling of the coated substrate during the coating process, which causes instability of coated implant. Post coating heat treatment has been expected to minimize these phases and also enhance the long term reliability of hydroxyapatite coatings on metal substrates. In this paper post coating heat treatment is carried out at different temperatures suggested by the literature to study its effect on the microstructural and mechanical properties of coating. Coated substrates were characterized by X-ray diffraction (XRD) and SEM/EDAX analysis.

Influence of anodization conditions on deposition of hydroxyapatite onα/βTi alloys for osseointegration:Atomic force microscopy analysis

Integrating titanium-based implants with the surrounding bone tissue remains challenging.This study aims to explore the impact of different anodization voltages(20−80 V)on the surface topography of two-phase(α/β)Ti alloys and to produce TiO_(2) films with enhanced bone formation abilities.Scanning electron microscopy coupled with energy dispersive spectroscopy(SEM−EDS)and atomic force microscopy(AFM)were applied to investigate the morphological,chemical,and surface topography of the prepared alloys and to confirm the growth of hydroxyapatite(HA)on their surfaces.Results disclosed that the surface roughness of TiO_(2) films formed on Ti−6Al−7Nb alloys was superior to that of Ti−6Al−4V alloys.Ti−6Al−7Nb alloy anodized at 80 V had the highest yields of HA after immersion in simulated body fluid with enhanced HA surface coverage.The developed HA layer had a mean thickness of(128.38±18.13)μm,suggesting its potential use as an orthopedic implantable material due to its promising bone integration and,hence,remarkable stability inside the human body.

High temperature characteristic of hydroxyapatite-titania

In order to provide the kinetic mechanism for optimizing the quality of the hydroxyapatite （Ca 10（PO4）6-（OH）2, HA） coating on Ti-alloy orthopedic devices, the high temperature behavior of HA-titania （TiO2） composite specimen was investigated using XRD, FTIR and 31P MAS NMR methods. Thermal treatment of HA-TiO2 mixture powders leads to dehydroxylate and decompound of HA as well as chemical reaction between the two materials. Evidence for the initiation of the dehydroxylation of hydroxyapatite was found at 700℃ in air. The decomposition product of β-tricalcium phosphate was proven at 900℃ in air. Additionally, the formation of CaTiO3, derived from the chemical reaction between HA and titania at 900℃, was confirmed.

Effect of cetyltrimethylammonium bromide on morphology and porous structure of mesoporous hydroxyapatite

The mesoporous hydroxyapatite （HA） was synthesized by hydrothermal method utilizing cationic surfactant cetyltrimethylammonium bromide （CTAB） as template. The crystalline phase, morphology and porous structure were characterized respectively by different detecting techniques. The results reveal that the particles are highly crystalline hydroxyapatite phase. The surfactant has little influence on the morphology of the crystals, but affects the porous structure obviously. The sample without CTAB has a low surface area not exceeding 33 m^2/g, and no distinct pores can be observed by TEM. While the samples obtained with the surfactant get better parameters. Numerous open-ended pores centered at 2-7 nm spread unequally on the surface of the hydroxyapatite nanorods. The N2 adsorption-desorption experiments show type IV isotherms with distinct hysteresis loops, illustrating the presence of mesoporous structure. When the mole ratio of CTAB to HA is 1：2, the sample has the largest surface area of 97.1 m^2/g and pore volume of 0.466 cm^3/g.

Arginine functionalized hydroxyapatite nanoparticles and its bioactivity for gene delivery

In order to further improve the transfection efficiency of hydroxyapatite nanoparticle （HAp）, arginine functionalized hydroxyapatite （HAp/Arg） was synthesized by hydrothermal synthesis. The morphology, crystallite size and zeta potential of the HAp/Arg were characterized by transmission electron microscopy （TEM）, atomic force microscopy （AFM） and zeta potential analyzer. The loading and protecting properties of HAp/Arg to DNA were tested by electrophoresis. Its cytotoxicity was also measured in Hela cells and HAEC cells by MTT and LDH, and its transfection efficiency was examined by fluorescence microscope and flow cytometry. The results reveal that HAp/Arg is short rod-like and nano single crystal, the mean diameter is 50-90 nm and zeta potential is 35.8 mV at pH 7.4. HAp/Arg to DNA can be condensed by electrostatic effect and protect DNA against degradation in DNase I, and shows high transfection efficiency without cytotoxicity. These results suggest that HAp/Arg can be a promising alternative as a novel gene delivery system.

Synthesis of Crystalline Hydroxyapatite from CaCO_3 and CaHPO_4·2H_2O by Mechanochemical Method

The mixture of CaHPO 4·2H 2O and CaCO 3 was ground in an aqueous system under appropriate conditions to investigate the mechanochemical reaction for the synthesis of crystalline hydroxyapatite (HA) powder. Hydroxyapatite of high crystallinity powder including trace Ca 10 (PO 4) 6CO 3(OH) and Ca 9HPO 4(PO 4) 6OH can be synthesized by mechanical activation without further thermal treatment at a high temperature. The synthesis reaction during the grinding process was almost completed within 1h. The as-ground powder exhibits a particle distribution of 20-100nm in size with a spherical or rodlike morphology. The composition and degree of crystallinity of the mechanochemical synthesized hydroxyapatite powders were coincident with the cement-type hydroxyapatite.

Synthesis and characterization of arginine-modified and europium-doped hydroxyapatite nanoparticle and its cell viability

The arginine-modified and europium-doped hydroxyapatite nanoparticles（HAP-Eu） were synthesized by hydrothermal synthesis.The prepared nanoparticles were characterized by transmission electron microscopy（TEM）,X-ray diffractometry（XRD）,Fourier transform infrared（FTIR） and zeta potential analyzer.The cell viability of HAP-Eu was tested by image flow cytometry.The results indicated that HAP-Eu is short column shapes and its size is approximately 100 nm,its zeta potential is about 30.10 mV at pH of 7.5,and shows no cytotoxicity in human epithelial cells and endothelial cells.

Effects of Nanometer Hydroxyapatite on Proliferation of Periodontal Ligament Fibroblasts

Objective:To investigate possible effects of nanophase powder of hydroxyapatite on proliferation of periodontal ligament cells. Methods: With sol-gel method, the nanophase hydroxyapatite powders were fabricated. These powders were proved nanopaticles by transmission electron microscope. The effects on proliferation of periodontal ligament cell(PDLC) were observed in vitro with MTT [3-(4,5dimethylthiazo;-2-yl)-2,5-diphenytetralium bromide] method. Results: On the 2nd,3rd,4th day after treated with nanoparticles of hydroxyapatite, the proliferate activity of the PDLC increases significantly, compared with those with dense hydroxyaoatite and control but no significant difference could be found between the dense hydroxyapatite and the control. Conclusion: Nanophase hydroxyapatite can promote the regeneration of periodontal tissue.

Cytotoxinic Mechanism of Hydroxyapatite Nanoparticles on Human Hepatoma Cell Lines

Stable and single dispersed HAP nanoparticles were synthesized with chemical method assisted by ultrasonic treatment.HAP nanoparticles were surveyed by AFM and Zataplus.The effect on the Bel-7402 human hepatoma cell lines treated with HAP nanoparticles was investigated by the MTT methods and observation of morphology,and the mechanism was studied in changes of cell cycle and ultrastructure.The result shows that inhibition of HAP nanoparticles on the Bel 7402 human hepatoma cell lines is obviously in vitro.HAP nanoparticles the entered cancer cytoplasm,and cell proliferation is stopped at G 1 phase of cell cycle,thus,cancer cells die directly.

Hydroxyapatite Bioceramic Coatings Prepared by Hydrothermal-electrochemical Deposition Method

The hydroxyapatite（HA） ceramic coating was successfully prepared on Ti6A14V alloy by the hydrothermal-electrochemical deposition method with constant voltage model. The phases of deposits were analyzed by X-ray diffraction. The releationship between crystallinity and depositing temperature was discussed. The microstructures of hydroxyapatite coating were observed by scanning electron microscope. The experimental results showed that the phases, crystaUinity and morphologies of deposits were influenced by depositing temperature （100℃, 120℃, 140℃, 160℃, 180℃ and 200℃, respectively）. The special hydrothermal environment can lower the crystallization temperature of HA. The crystallinity of HA increases firstly and then decreases with the increase of temperature. There is little hydroxyapatite deposited on the Ti6A14V surface when the depositing temperature is 100℃. The HA deposition increases with the increase of the depositing temperature. And the HA morphologies are influenced by the depositing temperature.

Biologically Inspired Self-assembling Synthesis of Bone-like Nano-hydroxyapatite/PLGA-(PEG-ASP)_n Composite: A New Biomimetic Bone Tissue Engineering Scaffold Material

A new biomimetic bone tissue engineering scaffold material, nano-HAI PLGA-（ PEG-Asp ）n composite, was synthesized by a biologically inspired self-assembling approach. A novel biodegradable PLGA- （ PEG-Asp ）n copolymer with pendant amine functional groups and enhanced hydrophilicity woo synthesized by bulk ring-opening copolymerization by DL-lactide（ DLLA） and glycolide（ GA ） with Aspartic acid （ Asp ）-Polyethylene glycol（PEG） alt-prepolymer. A Three-dimensional, porous scaffold of the PLGA-（ PEG- Asp）n copolymer was fabricated by a solvent casting , particulate leaching process. The scaffold woo then incubated in modified simulated body fluid （naSBF）. Growth of HA nanocrystals on the inner pore surfaces of the porous scaffold is confirmed by calcium ion binding analyses, SEM , mass increooe meoourements and quantification of phosphate content within scaffolds. SEM analysis demonstrated the nucleation and growth of a continuous bonelike, low crystalline carbonated HA nanocrystals on the inner pore surfaces of the PLGA- （ PEG-Asp ）n scaffolds. The amount of calcium binding, total mass and the mass of phosphate on experimental PLGA- （ PEG-Asp ） n scaffolds at different incubation times in mSBF was significantly greater than that of control PLGA scaffolds. This nano-HA/ PLGA-（ PEG- Asp ）n composite stunts some features of natural bone both in main composition and hierarchical microstrueture. The Asp- PEG alt-prepolymer modified PleA copolymer provide a controllable high surface density and distribution of anionic functional groups which would enhance nucleation and growth of bonelike mineral following exposure to mSBF. This biomimetic treatment provides a simple method for surface functionalization and sabsequent mineral nucleation and self-oosembling on bodegradable polymer scaffolds for tissue engineering.

Adsorption of Disperse Blue SBL dye by synthesized poorly crystalline hydroxyapatite

The present study has been undertaken to evaluate the adsorption in batch mode of a disperse dye (Disperse Blue SBL) by poorly crystalline hydroxyapatite synthesized by coprecipitation between Ca(NO3)2and (NH4)2HPO4 reagents in aqueous solution at room temperature. The adsorption experiments were carried out to investigate the factors that influence the dye uptake by the adsorbent, such as the contact time under agitation, adsorbent dosage, initial dye concentration, solution temperature, and pH. The experimental results show that the percentage of dye removal increases with increasing the amount of adsorbent, until the total discoloration. The adsorption isotherms follow the model of Langmuir with a high adsorption capacity. The adsorption was pH and temperature dependent.

Plasmid-based Stat3 siRNA delivered by hydroxyapatite nanoparticles suppresses mouse prostate tumour growth in vivo

DNA vector-based Stat3-specific RNA interference （si-Stat3） blocks Stat3 signalling and inhibits prostate tumour growth. However, the antitumour activity depends on the efficient delivery of si-Stat3. The effects on the growth of mouse prostate cancer cells of si-Stat3 delivered by hydroxyapatite were determined in this study. RM-1 tumour blocks were transplanted into C57BIJ6 mice. CaCl2-modified hydroxyapatite carrying si-Stat3 plasmids were injected into tumours, and tumour growth and histology were determined. The expression levels of Star3, pTyr-Stat3, Bcl-2, Bax, Caspase3, VEGFand cyclin D1 were measured by western blot analysis. Amounts of apoptosis in cancer cells were analysed with immunohistochemistry and the terminal deoxyribonucleotidyl transferase-mediated dUTP-digoxigenin nick end-labelling （TUNEL） assay. The results showed that hydroxyapatite-delivered si-Stat3 significantly suppressed tumour growth up to 74% （P〈0.01）. Stat3 expression was dramatically downregulated in the tumours. The immunohistochemistry and TUNEL results showed that si-Stat3-induced apoptosis （up to 42%, P〈0.01）. The Stat3 downstream genes Bcl-2, VEGFand cyclin DI were also strongly downregulated in the tumour tissues that also displayed significant increases in Bax expression and Caspase3 activity. These results suggest that hydroxyapatite can be used for the in vivo delivery of plasmid-based siRNAs into tumours.

Growth of Hydroxyapatite Crystal in the Presence of Origanic Film

The growth of hydroxyapatite (HAp) crystal in the presence of hexadecylamine was investigated. Due to its high polarity and high charge density, the organic film could increase the ion supersaturation on its surface. Therefore the growth of pure HAp crystals was accelerated. Moreover, the positive headgroups of the organic film could act as recognized nucleation sites and orient the growth of HAp crystals along the <0001> direction.