Synthesis of Chitosan-Hydroxyapatite Composites and Its Effect on the Properties of Bioglass Bone Cement

Chitosan-hydroxyapatite （CS-HA） composite powders were synthesized via in situ co-precipitation method, through the reaction of Ca（NO3）2 and H3PO4 in the simulated body fluid （SBF） containing appropri- ate amount of chitosan. The thermal evolution, microstructure and morphology were studied by TG-DTA （thermogravimetry-differential thermal analysis）, XRD （X-ray diffraction）, FTIR （Fourier transform infrared spectroscopy） and TEM （transmission electron microscopy）. The in vitro bioactivity test showed that the obtained CS-HA composites had higher capability of inducing calcium ions deposition. Effects of CS-HA com- posites on the bioactivity and compressive strength of bioglass bone cement were investigated. The results indicated that the bioactivity of bioglass bone cement could be improved further when CS-HA composite pow- ders were added into the cement, and appropriate amount of CS-HA additive was favorable for compressive strength improvement of bioglass bone cement.

Properties and Structure of Microcrystalline Chitosan and Hydroxyapatite Composites

The skeletal system in the human body is very important, provides support and gives shape to the body and provides a network between all soft tissues. The most common problems in hard tissues are bone fractures, defects or diseases which needed to be treated. The developments in artificial bone area seem to solve most of the hard tissue problems, on the other hand artificial bones themselves may cause other problems and in many cases they do not have sufficient mechanical properties and/or good biocompatibility. The importance of chitosan and its derivatives like microcrystalline chitosan has grown significantly over the last two decades due to its renewable and biodegradable source, and also because of the increase in the knowledge of its functionality in the technological and biomedical applications. The excellent biocompability, biofunctionality, and non-antigenic property make the chitosan and its derivatives as a microcrystalline chitosan an ideal material for tissue regeneration. To improve the suitability of chitosan for bone tissue engineering, the composites of MCCh and hydroxyapatite were studied. In the present work the characterization of the MCCh and composites with HAp in form of films and sponges, is based on physico-chemical tests, morphology, structure, particle size of HAp powder and distribution in the polymer matrix. The compositions with film and sponge shape are derived from the junction of two different materials, containing organic and inorganic substances. All sponge preparations, with HAp/MCCh have a well-shaped 3-dimensional structure, which could be used as implants in orthopedic surgery for a scaffolds base for medical applications.

Experimental study of natural hydroxyapatite/chitosan composite on reconstructing bone defects

Objective：To study the possibility of natural hydroxyapatite/chitosan composite on repairing bone defects. Methods：We developed a natural hydroxyapatite/chitosan composite that could be molded into any desired shape. The powder component consists of natural hydroxyapatite, which is epurated from bone of pigs. The liquid component consists of malic acid and chitosan. Operations were performed on the left tibias of 15 white rabbits to create two square bone defects. One of the defects was reconstructed with the composite, while the other was not repaired and used as a blank control. Three of the animals were killed at the end of 2 weeks, 4 weeks, 8 weeks, 12 weeks and 16 weeks respectively and implants were evaluated anatomically and histologically. Results：No apparent rejection reaction was found, except for a mild inflammatory infiltration observed 2 weeks after surgery. Fibrous tissue became thinner 2 -8 weeks after surgery and bony connections were detected 12 weeks after surgery. The new bone was the same as the recipient bone by the 16th postoperative week. Conclusion：The hydroxyapatite/chitosan composite has good biocompatibility and osteoconduction. It is a potential repairing material for clinical application.

Synthesis and Characterization of Core-shell Hydroxyapatite/chitosan Biocomposite Nanospheres

Novel core-shell hydroxyapatite/chitosan biocomposite nanospheres were synthesized in a multiple emulsion. The multiple emulsion was a w/o/w emulsion, made of diammonium phosphate solution as an inner aqueous phase, cyclohexane as an oil phase, and calcium nitrate solution and chitosan solution as an outer aqueous. The forming mechanism of core-shell spheres and the influence of temperature on the morphology of the nanospheres were investigated. The diameter of the resulting core-shell nanospheres was 100-200 nm and the thickness of the chitosan shell was about 10 nm. And it concluded that at different reaction temperature the morphologies of the products would be changed. The core-shell nanospheres have potential applications for the development of new biomedical materials.

Simultaneous removal of copper and zinc ions by low cost natural snail shell/hydroxyapatite/chitosan composite

In this work,the snail shell/hydroxyapatite/chitosan composite was prepared as adsorbent.The adsorption potential of the composite was studied for simultaneous sorption behavior of Zn(Ⅱ)and Cu(Ⅱ)ions in a batch system.Chitosan and hydroxyapatite(HAP)were extracted from shrimp shell and bone ash,respectively,so this is a low cost natural composite.To prepare the composite,chitosan was dissolved in acetic acid,then HAP and snail shell powders were added to the chitosan solution.The morphology and characterization of the composite was studied by SEM and EDX analysis.Atomic adsorption was used to measure the amount of the ions.Experimental parameters were optimized with Design Expert Software and five parameters such as the concentration of ions,pH,adsorbent amount and contact time were studied at room temperature.Optimized value for the parameters of Zn(Ⅱ)and Cu(Ⅱ)concentrations,pH,adsorbent dose,and contact time were 3.01 mg·L^(-1),5.5,0.02 g and 95 min,respectively.The adsorption isotherms for Zn(Ⅱ)and Cu(Ⅱ)showed Langmuir and Tempkin,respectively.Kinetic and equilibrium studies showed the experimental data of Zn(Ⅱ)and Cu(Ⅱ)ions were best described by the pseudo-second-order model.Studies on thermodynamic show the adsorption process were physical and spontaneous.

Biotribological behavior of ultra high molecular weight polyethylene composites containing bovine bone hydroxyapatite

Wear particles of ultrahigh molecular weight polyethylene （UHMWPE） are the main cause of long-term failure of total joint replacements. Therefore, increasing its wear resistance or bioactivity will be very useful in order to obtain high quality artificial joints. In our study, UHMWPE composites filled with the bovine bone hydroxyapatite （BHA） were prepared by the method of compression moulding. A ball-on-disc wear test was carried out with a Universal Micro-Tribometer to investigate the friction and wear behavior of a Si3N4 ceramic ball, cross-sliding against the UHMWPE/BHA composites with human plasma lubrication. At the same time, the profiles of the worn grooves on the UHMWPE/BHA surface were scanned. The experimental results indicate that the addition of BHA to UHMWPE had a significant effect on the biotribological behavior of UHMWPE cross-sliding against the Si3N4 ceramic ball. The addition of BHA powder enhanced the hardness and modulus of elasticity of these composites and decreased the friction coefficients and wear rates under conditions of human plasma lubrication. When the added amount of BHA powders was up to 20%-30%, UHMWPE/BHA composites demonstrated the designed performance of the mechanical properties and biotribological behavior.

Preparation and characterization of chitosan/nano-hydroxyapatite composite used as bone substitute materials

Chitosan/nano-hydroxyapatite composites with different weight ratios were prepared through a co-precipitation method using Ca（OH）2, H3PO4 and chitosan as starting materials. The properties of these composites were characterized by means of TEM, IR, XRD, TGA, burn-out tests and universal matertial testing machine. The results showed that the HA synthesized here was poorly crystalline carbonated nanometer crystals and dispersed uniformly in chitosan phase and there was no phase-separation between the two phases. The addition of n-HA resulted in a decrease of decomposing temperature of chitosan. Because of the interactions between chitosan and n-HA, the mechanical properties of these composites were improved, and the maximum value of the compressive strength was measured to be about 120MPa corresponding to the chitosan/n-HA composite with a weight ratio of 30/70.

Preparation of Hydroxyapatite/Polylactide Bicomposites by Absorption Process in Liquid Phase

The hydroxyapatite/polylactide biocomposites were prepared by absorption process in liquid phase. The method avoided many disadvantages, such as inaterfusion of chemical impurity substances, nonuniformity dispersal of HA in PLA, low molecular weight of PLA . HA particles were uniformly dispersed in PLA matrix, and showed well ndhesion with PLA matrix. The biocomposites have the higher mechanical properties and suitable decomposable capability.

Preparation and Characterization of Homogeneous Hydroxyapatite/Chitosan Composite Scaffolds via In-Situ Hydration

Hydroxyapatite(HAP)/Chitosan(CS) composite is a biocompatible and bioactive material for tissue engineering. A novel homogeneous HAP/CS composite scaffold was developed via lyophilization and in situ hydration. A model CS solution with a Ca/P atom ratio of 1.67 was prepared through titration and stirring so as to attain a homogeneous dispersion of HAP particles. After lyophilization and in situ hydration, rod-shaped HAP particles (5 μm in diameter) within the CS matrix homogeneously scattered at the pore wall of the CS scaffold. X-ray diffraction (XRD) and Fouri-er-Transformed Infrared spectroscopy (FTIR) confirmed the formation of HAP crystals. The compressive strength in the composite scaffold indicated a significant increment over a CS-only scaffold. Bioactivity in vitro was completed by immersing the scaffold in simulated body fluid (SBF), and the result suggested that there was an increase in apatite formation on the HAP/CS scaffolds. Biological in vivo cell culture with MC 3T3-E1 cells for up to 7 days demonstrated that a homogeneous incorporation of HAP particles into CS scaffold led to higher cell viability compared to that of the pure CS scaffold or the HAP/CS scaffold blended. The results suggest that the homogeneous composite scaffold with better strength, bioactivity and biocompatibility can be prepared via in vitro hydration, which may serve as a good scaffold for bone tissue engineering.

Hybrid Composites of Phosphate Glass Fibre/Nano-Hydroxyapatite/Polylactide: Effects of Nano-Hydroxyapatite on Mechanical Properties and Degradation Behaviour

Hydroxyapatite/polylactide (HA/PLA) composites have been intensively investigated for their potential as biodegradable fixation devices to heal bone fractures. However, most of these composites failed to achieve a bone-mimicking level of mechanical properties, which is an essential demand of the targeted application. In this study, the nano-hydroxyapatite/polylactide composites were used as the matrix and continuous phosphate glass fibres (PGF) served as the major reinforcement to obtain the nano-HA/PGF/PLA hybrid composites. While the PGF volume fraction remained constant (25%), the nano-HA content (in weight) varied from 0% to 20%. As nano-HA loading increased, the flexural modulus of the composites increased from 8.70 ± 0.35 GPa to 14.97 ± 1.30 GPa, and the flexural strengths were enhanced from 236.31 ± 10.83 MPa to 310.55 ± 22.88 MPa. However, it is found that the degradation rates are higher with more nano-HA loaded. Enhanced water absorption ability, as well as increased voids in the composites is possible reasons for the accelerated degradation of composites with higher nano-HA loading. The hybrid composites possess mechanical properties that are superior to most of the HA/PLA composites in previous research while maintaining the biodegradability. With a proper loading of nano-HA in composites of 10 weight percent, the composites are also found with improved mechanical properties without catastrophic degradation. The composites developed in this study have great potential as biodegradable bone fixation device with enhanced load-bearing ability as confirmed and superior bioactivity as anticipated.

Adsorption of Heavy Metal Ions,Dyes and Proteins by Chitosan Composites and Derivatives-A Review

Chitosan composites and derivatives have gained wide attentions as effective biosorbents due to their low costs and high contents of amino and hydroxyl functional groups.They have showed significant potentials of removing metal ions,dyes and proteins from various media.Chemical modifications that lead to the formation of the chitosan derivatives and chitosan composites have been extensively studied and widely reported in literatures.The aims of this review were to summarize the important information of the bioactivities of chitosan,highlight the various preparation methods of chitosan-based active biosorbents,and outline its potential applications in the adsorption of heavy metal ions,dyes and proteins from wastewater and aqueous solutions.

Morphology and Phase Compositions of Hydroxyapatite Powder Particles Plasma-sprayed into Water

Hydroxyapatite powder particles were plasma sprayed into water, their inner structures and phase compositions were studied by using scanning electron microscope(SEM) and X-ray diffractometer. The results show that the molten HA particles have a central hollow morphology and high crystallinity. The hollow morphology was caused by sublimated P2O5 and H2O, which will have an effect on surface morphology, cohesive and adhesive strength as well as dissolution and degradation of coating. The high crystallinity is attributed to lower cooling speed in water.

Evaluation of different crosslinking methods in altering the properties of extrusion-printed chitosan-basedmulti-material hydrogel composites

Three-dimensional printing technologies exhibit tremendous potential in the advancing fields of tissue engineering and regenerative medicine due to the precise spatial control over depositing the biomaterial.Despite their widespread utilization and numerous advantages,the development of suitable novel biomaterials for extrusion-based 3D printing of scaffolds that support cell attachment,proliferation,and vascularization remains a challenge.Multi-material composite hydrogels present incredible potential in this field.Thus,in this work,a multi-material composite hydrogel with a promising formulation of chitosan/gelatin functionalized with egg white was developed,which provides good printability and shape fidelity.In addition,a series of comparative analyses of different crosslinking agents and processes based on tripolyphosphate(TPP),genipin(GP),and glutaraldehyde(GTA)were investigated and compared to select the ideal crosslinking strategy to enhance the physicochemical and biological properties of the fabricated scaffolds.All of the results indicate that the composite hydrogel and the resulting scaffolds utilizing TPP crosslinking have great potential in tissue engineering,especially for supporting neo-vessel growth into the scaffold and promoting angiogenesis within engineered tissues.

Comparative study of chitosan/fibroin–hydroxyapatite and collagen membranes for guided bone regeneration in rat calvarial defects: micro-computed tomography analysis

This study aimed to utilize micro-computed tomography （micro-CT） analysis to compare new bone formation in rat calvarial defects using chitosan/fibroin-hydroxyapatite （CFB-HAP） or collagen （Bio-Gide） membranes. Fifty-four （54） rats were studied. A circular bony defect （8 mm diameter） was formed in the centre of the calvaria using a trephine bur. The CFB-HAP membrane was prepared by thermally induced phase separation. In the experimental group （n= 18）, the CFB-HAP membrane was used to cover the bony defect, and in the control group （n= 18）, a resorbable collagen membrane （Bio-Gide） was used. In the negative control group （n= 18）, no membrane was used. In each group, six animals were euthanized at 2, 4 and 8 weeks after surgery. The specimens were then analysed using micro-CT. There were significant differences in bone volume （BV） and bone mineral density （BMD） （P〈O.05） between the negative control group and the membrane groups. However, there were no significant differences between the CFB-HAP group and the collagen group. We concluded that the CFB-HAP membrane has significant potential as a guided bone regeneration （GBR） membrane.

Hydroxyapatite/β-tricalcium Phosphate Composite for Guiding Bone Tissue Growth into a Titanium Tube in 8 mm Dog Tibia Cavity Defects

We developed a fixation method and evaluate bone regrowth in the cavities of a Ф4 mm× 8 mm titanium（Ti）tube through porous hydroxyapatite（HAP）/β-tricalcium phosphate（β-TCP）composite filling（group A）,chitosan/calcium phosphate composite filling（group B）,and HAP particle modification（group C）.After 2 and 5 months of implantation in dog tibia defects,new bone formation in the three groups was studied by histology and histomorphometry.Group A displayed the most bone regenerated area in both 2 and 5 months post-operation.The chitosan/calcium phosphate composite in group B mostly degraded 2 months after implantation,leading to fibrous tissue invasion after 5 months.By contrast,less bone formation was observed in group C.These results indicated that filling the cavities of metalprostheses with a porous HAP/β-TCP composite can be used for stable long-term fixation in clinicalsettings.

Corrosion behavior of composite coatings containing hydroxyapatite particles on Mg alloys by plasma electrolytic oxidation: A review

Mg and its alloys have been introduced as promising biodegradable materials for biomedical implant applications due to their excellent biocompatibility, mechanical behavior, and biodegradability. However, their susceptibility to rapid corrosion within the body poses a significant challenge and restricts their applications. To overcome this issue, various surface modification techniques have been developed to enhance the corrosion resistance and bioactivity of Mg-based implants. PEO is a potent technique for producing an oxide film on a surface that significantly minimizes the tendency to corrode. However, the inevitable defects due to discharges and poor biological activity during the coating process remain a concern. Therefore, adding suitable particles during the coating process is a suitable solution. Hydroxyapatite(HAp)has attracted much attention in the development of biomedical applications in the scientific community. HAp shows excellent biocompatibility due to its similarity in chemical composition to the mineral portion of bone. Therefore, its combination with Mg-based implants through PEO has shown significant improvements in their corrosion resistance and bioactivity. This review paper provides a comprehensive overview of the recent advances in the preparation, characterization, corrosion behavior and bioactivity applications of HAp particles on Mg-based implants by PEO.

Electrophoretic deposition of titanium/silicon-substituted hydroxyapatite composite coating and its interaction with bovine serum albumin

Silicon-substituted hydroxyapatite (Ca10(PO4)6-x(SiO4)x(OH)2-x, Si-HA) composite coatings on a bioactive titanium substrate were prepared by electrophoretic deposition technique with the addition of triethanolamine (TEA) to enhance the ionization degree of Si-HA suspension. The surface structure was characterized by XRD, SEM, XRF, EDS and FTIR. The bond strength of the coating was investigated. The results show that the depositing thickness and the images of Si-HA coating can be changed with the variation of deposition time. The XRD spectra of Ti/Si-HA coatings show the characteristic diffraction peaks of HA, and the incorporation of silicon changes the lattice parameter of the crystal. The FTIR spectra shows that the most notable effect of silicon substitution is the decrease of intensities of —OH and PO43- groups with the silicon contents increasing. XRD and EDS element analyses present that the content of silicon in the coating increases with increasing silicon concentration in the suspension. The bioactive TiO2 coating formed may improve the bond strength of the coatings. The interaction of Ti/Si-HA coating with BSA is much greater than that of Ti/HA coating, suggesting that the incorporation of silicon in HA is significant to improve the bioactive performance of HA.

Electrospun Nanofibers of Hydroxyapatite / Collagen / Chitosan Promote Osteogenic Differentiation of BMSCs

Bone tissue engineering, aiming at developing bone substitutes for repair and regeneration of bone defects instead of using autologous bone grafts,has attracted wide attention in the field of tissue engineering and regenerative medicine.Developing biomimetic biomaterial scaffolds able to regulate osteogenic differentiation of stem cells could be a promising strategy to improve the therapeutic efficacy.In this study, electrospun composite nanofibers of hydroxyapatite / collagen / chitosan( HAp / Col / CTS)resembling the fibrous nanostructure and constituents of the hierarchically organized natural bone,were prepared to investigate their capacity for promoting bone mesenchymal stem cells( BMSCs)to differentiate into the osteogenic lineage in the absence and presence of the osteogenic supplementation, respectively.Cell morphology,proliferation and quantified specific osteogenic protein expression on the electrospun HAp / Col / CTS scaffolds were evaluated in comparison with different controls including electrospun nanofibrous CTS,HAp / CTS and tissue culture plate.Our results showed that the nanofibrous HAp / Col / CTS scaffolds supported better spreading and proliferation of the BMSCs than other substrates( P < 0.01).Expressions of osteogenesis protein markers,alkaline phosphatase( ALP) and Col,were significantly upregulated on the HAp / Col / CTS than those on the CTS( P < 0.01) and HAp /CTS( P < 0.05) scaffolds in the absence of the osteogenic supplementation.Moreover,presence of osteogenic supplementation also proved to enhance osteogenic differentiation of BMSCs on HAp /Col / CTS scaffolds, indicative of a synergistic effect.This study highlights the potential of BMSCs / HAp / Col / CTS cell-scaffold system for functional bone repair and regeneration applications.

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.

In Vitro Immersion Behavior of Cold Sprayed Hydroxyapatite/Titanium Composite Coatings

In previous study, dense and homogenous 20wt% HAP/Ti composite coatings were successfully deposited on Ti substrates by cold gas dynamic spray technique. The results revealed that the phase composition of the HAP in the deposit is identical to that of the precursor powder and the bonding strength of the deposit is comparable/better to that of the plasma sprayed HAP. A relatively higher corrosion current of HAP/Ti composite than that of pure Ti coating in simulated body fluid indicates a good bioactivity for composite coating. In the present study, in vitro immersion test is carried out for various period of time and the formation of apatite layer on surface of composite coating proves the good bioactivity of the composite coating further. The cold sprayed HAP/Ti composite can be anticipated to be a promising load-bearing implant material for biomedical applications.