Zhiguang Huan

Novel bioactive composite bone cements based on the β-tricalcium phosphate–monocalcium phosphate monohydrate composite cement system

Bioactive composite bone cements were obtained by incorporation of tricalcium silicate (Ca3SiO5, C3S) into a brushite bone cement composed of beta-tricalcium phosphate [beta-Ca3(PO4)2, beta-TCP] and monocalcium phosphate monohydrate [Ca(H2PO4)2.H2O, MCPM], and the properties of the new cements were studied and compared with pure brushite cement. The results indicated that the injectability, setting time and short- and long-term mechanical strength of the material are higher than those of pure brushite cement, and the compressive strength of the TCP/MCPM/C3S composite paste increased with increasing aging time. Moreover, the TCP/MCPM/C3S specimens showed significantly improved in vitro bioactivity in simulated body fluid and similar degradability in phosphate-buffered saline as compared with brushite cement. Additionally, the reacted TCP/MCPM/C3S paste possesses the ability to stimulate osteoblast proliferation and promote osteoblastic differentiation of the bone marrow stromal cells. The results indicated that the TCP/MCPM/C3S cements may be used as a bioactive material for bone regeneration, and might have significant clinical advantage over the traditional beta-TCP/MCPM brushite cement.

Novel tricalcium silicate/magnesium phosphate composite bone cement having high compressive strength, in vitro bioactivity and cytocompatibility

Although inorganic bone cements such as calcium phosphate cements have been widely applied in orthopaedic and dental fields because of their self-setting ability, development of high-strength bone cement with bioactivity and biodegradability remains a major challenge. Therefore, the purpose of this study is to prepare a tricalcium silicate/magnesium phosphate (C3S/MPC) composite bone cement, which is intended to combine the excellent bioactivity of C3S with remarkable self-setting properties and mechanical strength of MPC. The self-setting and mechanical properties, in vitro induction of apatite formation and degradation behaviour, and cytocompatibility of the composite cements were investigated. Our results showed that the C3S/MPC composite cement with an optimal composition had compressive strength up to 87 MPa, which was significantly higher than C3S (25 MPa) and MPC (64 MPa). The setting time could be adjusted between 3 min and 29 min with the variation of compositions. The hydraulic reaction products of the C3S/MPC composite cement were composed of calcium silicate hydrate (CSH) derived from the hydration of C3S and gel-like amorphous substance. The C3S/MPC composite cements could induce apatite mineralization on its surface in SBF solution and degraded gradually in Tris-HCl solution. Besides, the composite cements showed good cytocompatibility and stimulatory effect on the proliferation of MC3T3-E1 osteoblast cells. Our results indicated that the C3S/MPC composite bone cement might be a new promising high-strength inorganic bioactive material which may hold the potential for bone repair in load-bearing site.

Three-Dimensional Printing of Hollow-Struts-Packed Bioceramic Scaffolds for Bone Regeneration

Three-dimensional printing technologies have shown distinct advantages to create porous scaffolds with designed macropores for application in bone tissue engineering. However, until now, 3D-printed bioceramic scaffolds only possessing a single type of macropore have been reported. Generally, those scaffolds with a single type of macropore have relatively low porosity and pore surfaces, limited delivery of oxygen and nutrition to surviving cells, and new bone tissue formation in the center of the scaffolds. Therefore, in this work, we present a useful and facile method for preparing hollow-struts-packed (HSP) bioceramic scaffolds with designed macropores and multioriented hollow channels via a modified coaxial 3D printing strategy. The prepared HSP scaffolds combined high porosity and surface area with impressive mechanical strength. The unique hollow-struts structures of bioceramic scaffolds significantly improved cell attachment and proliferation and further promoted formation of new bone tissue in the center of the scaffolds, indicating that HSP ceramic scaffolds can be used for regeneration of large bone defects. In addition, the strategy can be used to prepare other HSP ceramic scaffolds, indicating a universal application for tissue engineering, mechanical engineering, catalysis, and environmental materials.

In vitro degradation behavior and bioactivity of magnesium-Bioglass® composites for orthopedic applications†

To improve the bioactivity and degradation behavior of biodegradable magnesium, biodegradable metal matrix composites with the ZK30 magnesium alloy as the matrix and bioactive glass (BG, 45S5) as the reinforcement were prepared. The microstructures of the ZK30-BG composites showed homogeneous dispersion of BG particles throughout the matrix. XRD and EDX analyses confirmed the retention of the morphological characteristics and composition of BG particles in the composites. Immersion tests in the minimum essential medium with Earles balanced salts at 37°C showed that the composites with 5 and 10% BG had lower rates of degradation and hydrogen evolution than the matrix alloy. In addition, the tests confirmed that the composites possessed an enhanced ability to induce calcium and phosphate ion deposition on sample surfaces during degradation, suggesting accelerated surface mineralization that would lead to improved bioactivity when compared with the matrix alloy. In vitro cytotoxicity tests showed that the ionic products of the composites formed during degradation possessed a superior ability to support the survival, proliferation, and osteoblastic differentiation of bone marrow stromal cells to those of the ZK30 alloy. The ZK30-BG composites with enhanced bioactivity and reduced degradation rate could be promising biodegradable materials for orthopedic implants.

Synthesis and characterization of hybrid micro/nano-structured NiTi surfaces by a combination of etching and anodizing

The purpose of this study was to generate hybrid micro/nano-structures on biomedical nickel-titanium alloy (NiTi). To achieve this, NiTi surfaces were firstly electrochemically etched and then anodized in fluoride-containing electrolyte. With the etching process, the NiTi surface was micro-roughened through the formation of micropits uniformly distributed over the entire surface. Following the subsequent anodizing process, self-organized nanotube structures enriched in TiO2 could be superimposed on the etched surface under specific conditions. Furthermore, the anodizing treatment significantly reduced water contact angles and increased the surface free energy compared to the surfaces prior to anodizing. The results of this study show for the first time that it is possible to create hybrid micro/nano-structures on biomedical NiTi alloys by combining electrochemical etching and anodizing under controlled conditions. These novel structures are expected to significantly enhance the surface biofunctionality of the material when compared to conventional implant devices with either micro- or nano-structured surfaces.

Effect of Sodium Carbonate Solution on Self-setting Properties of Tricalcium Silicate Bone Cement

In this study, the effects of sodium carbonate (Na(2)CO(3) ) solution with different concentrations (10, 15, 20, and 25 wt%) as liquid phase on the setting time and compressive strength of tricalcium silicate bone cements are investigated. The in vitro bioactivity and degradability of the resultant Ca(3)SiO(5)-Na(2)CO(3) solution paste was also studied. The results indicate that as the concentration of Na(2)CO(3) solution varies from 0 to 25 wt%, the initial and final setting time of the cement decrease significantly from 90 to 20 min and from 180 to 45 min, respectively. After setting for 24 h, the compressive strength of Ca(3)SiO(5)-Na(2)CO(3) solution paste reaches 5.1 MPa, which is significantly higher than that of Ca( 3)SiO(5)-water cement system. The in vitro bioactivity of the cements is investigated by soaking in simulated body fluid (SBF) for 7 days. The results show that the Ca(3)SiO(5)-Na(2)CO( 3) solution bone cement has a good bioactivity and can degrade in Ringers solution. The results indicate that Na(2)CO(3) solution as a liquid phase significantly improves the self-setting properties of Ca( 3)SiO(5) cement as compared to water. The Ca(3)SiO( 5) cement paste prepared using Na(2)CO(3) solution shows good bioactivity and moderate degradability, and the Ca(3)SiO( 5)-Na(2)CO(3) solution system may be used as degradable and bioactive bone defect filling materials.In this study, the effects of sodium carbonate (Na2CO3 ) solution with different concentrations (10, 15, 20, and 25 wt%) as liquid phase on the setting time and compressive strength of tricalcium silicate bone cements are investigated. The in vitro bioactivity and degradability of the resultant Ca3SiO5-Na2CO3 solution paste was also studied. The results indicate that as the concentration of Na2CO3 solution varies from 0 to 25 wt%, the initial and final setting time of the cement decrease significantly from 90 to 20 min and from 180 to 45min, respectively. After setting for 24 h, the compressive strength of Ca3SiO5-Na2CO3 solution paste reaches 5.1MPa, which is significantly higher than that of Ca 3SiO5-water cement system. The in vitro bioactivity of the cements is investigated by soaking in simulated body fluid (SBF) for 7 days. The results show that the Ca3SiO5-Na2CO 3 solution bone cement has a good bioactivity and can degrade in Ringers solution. The results indicate that Na2CO3 solution as a liquid ...

3D-Printed Bioactive Ca3SiO5 Bone Cement Scaffolds with Nano Surface Structure for Bone Regeneration

Silicate bioactive materials have been widely studied for bone regeneration because of their eminent physicochemical properties and outstanding osteogenic bioactivity, and different methods have been developed to prepare porous silicate bioactive ceramics scaffolds for bone-tissue engineering applications. Among all of these methods, the 3D-printing technique is obviously the most efficient way to control the porous structure. However, 3D-printed bioceramic porous scaffolds need high-temperature sintering, which will cause volume shrinkage and reduce the controllability of the pore structure accuracy. Unlike silicate bioceramic, bioactive silicate cements such as tricalcium silicate (Ca3SiO5 and C3S) can be self-set in water to obtain high mechanical strength under mild conditions. Another advantage of using C3S to prepare 3D scaffolds is the possibility of simultaneous drug loading. Herein, we, for the first time, demonstrated successful preparation of uniform 3D-printed C3S bone cement scaffolds with controllable 3D structure at room temperature. The scaffolds were loaded with two model drugs and showed a loading location controllable drug-release profile. In addition, we developed a surface modification process to create controllable nanotopography on the surface of pore wall of the scaffolds, which showed activity to enhance rat bone-marrow stem cells (rBMSCs) attachment, spreading, and ALP activities. The in vivo experiments revealed that the 3D-printed C3S bone cement scaffolds with nanoneedle-structured surfaces significantly improved bone regeneration, as compared to pure C3S bone cement scaffolds, suggesting that 3D-printed C3S bone cement scaffolds with controllable nanotopography surface are bioactive implantable biomaterials for bone repair.

3D plotting of highly uniform Sr5(PO4)2SiO4 bioceramic scaffolds for bone tissue engineering

Bioceramics play an important role in bone regeneration. However, it is challenging to design bioceramic scaffolds with suitable ionic components and beneficial osteo/angio-stimulation ability for enhanced bone regeneration. In this study, we successfully synthesized a pure-phase Sr5(PO4)2SiO4 (SPS) bioactive ceramic through a solid-state reaction method and further prepared highly uniform SPS bioceramic scaffolds with controlled macropore sizes and mechanical strength by a 3D-plotting technique, and the biological responses of rabbit bone marrow stromal cells (rBMSCs) and human umbilical vein endothelial cells (HUVECs) after culturing with different concentrations of SPS extracts and porous scaffolds were systematically studied. The results showed that the ionic products from SPS bioceramics significantly stimulated the proliferation, alkaline phosphate (ALP) activity and osteogenesis-related gene expression (Runx2, ALP, OCN, OPN) of rBMSCs as well as the proliferation and angiogenesis-related gene expression (VEGF, KDR, eNOS, HIF 1α) of HUVECs. 3D-plotted SPS scaffolds could effectively support the attachment and proliferation of both rBMSCs and HUVECs, and the proliferation rates of the two kinds of cells in SPS scaffolds were distinctively higher than those in β-tricalcium phosphate (β-TCP) scaffolds prepared by the same method. In addition, the compressive strength of SPS scaffolds could be well controlled in the range 8-30 MPa when their pore size varied from 100 to 300 μm, which was significantly higher than those of β-TCP scaffolds with similar pore sizes (∼1.5 times). Our results demonstrated that 3D-plotted SPS bioceramic scaffolds with such a specific ionic combination and high mechanical strength as well as good degradability possessed the ability to stimulate both osteogenic and angiogenic differentiation of tissue cells, indicating that they might be promising biomaterials for bone tissue engineering.

Porous TiO2 surface formed on nickel‐titanium alloy by plasma electrolytic oxidation: A prospective polymer‐free reservoir for drug eluting stent applications

In this study, a porous oxide layer was formed on the surface of nickel-titanium alloy (NiTi) by plasma electrolytic oxidation (PEO) with the aim to produce a polymer-free drug carrier for drug eluting stent (DES) applications. The oxidation was performed galvanostatically in concentrated phosphoric acid electrolyte at low temperature. It was found that the response of NiTi substrate during the PEO process was different from that of bulk Ti, since the presence of large amount of Ni delayed the initial formation of a compact oxide layer that is essential for the PEO to take place. Under optimized PEO conditions, the resultant surface showed porosity, pore density and oxide layer thickness of 14.11%, 2.40 × 10⁵ pores/mm² and 0.8 μm, respectively. It was additionally noted that surface roughness after PEO did not significantly increase as compared with that of original NiTi substrate and the EDS analyses revealed a decrease in Ni/Ti ratio on the surface after PEO. The cross-section morphology showed no discontinuity between the PEO layer and the NiTi substrate. Furthermore, wettability and surface free energy of the NiTi substrate increased significantly after PEO treatment. The PEO process could be successfully translated to NiTi stent configuration proving for the first time its feasibility for such a medical device and offering potential for development of alternative, polymer-free drug carriers for NiTi DES.

Fabrication of novel magnesium-matrix composites and their mechanical properties prior to and during in vitro degradation

In our previous study, we developed Mg-matrix composites with bredigite as the reinforcing phase and achieved improved degradation resistance in comparison with Mg. However, the effects of materials processing method and process parameters on the mechanical behavior of the composites before and during degradation were still unknown. This research was aimed at determining the mechanical properties of Mg-bredigite composites prior to and during degradation. It was found that by optimizing the process parameters of Pressure Assisted Sintering (PAS), low-porosity Mg-bredigite composites with strong interfaces between homogeneously distributed bredigite particles and the Mg matrix could be fabricated. By reinforcing Mg with 20vol% bredigite particles, the ultimate compressive strength and ductility of Mg increased by 67% and 111%, respectively. The in vitro degradation rate of the Mg-20% bredigite composite in a cell culture medium was 24 times lower than that of monolithic Mg. As a result of retarded degradation, the mechanical properties of the composite after 12 days of immersion in the cell culture medium were comparable to those of cortical bone. The encouraging results of this research warrant further investigations on the in vivo degradation behavior and mechanical properties of the composites.