Self-reinforced composites of bioabsorbable polymer and bioactive glass with different bioactive glass contents. Part II: In vitro degradation

The in vitro degradation behavior of self-reinforced bioactive glass-containing composites was investigated comparatively with plain self-reinforced matrix polymer. The materials used were spherical bioactive glass 13-93 particles, with a particle size distribution of 50-125 microm, as a filler material and bioabsorbable poly-L,DL-lactide 70/30 as a matrix material. The composites containing 0, 20, 30, 40 and 50 wt.% of bioactive glass were manufactured using twin-screw extruder followed by self-reinforcing. The samples studied were characterized determining the changes in mechanical properties, thermal properties, molecular weight, mass loss and water absorption in phosphate-buffered saline at 37 degrees C for up to 104 weeks. The results showed that the bioactive glass addition modified the degradation kinetics and material morphology of the matrix material. It was concluded that the optimal bioactive glass content depends on the applications of the composites. The results of this study could be used as a guideline when estimating the best filler content of other self-reinforced osteoconductive filler containing composites which are manufactured in a similar way.     

Bioactive glass/polymer composite materials with mechanical properties matching those of cortical bone

Stress shielding resulting from mismatch in dynamic mechanical properties contributes to the reduced stability of osseous implants. Our objective was to develop biocompatible composites having mechanical properties similar to those of cortical bone. Polymers of urethane dimethacrylate (UDMA) and 2-hydroxyethyl methacrylate (HEMA, 0-20%) and composites containing bioactive glass particles (70% SiO(2), 25% CaO, and 5% P(2)O(5)), with or without silane treatment were prepared. Young's moduli of composites containing silane-treated glass (16 GPa) were significantly greater than those of composites containing untreated glass (12-13 GPa) or of unfilled polymers (5-6 GPa). Bioactive glass reduced water sorption by the composites and incorporation of silane-treated glass prevented HEMA-induced increases in water sorption. Osteoblast-like cells attached equally well to UDMA polymer and composite containing silane-treated bioactive glass. Thus, silane treatment improved the mechanical properties of bioactive glass composites without compromising biocompatibility. This material has a Young's modulus comparable to that of cortical bone. Therefore, silane-treated bioactive glass composites, when used as implant or cement materials, would reduce stress shielding and improve implant stability.     

Degradation, Bioactivity, and Osteogenic Potential of Composites Made of PLGA and Two Different Sol�CGel Bioactive Glasses

We have developed poly(L: -lactide-co-glycolide) (PLGA) based composites using sol-gel derived bioactive glasses (S-BG), previously described by our group, as composite components. Two different composite types were manufactured that contained either S2-high content silica S-BG, or A2-high content lime S-BG. The composites were evaluated in the form of sheets and 3D scaffolds. Sheets containing 12, 21, and 33?vol.% of each bioactive glass were characterized for mechanical properties, wettability, hydrolytic degradation, and surface bioactivity. Sheets containing A2 S-BG rapidly formed a hydroxyapatite surface layer after incubation in simulated body fluid. The incorporation of either S-BG increased the tensile strength and Young's modulus of the composites and tailored their degradation rates compared to starting compounds. Sheets and 3D scaffolds were evaluated for their ability to support growth of human bone marrow cells (BMC) and MG-63 cells, respectively. Cells were grown in non-differentiating, osteogenic or osteoclast-inducing conditions. Osteogenesis was induced with either recombinant human BMP-2 or dexamethasone, and osteoclast formation with M-CSF. BMC viability was lower at higher S-BG content, though specific ALP/cell was significantly higher on PLGA/A2-33 composites. Composites containing S2 S-BG enhanced calcification of extracellular matrix by BMC, whereas incorporation of A2 S-BG in the composites promoted osteoclast formation from BMC. MG-63 osteoblast-like cells seeded in porous scaffolds containing S2 maintained viability and secreted collagen and calcium throughout the scaffolds. Overall, the presented data show functional versatility of the composites studied and indicate their potential to design a wide variety of implant materials differing in physico-chemical properties and biological applications. We propose these sol-gel derived bioactive glass-PLGA composites may prove excellent potential orthopedic and dental biomaterials supporting bone formation and remodeling.     

Self-reinforced composites of bioabsorbable polymer and bioactive glass with different bioactive glass contents. Part I: Initial mechanical properties and bioactivity

Spherical bioactive glass 13-93 particles, with a particle size distribution of 50-125 microm, were combined with bioabsorbable poly-L,DL-lactide 70/30 using twin-screw extrusion. The composite rods containing 0, 20, 30, 40 and 50 wt% of bioactive glass were further self-reinforced by drawing to a diameter of approximately 3 mm. The bioactive glass spheres were well dispersed and the open pores were formed on the composite surface during drawing. The initial mechanical properties were studied. The addition of bioactive glass reduced the bending strength, bending modulus, shear strength, compression strength and torsion strength of poly-L,DL-lactide. However, the strain at maximum bending load increased in self-reinforced composites. Initially brittle composites became ductile in self-reinforcing. The bioactivity was studied in phosphate buffered saline for up to 12 days. The formation of calcium phosphate precipitation was followed using scanning electron microscopy and energy dispersive X-ray analysis. Results showed that the bioactive glass addition affected the initial mechanical properties and bioactivity of the composites. It was concluded that the optimal bioactive glass content depends on the applications of the composites.     

Comparison of nanoscale and microscale bioactive glass on the properties of P(3HB)/Bioglass composites

This study compares the effects of introducing micro (m-BG) and nanoscale (n-BG) bioactive glass particles on the various properties (thermal, mechanical and microstructural) of poly(3hydroxybutyrate) (P(3HB))/bioactive glass composite systems. P(3HB)/bioactive glass composite films with three different concentrations of m-BG and n-BG (10, 20 and 30 wt%, respectively) were prepared by a solvent casting technique. The addition of n-BG particles had a significant stiffening effect on the composites, modulus when compared with m-BG. However, there were no significant differences in the thermal properties of the composites due to the addition of n-BG and m-BG particles. The systematic addition of n-BG particles induced a nanostructured topography on the surface of the composites, which was not visible by SEM in m-BG composites. This surface effect induced by n-BG particles considerably improved the total protein adsorption on the n-BG composites compared to the unfilled polymer and the m-BG composites. A short term in vitro degradation (30 days) study in simulated body fluid (SBF) showed a high level of bioactivity as well as higher water absorption for the P(3HB)/n-BG composites. Furthermore, a cell proliferation study using MG-63 cells demonstrated the good biocompatibility of both types of P(3HB)/bioactive glass composite systems. The results of this investigation confirm that the addition of nanosized bioactive glass particles had a more significant effect on the mechanical and structural properties of a composite system in comparison with microparticles, as well as enhancing protein adsorption, two desirable effects for the application of the composites in tissue engineering.     

Bioactive composites consisting of PEEK and calcium silicate powders

Bioactive bone-repairing materials with mechanical properties analogous to those of natural bone can be obtained through the combination of bioactive ceramic fillers with organic polymers. Previously, we developed novel bioactive microspheres in a binary CaO-SiO2 system produced through a sol-gel process as filler for the fabrication of composites. In this study, we fabricate bioactive composites in which polyetheretherketone is reinforced with 0-50 vol% 30CaO x 70SiO2 (CS) microspheres. The prepared composites reinforced with CS particles form hydroxyapatite on their surfaces in simulated body fluid. The induction periods of hydroxyapatite formation on the composites decrease with increasing amount of CS particles. The mechanical properties of the composites are evaluated by three-point bending test. The composites reinforced with 20 vol% CS particles show 123.5 MPa and 6.43 GPa in bending strength and Young's modulus, respectively.     

Novel porous hydroxyapatite prepared by combining H2O2 foaming with PU sponge and modified with PLGA and bioactive glass

Porous hydroxyapatite (HA) scaffolds have been intensively studied and developed for bone tissue engineering, but their mechanical properties remain to be improved. The aim of this study is to prepare HA-based composite scaffolds that have a unique macroporous structure and special struts of a polymer/ceramic interpenetrating composite and a bioactive coating. A novel combination of a polyurethane (PU) foam method and a hydrogen peroxide (H(2)O( 2)) foaming method is used to fabricate the macroporous HA scaffolds. Micropores are present in the resulting porous HA ceramics after the unusual sintering of a common calcium phosphate cement and are infiltrated with the poly(D,L-lactic-co-glycolic acid) (PLGA) polymer. The internal surfaces of the macropores are further coated with a PLGA-bioactive glass composite coating. The porous composite scaffolds are characterized in terms of microstructure, mechanical properties, and bioactivity. It is found that the HA scaffolds fabricated by the combined method show high porosities of 61-65% and proper macropore sizes of 200-600 microm. The PLGA infiltration improved the compressive strengths of the scaffolds from 1.5-1.8 to 4.0-5.8 MPa. Furthermore, the bioactive glass-PLGA coating rendered a good bioactivity to the composites, evidenced by the formation of an apatite layer on the sample surfaces immersed in the simulated body fluid (SBF) for 5 days. The porous HA-based composites obtained from this study have suitable porous structures, proper mechanical properties, and a high bioactivity, and thus finds potential application as scaffolds for bone tissue engineering.     

Processing, properties, and in vitro bioactivity of polysulfone-bioactive glass composites

The mismatch between the mechanical properties of bioceramics and natural tissue has restricted in several cases a wider application of ceramics in medical and dental fields. To overcome this problem, polymer matrix composites can be designed to combine bioactive properties of some bioceramics with the superior mechanical properties of some engineering plastics. In this work, polymer particulate composites composed of a high mechanical-property polymer and bioactive glass particles were produced and both the in vitro bioactivity and properties of the system were investigated. Composites with different volume fraction and particle size were prepared. In vitro tests showed that hydroxy-carbonate-apatite can be deposited on the surface of a composite as early as 20 h in a simulated body fluid. Ionic evolution from a composite with 40% volume fraction of particles was demonstrated to be similar to bulk bioactive glasses. The mechanical properties of some of the obtained composites had values comparable with the ones reported for bone. Moreover, a physical model based on dynamical mechanical tests showed evidences that the interface of the composite was aiding in the stress transfer process.     

Development of a bioactive glass fiber reinforced starch-polycaprolactone composite

For bone regeneration and repair, combinations of different materials are often needed. Biodegradable polymers are often combined with osteoconductive materials, such as bioactive glass (BaG), which can also improve the mechanical properties of the composite. The aim of this work was to develop and characterize BaG fiber reinforced starch-poly-epsilon-caprolactone (SPCL) composite. Sheets of SPCL (30/70 wt %) were produced using single-screw extrusion. They were then cut and compression-molded in layers with BaG fibers to form composite structures with different combinations. Mechanical and degradation properties of the composites were studied. The actual amount of BaG in the composites was determined using combustion tests. Initial mechanical properties of the reinforced composites were at least 50% better than the properties of the nonreinforced specimens. However, the mechanical properties of the composites after 2 weeks of hydrolysis were comparable to those of the nonreinforced samples. During the 6 weeks hydrolysis the mass of the composites had decreased only by about 5%. The amount of glass in the composites remained as initial for the 6-week period of hydrolysis. In conclusion, it is possible to enhance initial mechanical properties of SPCL by reinforcing it with BaG fibers. However, mechanical properties of the composites are typical for bone fillers and strength properties need to be further improved for allowing more demanding bone applications.     

A-W生物活性玻璃陶瓷的研究和发展

生物活性玻璃陶瓷和玻璃陶瓷是生物医用材料领域的一个重要研究方向，其生物活性使材料被植入后能与骨形成紧密的化学键结合。A-W(Apatite／Wollastonite)生物活性玻璃陶瓷作为此类材料的杰出代表，不但拥有出色的生物活性和生物相容性，还具有优异的力学性能，因此在临床上得到了大量应用和发展。本文主要介绍了A-W生物活性玻璃陶瓷的研究进展、研制方法、性能、应用及骨结合机理，并对A-W生物活性玻璃陶瓷的研究和发展作出了展望。     

Characterization of bioactive glass-reinforced HAP-polymer composites

The effect of bioactive glass on the mechanical properties of hydroxyapatite-Ca polyacrylate composites was studied. Powder mixtures of tetracalcium phosphate (TetCP), poly(acrylic-co-itaconic) and bioactive glass (up to 50% by weight) were hot pressed for 30 min at 300 degrees C and 40 kpsi. Tensile strengths, elastic moduli, and microstructures of the composites produced were investigated. Results showed the mechanical properties of these composites were enhanced by the addition of bioactive glass. The highest values of tensile strength and elastic modulus were achieved with the addition of 10% bioactive glass. Composites were immersed in SBF for up to 10 days, then in 1.5 simulated body fluid (SBF) for a week. The changes in the concentrations of Ca, P, and Si ions of these solutions were measured. The microstructures of these composites after SBF immersion were also evaluated. Concentrations of Ca, P, and Si increased with the time of immersion in SBF owing to the formation of an apatite layer on their surfaces as found by SEM with energy-dispersive spectroscopy attachment.     

Polyurethane/nano-hydroxyapatite composite films as osteogenic platforms

A wide variety of biomaterials are utilized in tissue engineering to promote cell proliferations in vitro or tissue growth in vivo. The combination of cells, extracellular matrices, and biocompatible materials may make it possible to grow functional living tissues ranging from bone to nerve cells. In bone regeneration, polymeric scaffolds can be enhanced by the addition of bioactive materials. To this end, this study designed several ratios of polyurethane (PU) and nano-hydroxyapatite (nHA) composites (PU-nHA ratios: 100/0, 90/10, 80/20, 70/30, 60/40 w/w). The physical and mechanical properties of these composites and their relative cellular compatibility in vitro were determined. The chemical composition and crystallinity of the composites were confirmed using X-ray diffraction, X-ray photoelectron spectroscopy, and thermogravimetric analyses. Atomic force microscopy, nano-indentation, and contact angle measurements were used to evaluate surface properties. The results showed a significant increase in surface roughness and a decrease in contact angle when the nHA concentration increased above 20%, resulting in a significant increase in hydrophilicity. These surface property changes influenced cellular behavior when MC 3T3-E1 cells were seeded on the composites. All composites were cytocompatible. There was a linear increase in cell proliferation on the 80/20 and 70/30 composites only, whereas subjective evaluation demonstrated noticeable clusters or nodules of cells (considered hallmarks of osteogenic differentiation) in the absence of any osteogenic inducers only on the 90/10 and 80/20 composites. Cellular data suggests that the 80/20 composite was an optimal environment for cell adhesion, proliferation, and, potentially, osteogenic differentiation in vitro.     

New biomorphic SiC ceramics coated with bioactive glass for biomedical applications

A new generation of light, tough and high-strength material for medical implants for bone substitutions with a good biological response is presented. The innovative product that fulfills all these requirements is based on biomorphic silicon carbide ceramics coated with a bioactive glass layer. The combination of the excellent mechanical properties and low density of the biomorphic SiC ceramics, used as a base material for implants, with the osteoconducting properties of the bioactive glass materials opens new possibilities for the development of alternative dental and orthopedic implants with enhanced mechanical and biochemical properties that ensures optimum fixation to living tissue. Biomorphic SiC is fabricated by molten-Si infiltration of carbon templates obtained by controlled pyrolysis of wood. Through this process, the microstructure of the final SiC product mimics that of the starting wood, which has been perfected by natural evolution. The basic features of such microstructure are its porosity (ranging from 30% to 70%) and its anisotropy, which resembles the cellular microstructure and the mechanical characteristics of the bone. The SiC ceramics have been successfully coated with a uniform and adherent bioactive glass film by pulsed laser ablation using an excimer ArF laser. The excellent coverage of the SiC rough surface without film spallation or detachment is demonstrated. In order to assess the coating bioactivity, in vitro tests by soaking the samples in simulated body fluid have been carried out. After 72 h, the formation of a dense apatite layer has been observed even in interconnecting pores by SEM and energy dispersive X-ray spectroscopy analysis demonstrating the bioactive response of this product.     

硬组织替换用羟基磷灰石复合材料的研究进展

羟基磷灰(HA)石具有与人骨无机质相似的化学成分和晶体结构，被认为是一种很有潜力的人体硬组织替换材料，但脆性太大限制了其在承载部位骨替换中的应用。因而各种羟基磷灰石复合材料受到了极大的关注。本文按照增强体的种类对羟基磷灰石复合材料进行了分类介绍。生物活性陶瓷、生物活性玻璃及玻璃陶瓷、生物惰性陶瓷、聚合物及金属等都被用来制备羟基磷灰石复合材料，但仍没有一种材料能够很好的满足硬组织替换的需要。现有HA复合材料存在的关键问题是生物性能与力学性能之间不能很好地匹配。     

Fabrication and characterization of bioactive and antibacterial composites for dental applications

There is an increasing clinical need to design novel dental materials that combine regenerative and antibacterial properties. In this work the characterization of a recently developed sol–gel-derived bioactive glass ceramic containing silver ions (Ag-BG) is presented. The microstructural characteristics, ion release profile, zeta potential value and changes in weight loss and pH value as a function of the immersion time of Ag-BG in Tris buffer are evaluated. Ag-BG is also incorporated into natural extracellular matrix (ECM) hydrogel to further enhance its regenerative properties. Then, the micro and macro architectures of these new composites (ECM/Ag-BG) are characterized. In addition, the antibacterial properties of these new composites are tested against Escherichia coli and Enterococcus faecalis, a bacterium commonly implicated in the pathogenesis of dental pulp infections. Cell–material interaction is also monitored in a primary culture of dental pulp cells. Our study highlights the benefits of the successful incorporation of Ag in the bioactive glass, resulting in a stable antibacterial material with long-lasting bactericidal activity. Furthermore, this work presents for the first time the fabrication of new Ag-doped composite materials, with inductive pulp-cell proliferation and antibacterial properties (ECM/Ag-BG). This advanced composite made of Ag-BG incorporated into natural ECM possesses improved properties that may facilitate potential applications in tooth regeneration approaches.     

Surface modification of bioactive glasses and preparation of PDLLA/bioactive glass composite films

In order to improve the homogeneous dispersion of particles in the polymeric matrix, 45S5, mesoporous 58S, and 58S bioactive glasses were surface modified by esterification reactions with dodecyl alcohol at reflux temperature of 260 degrees C (named as m-45S5, m-mesoporous 58S, and m-58S, respectively). The modified particles showed better hydrophobicity and longer time of suspension in organic matrix. The PDLLA/bioactive glass composite films were fabricated using surface modified bioactive glass particles through solvent casting-evaporation method. Surface morphology, mechanical property, and bioactivity were investigated. The results revealed that the inorganic particle distribution and tensile strength of the composite films with modified bioactive glass particles were significantly improved while great bioactive properties were maintained. Scanning electron microscopy (SEM) observation illustrated that the modified bioactive glass particles were homogeneously dispersed in the PDLLA matrix. The maximum tensile strengths of composite films with modified bioactive glass particles were higher than that of composite films with unmodified bioactive glass particles. The bioactivity of the composite films were evaluated by being soaked in the simulated body fluid (SBF) and the SEM observation of the films suggested that the modified composite films were still bioactive in that they could induce the formation of HAp on its surface and the distribution of HAp was even more homogeneous on the film. The results mentioned above indicated that the surface modification of bioactive glasses with dodecyl alcohol was an effective method to prepare PDLLA/bioactive glass composites with enhanced properties. By studying the comparisons of modification effects among the three types of bioactive glasses, we could get the conclusion that the size and morphology of the inorganic particles would greatly affect the modification effects and the properties of composites.     

Casein and soybean protein-based thermoplastics and composites as alternative biodegradable polymers for biomedical applications

This work reports on the development and characterization of novel meltable polymers and composites based on casein and soybean proteins. The effects of inert (Al(2)O(3)) and bioactive (tricalcium phosphate) ceramic reinforcements over the mechanical performance, water absorption, and bioactivity behavior of the injection-molded thermoplastics were examined. It was possible to obtain materials and composites with a range of mechanical properties, which might allow for their application in the biomedical field. The incorporation of tricalcium phosphate into the soybean thermoplastic decreased its mechanical properties but lead to the nucleation of a bioactive calcium-phosphate film on their surface when immersed in a simulated body fluid solution. When compounded with 1% of a zirconate coupling agent, the nucleation and growth of the bioactive films on the surface of the referred to composites was accelerated. The materials degradation was studied for ageing periods up to 60 days in an isotonic saline solution. Both water uptake and weight loss were monitored as a function of the immersion time. After 1 month of immersion, the materials showed signal of chemical degradation, presenting weight losses up to 30%. However, further improvement on the mechanical performance and the enhancement of the hydrolytic stability of those materials will be highly necessary for applications in the biomedical field.     

Tensile properties,tension-tension fatigue and biological response of polyetheretherketone-hydroxyapatite composites for load-bearing orthopedic implants

Polyetheretherketone-hydroxyapatite composites were developed as alternative materials for load-bearing orthopedic applications. The amount of hydroxyapatite (HA) incorporated into the polyetheretherketone (PEEK) polymer matrix ranges from 5 to 40 vol% and these materials were successfully fabricated by injection molding. This study presents the mechanical and biological behavior of the composite materials developed. It was found that the amount of HA in the composite influenced the tensile properties. Dynamic behavior under tension-tension fatigue revealed that the fatigue-life of PEEK-HA composites were dependent on the HA content as well as the applied load. The biological responses of PEEK-HA composites carried out in vivo verified the biocompatibility and bioactive nature of the composite materials.     

Characterization of carbon nanotube (MWCNT) containing P(3HB)/bioactive glass composites for tissue engineering applications

Poly(3-hydroxybutyrate) (P(3HB)) composites with bioactive glass particles and multiwall carbon nanotubes (MWCNTs) were prepared and used to identify whether the electrical properties of MWCNTs can be used to detect the bioactivity of P(3HB)/bioactive glass composites. The presence of MWCNTs (2–7 wt.%) increased the surface roughness of the composites. The presence of MWCNTs in low quantity enhanced MG-63 osteoblast-like cell attachment and proliferation compared to composites with higher concentration of MWCNTs. Current–voltage measurements demonstrated that the electrical resistance of the composites containing bioactive glass particles decreased over a 45-day immersion period in SBF, whereas composites without bioactive glass showed no significant change over the same period.     

胶原/生物活性玻璃/壳聚糖增强型复合支架

背景：生物活性玻璃/胶原复合材料具有优良的成骨活性和的生物学性能,然而其在人体环境中易降解而导致支架溃散、力学性能下降。 目的：构建具有良好力学性能、抗降解性能和骨修复特性的胶原/生物活性玻璃/壳聚糖增强型复合支架。 方法：以壳聚糖作为分散剂,将生物活性玻璃粉体预先在壳聚糖溶液中均匀分散,然后与胶原溶液混合,结合冷冻干燥法制备多孔胶原/生物活性玻璃/壳聚糖增强型复合骨修复支架。采用傅里叶变换红外光谱仪、场发射扫描电子显微镜、X射线衍射仪、动态生物力学试验机等对复合支架的结构和性能进行表征。 结果与结论：由于壳聚糖和生物活性玻璃粉体在微酸性环境下的电荷吸引,使在壳聚糖中预分散的生物活性玻璃颗粒在复合支架中分散更均匀;壳聚糖的引入大量增加了机体中的羟基和氨基,使分子间的相互作用增强,显著提高了材料的抗压模量和强度;壳聚糖和胶原在分子尺度的混合,使胶原分子被壳聚糖包裹,降低了胶原酶对胶原分子的酶切能力,显著提高了复合支架的抗胶原酶解性;壳聚糖分子使生物活性玻璃颗粒更均匀的包裹在大分子基相中,减少了生物活性玻璃颗粒的团聚和暴露,导致复合支架在模拟体液中的矿化活性略微降低。中国组织工程研究杂志出版内容重点：生物材料;骨生物材料; 口腔生物材料; 纳米材料; 缓释材料; 材料相容性;组织工程全文链接：