Hydrothermal Synthesis and Processing of Barium Titanate Nanoparticles Embedded in Polymer Films.

Barium titanate nanoparticles embedded in flexible polymer films were synthesized using hydrothermal processing methods. The resulting films were characterized with respect to material composition, size distribution of nanoparticles, and spatial location of particles within the polymer film. Synthesis conditions were varied based on the mechanical properties of the polymer films, ratio of polymer to barium titanate precursors, and length of aging time between initial formulations of the solution to final processing of nanoparticles. Block copolymers of poly(styrene-co-maleic anhydride) (SMAh) were used to spatially separate titanium precursors based on specific chemical interactions with the maleic anhydride moiety. However, the glassy nature of this copolymer restricted mobility of the titanium precursors during hydrothermal processing. The addition of rubbery butadiene moieties, through mixing of the SMAh with poly(styrene-butadiene-styrene) (SBS) copolymer, increased the nanoparticle dispersion as a result of greater diffusivity of the titanium precursor via higher mobility of the polymer matrix. Additionally, an aminosilane was used as a means to retard cross-linking in polymer-metalorganic solutions, as the titanium precursor molecules were shown to react and form networks prior to hydrothermal processing. By adding small amounts of competing aminosilane, excessive cross-linking was prevented without significantly impacting the quality and composition of the final barium titanate nanoparticles. X-ray diffraction and X-ray photoelectron spectroscopy were used to verify nanoparticle compositions. Particle sizes within the polymer films were measured to be 108 ± 5 nm, 100 ± 6 nm, and 60 ± 5 nm under different synthetic conditions using electron microscopy. Flexibility of the films was assessed through measurement of the glass transition temperature using dynamic mechanical analysis. Dielectric permittivity was measured using an impedance analyzer.

Nanocrystalline hydroxyapatite/titania coatings on titanium improves osteoblast adhesion.

Bulk hydroxyapatite (HA) and titania have been used to improve the osseointegration of orthopedic implants. For this reason, composites of HA and titania have been receiving increased attention in orthopedics as novel coating materials. The objective of this in vitro study was to produce nanophase (i.e., materials with grain size less than 100 nm) HA/titania coatings on titanium. The adhesion of bone forming cells (osteoblasts) on the composite coatings were also assessed and compared with single-phase nanotitania and nano-HA titanium coatings. Nanocrystalline HA powders were synthesized through wet chemistry and hydrothermal treatments at 200 degrees C. Nanocrystalline titania powders obtained commercially were mixed with the nanocrystalline HA powders at various weight ratios. The mixed powders were then deposited on titanium utilizing a room-temperature coating process called IonTite. The results of the present study showed that such coatings maintained the chemistry and crystallite size of the original HA and titania powders. Moreover, osteoblasts adherent on single-phase nanotitania coatings were well-spread whereas they became more round and extended distinct filopodia on the composite and single-phase HA coatings. Interestingly, the number of osteoblasts adherent on the nanotitania/HA composite coatings at weight ratios of 2/1 and 1/2 were significantly greater compared with single-phase nanotitania coatings, currently-used plasma-sprayed HA coatings, and uncoated titanium. These findings suggest that nanotitania/HA coatings on titanium should be further studied for improved orthopedic applications.

Enhanced osteoblast functions on anodized titanium with nanotube-like structures.

Previous studies have demonstrated increased osteoblast (bone-forming cells) adhesion on titanium and Ti-6Al-4V anodized to possess nanometer features compared with their unanodized counterparts. In this study, osteoblast long-term functions (specifically, synthesis of intracellular proteins, synthesis of intracellular collagen, alkaline phosphatase activity, and deposition of calcium-containing minerals) were determined on titanium anodized to possess either heterogeneous nanoparticles or ordered nanotubes. Titanium was anodized in dilute hydrofluoric acid at 20 V for 20 min to possess nanotubes, while titanium was anodized at 10 V for 20 min to possess nanoparticles. Most importantly, results showed that calcium deposition significantly increased on anodized titanium with nanotube-like structures compared with unanodized titanium and anodized titanium with nanoparticulate structures after 21 days of osteoblast culture. In this manner, the results of the present in vitro study indicated that anodization might be a promising quick and inexpensive method to modify the surface of titanium-based implants to induce better bone cell functions important for orthopedic applications.

Increased osteoblast functions among nanophase titania/poly(lactide-co-glycolide) composites of the highest nanometer surface roughness.

Currently, the scientific challenges for bone tissue engineering lie in the development of suitable scaffold materials that can improve bone cell adhesion, proliferation, and differentiation. The design of nanophase titania/poly(lactide-co-glycolide) (PLGA) composites offers an exciting approach to combine the advantages of a degradable polymer with nanosize ceramic particles to optimize the physical and biological properties necessary for bone regeneration. Moreover, because of the presence of nanosized ceramics, such composites can be formulated to match the surface roughness of bone. For these reasons, the objective of the present in vitro study was to investigate osteoblast (bone-forming cell) adhesion and long-term functions on nanophase titania/PLGA composites that mimic the surface roughness of bone. Various sonication powers were applied in this study to manipulate titania dispersions in PLGA and consequently control their surface roughness. Most importantly, results correlated better osteoblast adhesion and long-term functions (such as collagen, alkaline phosphatase activity, and calcium-containing mineral deposition) among nanophase titania/PLGA composites that had surface roughness values closer to natural bone. In this manner, this present study demonstrated that the nanophase titania/PLGA composites sonicated to have nanometer surface roughness values can improve osteoblast functions necessary for enhanced bone tissue engineering applications.

Increased osteoblast functions on undoped and yttrium-doped nanocrystalline hydroxyapatite coatings on titanium.

In order to improve orthopedic implant performance, the objective of this in vitro study was to synthesize nanocrystalline hydroxyapatite (HA) powders to coat titanium. HA was synthesized through a wet chemical process. The precipitated powders were either sintered at 1100 degrees C for 1h in order to produce UltraCap HA (or microcrystalline size HA) or were treated hydrothermally at 200 degrees C for 20 h to produce nanocrystalline HA. Some of the UltraCap and nanocrystalline HA powders were doped with yttrium (Y) since previous studies demonstrated that Y-doped HA in bulk improved osteoblast (or bone-forming cell) function over undoped HA. The original HA particles were characterized using X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), BET, a laser particle size analyzer, and scanning electron microscopy (SEM). These powders were then deposited onto titanium by a novel room-temperature process, called IonTite. The properties of the resulting HA-coatings on titanium were compared to respective properties of the original HA powders. The results showed that the chemical and physical properties of the original HA powders were retained when coated on titanium by IonTite, as determined by XRD, SEM, and atomic force microscopy (AFM) analysis. More importantly, results showed increased osteoblast adhesion on the nanocrystalline HA IonTite coatings compared to traditionally used plasma-sprayed HA coatings. Results also demonstrated greater amounts of calcium deposition by osteoblasts cultured on Y-doped nanocrystalline HA coatings compared to either UltraCap IonTite coatings or plasma-sprayed HA coatings. These results encourage further studies on nanocrystalline IonTite HA coatings on titanium for improved orthopedic applications.

Less harmful acidic degradation of poly(lacticco-glycolic acid) bone tissue engineering scaffolds through titania nanoparticle addition.

In the last 10 years, biodegradable aliphatic polyesters, such as poly(lactic-co-glycolic acid) (PLGA), have attracted increasing attention for their use as scaffold materials in bone tissue engineering because their degradation products can be removed by natural metabolic pathways. However, one main concern with the use of these specific polymers is that their degradation products reduce local pH, which in turn induces an inflammatory reaction and damages bone cell health at the implant site. Thus, the objective of the present in vitro study was to investigate the degradation behavior of PLGA when added with dispersed titania nanoparticles. The results of this study provided the first evidence that the increased dispersion of nanophase titania in PLGA decreased the harmful change in pH normal for PLGA degradation. Moreover, previous studies have demonstrated that the increased dispersion of titania nanoparticles into PLGA significantly improved osteoblast (bone-forming cell) functions (such as adhesion, collagen synthesis, alkaline phosphatase activity, and calcium-containing minerals deposition). In this manner, nanophase titania-PLGA composites may be promising scaffold materials for more effective orthopedic tissue engineering applications.

Increased osteoblast functions on nanophase titania dispersed in poly-lactic-co-glycolic acid composites.

The design of nanophase titania/poly-lactic-co-glycolic acid (PLGA) composites offers an exciting approach to combine the advantages of a degradable polymer with nano-size ceramic grains to optimize physical and biological properties for bone regeneration. Importantly, nanophase titania mimics the size scale of constituent components of bone since it is a nanostructured composite composed of nanometre dimensioned hydroxyapatite well dispersed in a mostly collagen matrix. For these reasons, the objective of the present in vitro study was to investigate osteoblast (bone-forming cell) adhesion and long-term functions on nanophase titania/PLGA composites. Since nanophase titania tended to significantly agglomerate when added to polymers, different sonication output powers were applied in this study to improve titania dispersion. Results demonstrated that the dispersion of titania in PLGA was enhanced by increasing the intensity of sonication and that greater osteoblast adhesion correlated with improved nanophase titania dispersion in PLGA. Moreover, results correlated better osteoblast long-term functions, such as alkaline phosphatase activity and calcium-containing mineral deposition, on nanophase titania/PLGA composites compared to plain PLGA. In fact, the greatest collagen production by osteoblasts occurred when cultured on nanophase titania sonicated in PLGA at the highest powers. In this manner, the present study demonstrates that PLGA composites with well dispersed nanophase titania can enhance osteoblast functions necessary for improved bone tissue engineering applications.

Enhanced osteoblast adhesion on hydrothermally treated hydroxyapatite/titania/poly(lactide-co-glycolide) sol-gel titanium coatings.

Sol-gel processing was used to coat titanium substrates with hydroxyapatite (HA), TiO2, and poly(DL-lactic-glycolic acid). Coating surface characteristics were analyzed with XRD, EDS, AFM, SEM, and water contact angle measurements which indicated that the coatings had a high degree of crystallinity and good resistance to cracking. Coatings were also evaluated by cytocompatibility testing with osteoblast-like cells (or bone-forming cells). The cytocompatibility of the HA composite coatings prepared in the present in vitro study was compared to that of a traditional plasma-sprayed HA coating. Results showed that osteoblast-like cell adhesion was promoted on the novel HA sol-gel coating compared to the traditional plasma-sprayed HA coating. In addition, hydrothermal treatment of the sol-gel coating improved osteoblast-like cell adhesion. Since osteoblast adhesion is a necessary prerequisite for subsequent formation of bone, these results provided evidence that hydrothermally sol-gel processed HA may improve bonding of titanium implants to juxtaposed bone and, thus, warrants further investigation.