Physicochemical and biological properties of nanohydroxyapatite grafted with star-shaped poly(ε-caprolactone).

To overcome the disadvantages generated by the lack of interfacial bonding between hydroxyapatite nanocrystals (HAPN) and agglomeration of particles in the development of biodegradable nanocomposites a chemical grafting method was applied to modify the surface of HAPN through grafting of the three-arms star-shaped poly(ε-caprolactone) (SPCL) onto the nanoparticles. The chemical grafting of SPCL onto HAPN (SPCL-g-HAPN) has been investigated using Fourier transform infrared spectroscopy, thermogravimetric analysis, transmission electron microscopy (TEM), photoelectron spectroscopy, X-ray diffraction, zeta potential (ZP) and contact angle (CA). TEM micrographs of the SPCL-g-HAPN revealed the existence of hybrid organic/inorganic (O/I) nanoscale domains. The results of albumin (HSA) and fibrinogen (HFb) adsorption indicate resistance to HFb adsorption by SPCL-g-HAPN relatively to unmodified HAPN. The ZP and CA measurement suggest a heterogeneous topology for SPCL-g-HAPN likely due to the existence of hydrophobic-hydrophilic regions on the nanocomposite surface. The enzyme degradation by cholesterol esterase and lipase indicates that the rates of hydrolysis for SPCL-g-HAPN were very slow relative to the SPCL/HAPN blends. The in vitro biological studies showed that the human osteoblast-like cells (MG-63) cells had normal morphology and they were able to attach and spread out on SPCL-g-HAPN surfaces. A higher overall cellular proliferation was observed on SPCL-g-HAPN scaffolds compared to pure HAPN or SPCL materials.

Electrochemical preparation and characterization of PNIPAM-HAp scaffolds for bone tissue engineering.

In the last decade, a variety of methods for fabrication of three-dimensional biomimetic scaffolds based on hydrogels have been developed for tissue engineering. However, many methods require the use of catalysts which compromises the biocompatibility of the scaffolds. The electrochemical polymerization (ECP) of acrylic monomers has received an increased attention in recent years due to its versatility in the production of highly biocompatible coatings for the electrodes used in medical devices. The main aim of this work was the use of ECP as scaffold fabrication technique to produce highly porous poly(N-isopropylacrylamide) (PNIPAM)/hydroxyapatite (HAp) composite for bone tissue regeneration. The prepared PNIPAM-HAp porous scaffolds were characterized by SEM, FTIR, water swelling, porosity measurements and X-ray diffraction (XRD) techniques. FTIR indicates that ECP promotes a successful conversion of NIPAM to PNIPAM. The water swelling and porosity were shown to be controlled by the HAp content in PNIPAM-HAp scaffolds. The PNIPAM-HAp scaffolds exhibited no cytotoxicity to MG63 cells, showing that ECP are potentially useful for the production of PNIPAM-HAp scaffolds. To address the osteomyelitis, a significant complication in orthopedic surgeries, PNIPAM-HAp scaffolds were loaded with the antibiotic oxacillin. The oxacillin release and the bacterial killing activity of the released oxacillin from PNIPAM-HAp against S. aureus and P. aeruginosa were demonstrated. These observations demonstrate that ECP are promising technique for the production of non-toxic, biocompatible PNIPAM-HAp scaffolds for tissue engineering.

Bioactive composites containing TEGDMA-functionalized calcium phosphate particles: Degree of conversion, fracture strength and ion release evaluation.

OBJECTIVE: To evaluate the strength and ion release of experimental composites containing TEGDMA-functionalized calcium phosphate particles. METHODS: Seven composites containing equal parts (in mols) of BisGMA and TEGDMA and 60vol% of fillers were manipulated. Filler phase was constituted by silanized barium glass and 0% (control), 10% or 20% (volume) of dicalcium phosphate dihydrate (DPCD) particles, either non-functionalized or functionalized with two different TEDGMA contents. DCPD particles were synthesized and characterized by X-ray diffraction (XRD), elemental analysis, surface area and dynamic light scattering. Composites were tested for degree of conversion (DC) by near-FTIR. Biaxial flexural strength (BFS) was determined after 24h and 28days in water. Calcium and phosphate release after 7days was assessed using inductively coupled plasma optical emission spectrometry (ICP-OES). Data were analyzed by ANOVA/Tukey test (alpha:5%). RESULTS: XRD confirmed the crystalline structure corresponding to DCPD. Elemental analysis revealed particles with zero, 14% or 22% TEGDMA, with similar D50 (around 19µm) and surface areas from 3.5 to 11.4m2/g. The presence of DCPD did not reduce DC. After 24h, functionalization (both 14% and 22% TEGDMA) improved composite strength in comparison to non-functionalized DCPD, both at 10% and 20% levels. After 28days, BFS of materials containing 10% functionalized DCPD were statistically similar to the control containing only barium glass. Among composites containing 10% DCPD, particle functionalization with 14% TEGDMA did not jeopardize ion release. SIGNIFICANCE: At 10vol%, the use of TEGDMA-functionalized CaP particles improved composite strength in relation to non-functionalized particles, while maintaining similar ion release levels.

Hydroxyapatite Dome for Bone Neoformation in Rabbit Tibia.

PURPOSE: To evaluate supracortical bone neoformation with the use of hydroxyapatite (HA) hollow domes specially manufactured for osteogenesis promotion. MATERIALS AND METHODS: Nine New Zealand rabbits were selected and 18 domes were placed, divided into three groups according to the filler: control (blood clot), vitamin complex, and particulate ß-tricalcium phosphate (ß-TCP). The healing period was 8 weeks, hence fluorescent markers were applied. After healing, the samples were embedded in resin to prepare slides for light and fluorescence microscopic evaluation of the amount of neoformed bone tissue. Energy dispersive spectroscopy was also used for chemical analysis of the material inside the domes. RESULTS: The quality of neoformed bone tissue with active bone remodeling areas was observed. As a filler, ß-TCP showed higher bone formation (14.1%), better quality of neoformed bone tissue with organized structures, and an area of mineralized tissue in the dome. Bone neoformation inside the dome filled with blood clot confirmed the osteoconductive property of HA, as indicated by the migration of osteogenic cells from the blood clot, without the action of another biomaterial (mean area of bone formation for blood clot filler = 7.5%). Bone neoformation was not favored in samples filled with vitamin complex because of the difficulty of blood penetration through the material. CONCLUSION: HA domes performed well as a scaffold for bone neoformation over the cortical bone of rabbits, and this is based on maintenance of good stability and good integration with bone tissue. ß-TCP presented higher values of neoformed bone area compared with the blood clot. HA domes have osteoconductive properties, especially when filled with blood clot, because of the migration of osteogenic cells without action of any other biomaterial. In domes filled with vitamin complex, no bone formation was noted because of the absence of resorption.

Biologic response to titanium implants with laser-treated surfaces.

PURPOSE: To examine the biologic response to titanium implant surfaces treated with a neodymium:yttrium-aluminum-garnet laser. MATERIALS AND METHODS: Sixty mini-implants made of grade 2 titanium were placed in the femora of 30 Wistar rats. Thirty implants had a machined surface and the other 30 had surfaces that were roughened by laser treatment. The animals were subdivided into three groups according to bone repair periods of 15, 30, and 60 days. The samples were observed under light and electron scanning microscopes and analyzed with the Student t test. RESULTS: Formation of new bone trabeculae toward the surface was apparent for the laser-treated implants at 15 days. Thin layers of bone matrix in intimate contact with the surface in the area of the central screw threads were observed, indicating high biocompatibility. Similar results were seen with machined implants after 30 days. A significant difference in bone formation was observed between the implant types at 15 days. CONCLUSION: Bone-to-implant contact was better on the surfaces subjected to laser treatment than on the machined titanium implants. The development of new laser treatments, which promote alterations in the surface energy as well as in the macro- and microstructures of titanium, may lead to improved bone-to-implant contact and thus better outcomes.

Physico-chemical characterization of zirconia-titania composites coated with an apatite layer for dental implants.

OBJECTIVES: To investigate the crystalline phases, morphological features and functional groups on the surface of sintered Y:TZP/TiO2 composite ceramics before and after the application of a biomimetic bone-like apatite layer. The effect of TiO2 content on the composite's characteristics was also evaluated. METHODS: Samples of Y:TZP containing 0-30mol% TiO2 were synthesized by co-precipitation, followed by filtration, drying and calcination. The powders were uniaxially pressed and sintered at 1500°C/1h. To obtain biomimetic coatings the samples were exposed to sodium silicate solution and then to a concentrated simulated body fluid solution. The surfaces, before and after coating, were characterized by diffuse reflectance infrared Fourier transformed spectroscopy, X-ray diffraction analysis and scanning electron microscopy. RESULTS: The surfaces of all Y:TZP/TiO2 samples were covered with a dense and uniform calcium phosphate layer with a globular microstructure. This layer was crystalline for specimens with 30% of TiO2 and amorphous for specimens with 0 and 10% of TiO2. Chemical analysis indicated that this layer was composed of type A carbonate apatite. Among the materials tested, the composite with 10% of TiO2 showed the best overall chemical and physical features, such as higher density and more cohesive amorphous apatite layer. SIGNIFICANCE: Y-TZP-based materials obtained in the present investigation by means of the successful association of a calcium phosphate biomimetic layer with small amounts TiO2 should be further explored as an option for ceramic dental implants with improved bioactivity.

Micro-morphological changes prior to adhesive bonding: high-alumina and glassy-matrix ceramics.

The aim of this study was to qualitatively demonstrate surface micro-morphological changes after the employment of different surface conditioning methods on high-alumina and glassy-matrix dental ceramics. Three disc-shaped high-alumina specimens (In-Ceram Alumina, INC) and 4 glassy-matrix ceramic specimens (Vitadur Alpha, V) (diameter: 5 mm and height: 5 mm) were manufactured. INC specimens were submitted to 3 different surface conditioning methods: INC1--Polishing with silicon carbide papers (SiC); INC2--Chairside air-borne particle abrasion (50 microm Al2O3); INC3 - Chairside silica coating (CoJet; 30 microm SiOx). Vitadur Alpha (V) specimens were subjected to 4 different surface conditioning methods: V1--Polishing with SiC papers; V2 - HF acid etching; V3--Chairside air-borne particle abrasion (50 microm Al2O3); V4--Chairside silica coating (30 microm SiOx). Following completion of the surface conditioning methods, the specimens were analyzed using SEM. After polishing with SiC, the surfaces of V specimens remained relatively smooth while those of INC exhibited topographic irregularities. Chairside air-abrasion with either aluminum oxide or silica particles produced retentive patterns on both INC and V specimens, with smoother patterns observed after silica coating. V specimens etched with HF presented a highly porous surface. Chairside tribochemical silica coating resulted in smoother surfaces with particles embedded on the surface even after air-blasting. Surface conditioning using air-borne particle abrasion with either 50 microm alumina or 30 microm silica particles exhibited qualitatively comparable rough surfaces for both INC and V. HF acid gel created the most micro-retentive surface for the glassy-matrix ceramic tested.

In vitro apatite formation on chemically treated (P/M) Ti-13Nb-13Zr.

OBJECTIVES: Titanium alloys are considered the material of choice when used as endosteal part of implants. However, they are not able to bond directly to bone. The objective of this study was to suggest a chemical surface treatment for Ti-13Nb-13Zr to initiate the formation of hydroxy carbonated apatite (HCA) during in vitro bioactivity tests in simulated body fluid (SBF). METHODS: Titanium, niobium, and zirconium hydride powders were blended, compacted and sintered. Sintered Ti-13Nb-13Zr samples were etched in HCl, H(3)PO(4), and in a mixture of HF+HNO(3), respectively, and subsequently pretreated in NaOH. The influence of acid etching conditions on the microstructure of the Ti-13Nb-13Zr alloys as well as on the rate of HCA formation was evaluated using SEM-EDS, FTIR, and gravimetric analyses. RESULTS: Sintered Ti-13Nb-13Zr alloys consist of a Widmannstätten (alpha+beta) microstructure. Exposure of chemically etched and NaOH activated samples to SBF for 1 week leads to the formation of a HCA layer on the surface of HCl as well as H(3)PO(4) treated samples. No HCA formation was found on HNO(3) treated samples. After 2 weeks in SBF the mass increase, that can be correlated to the HCA formation rate, was the highest for HCl pretreated samples (2.4 mg/cm(2)) followed by H(3)PO(4) (0.8 mg/cm(2)) and HNO(3) pretreated ones (0.2 mg/cm(2)). SIGNIFICANCE: Since the in vitro HCA formation from SBF is generally accepted as a typical feature for bioactive materials, it is supposed that HCl etching with subsequent NaOH treatment might enhance the in vivo bone-bonding ability of Ti-13Nb-13Zr.

Micro-morphological changes prior to adhesive bonding: high-alumina and glassy-matrix ceramics

The aim of this study was to qualitatively demonstrate surface micro-morphological changes after the employment of different surface conditioning methods on high-alumina and glassy-matrix dental ceramics. Three disc-shaped high-alumina specimens (In-Ceram Alumina, INC) and 4 glassy-matrix ceramic specimens (Vitadur Alpha, V) (diameter: 5 mm and height: 5 mm) were manufactured. INC specimens were submitted to 3 different surface conditioning methods: INC1 - Polishing with silicon carbide papers (SiC); INC2 - Chairside air-borne particle abrasion (50 µm Al2O3); INC3 - Chairside silica coating (CoJet; 30 µm SiOx). Vitadur Alpha (V) specimens were subjected to 4 different surface conditioning methods: V1 - Polishing with SiC papers; V2 - HF acid etching; V3 - Chairside air-borne particle abrasion (50 µm Al2O3); V4 - Chairside silica coating (30 µm SiOx). Following completion of the surface conditioning methods, the specimens were analyzed using SEM. After polishing with SiC, the surfaces of V specimens remained relatively smooth while those of INC exhibited topographic irregularities. Chairside air-abrasion with either aluminum oxide or silica particles produced retentive patterns on both INC and V specimens, with smoother patterns observed after silica coating. V specimens etched with HF presented a highly porous surface. Chairside tribochemical silica coating resulted in smoother surfaces with particles embedded on the surface even after air-blasting. Surface conditioning using air-borne particle abrasion with either 50 µm alumina or 30 µm silica particles exhibited qualitatively comparable rough surfaces for both INC and V. HF acid gel created the most micro-retentive surface for the glassy-matrix ceramic tested.