Biomedical Device Surface Treatment by Laser-Driven Hydroxyapatite Penetration-Synthesis Technique for Gapless PEEK-to-Bone Integration.

Polyetheretherketone (PEEK), a bioinert polymer known for its mechanical properties similar to bone, is capable of averting stress shielding. Due to these attributes, it finds applications in diverse fields like orthopedics, encompassing cervical disc replacement for the neck and spine, along with dentistry and plastic surgery. However, due to insufficient bonding with bone, various methods such as hydroxyapatite (HA) coating on the surface are attempted. Nonetheless, the interface between the polymer and ceramic, two different materials, tended to delaminate after transplantation, posing challenges in preventing implant escape or dislodgement. This research delves into the laser-driven hydroxyapatite penetration-synthesis technique. Differing from conventional coating methods that bond layers of dissimilar materials like HA and PEEK, this technology focuses on synthesizing and infiltrating ionized HA within the PEEK substrate resulting in an interface-free HA-PEEK surface. Conversely, HA-PEEK with this technology applied achieves complete, gap-free direct bone-implant integration.  Our research involved the analysis of various aspects. By means of these, we quantitatively assesed the enhanced bone bonding characteristics of HA-PEEK surfaces treated with this approach and offered and explanation for the mechanism responsible for direct bone integration.

Rapid Synthesis of Multifunctional Apatite via the Laser-Induced Hydrothermal Process.

Synthetic biomaterials are used to overcome the limited quantity of human-derived biomaterials and to impart additional biofunctionality. Although numerous synthetic processes have been developed using various phases and methods, currently commonly used processes have some issues, such as a long process time and difficulties with extensive size control and high-concentration metal ion substitution to achieve additional functionality. Herein, we introduce a rapid synthesis method using a laser-induced hydrothermal process. Based on the thermal interaction between the laser pulses and titanium, which was used as a thermal reservoir, hydroxyapatite particles ranging from nanometer to micrometer scale could be synthesized in seconds. Further, this method enabled selective metal ion substitution into the apatite matrix with a controllable concentration. We calculated the maximum temperature achieved by laser irradiation at the surface of the thermal reservoir based on the validation of three simplification assumptions. Subsequent linear regression analysis showed that laser-induced hydrothermal synthesis follows an Arrhenius chemical reaction. Hydroxyapatite and Mg2+-, Sr2+-, and Zn2+-substituted apatite powders promoted bone cell attachment and proliferation ability due to ion release from the hydroxyapatite and the selective ion-substituted apatite powders, which had a low crystallinity and relatively high solubility. Laser-induced hydrothermal synthesis is expected to become a powerful ceramic material synthesis technology.

Effect of grain size of dental zirconia on shear bond strength of composite resin cement.

The effect of grain size of dental zirconia on the shear bond strength of composite resin cement was newly studied. Disc-shaped dental zirconia with small (sample S) and large (sample L) grains were made by sintering of pre-sintered dental zirconia at 1450°C for 0.5 h and 40 h, respectively. After the sintering, the average grain size of sample S was 1.37 ± 0.15 µm, while that of sample L was 3.74 ± 0.50 µm. The sintered discs were successively polished with different grades of diamond and alumina slurries. The interfacial free energies were 63.5 ± 4.2 dyne/cm for sample S and 52.1 ± 5.5 dyne/cm for sample L. Stainless steel cylinders, previously sandblasted with 50 µm alumina powder, were bonded to the zirconia discs using composite resin cement. Next, samples were kept in an oven for 7 d at 36.5°C. The shear bond strength of sample S was 23.0 ± 4.5 MPa while that of sample L was 17.5 ± 4.6 MPa. After the fracture, the areal % values of composite resin cement remaining on the zirconia surfaces were 89.7 ± 5.9% for sample S and 61.6 ± 5.5% for sample L. The results suggest that grain size reduction has a potential to enhance the degree of bonding between a composite resin cement and a dental zirconia due to the increase of interfacial free energy.

Synthesis of a Ca3 SiO5 -Ca2 SiO4 -Ca3 Al2 O6 cement system with rapid setting capacity by spray-pyrolysis coupled with sol-gel method.

A modified mineral-trioxide-aggregate (mMTA) with rapid setting capacity was newly synthesized by spray-pyrolysis following a sol-gel reaction. Its faster setting capacity and initially higher compressive strength compared with Portland cement (PC) were evaluated. The precursor solution of the mMTA was prepared through condensation following hydrolysis among Ca(NO3 )2 ·4H2 O, Si(OC2 H5 )4 , and Al(NO3 )3 ·9H2 O under nitric acid. The mMTA powder was then synthesized by spray-pyrolysis at 1500°C. The particle shape was spherical with an average particle size of 0.8 ± 0.3 µm, while PC particles were irregular and 3.9 ± 3.0 µm in size. The mMTA consisted of mostly Ca3 SiO5 , Ca3 Al2 O6 , and partial Ca2 SiO4 phases, while the PC comprised mainly Ca3 SiO5 , Ca2 SiO4 , and partial Ca3 Al2 O6 phases. The final setting times of mMTA and PC measured under 95% relative humidity were about 11 min and 3 h, respectively. The early stage of setting in mMTA was dominated by the rapid formation of hexagonal-plate-like Ca3 Al2 O6 ·6H2 O crystals, while that in PC was dominated by needle-like calcium-silicate-hydrate gels and columnar-shaped Ca(OH)2 crystals. The late stage of setting in mMTA was dominated by calcium-silicate-hydrate gels and Ca(OH)2 crystals, while that in PC was dominated by Ca3 Al2 O6 ·6H2 O crystals. The compressive strengths of mMTA and PC after 30 min of setting were 4.5 and 0.2 MPa, respectively. The results suggest that mMTA has potential to be used as a filling material for accidental pulp-exposure or pulpal floor perforation cases that require rapid setting capacity and initial good strength. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 107B: 1440-1451, 2019.

Preparation of fluoride-loaded microcapsules for anticariogenic bacterial growth using a coaxial ultrasonic atomizer.

A new method to deliver fluoride using biodegradable poly(lactic-co-glycolic acid) microcapsules to suppress cariogenic bacterial growth during orthodontic treatment was investigated. A coaxial ultrasonic atomizer was used to encapsulate KF solution into microcapsules. The orthodontic adhesive resin disk containing fluoride loaded microcapsules (DFLM) was prepared by LED light curing. The microstructure of microcapsules, successful loading of KF, fracture strength, and shear bonding strength were assessed by FE-SEM, confocal laser scanning microscope, and general purpose testing machine, respectively. Fluoride release from the DFLM in phosphate buffered saline and pH changes were measured after different periods of soaking time. Antibacterial activity of the DFLM was assessed in tryptic soy broth containing mutant streptococci. The starting inoculum and the orthodontic resin disk containing microcapsules not loaded with KF were used as negative and positive controls, respectively. As results, the cumulative amount of KF after 49 days was about 85% of the initial amount of fluoride contained in the microcapsules. The fracture and shear bonding strengths of the orthodontic resin disks with and without the microcapsules were similar to each other. The DFLM showed lower bacterial growth than the control groups, whereas no statistically significant differences were found between the negative and positive controls. It can be concluded that the microcapsules loaded with fluoride prepared by a coaxial ultrasonic atomizer have good potential for application as an antibacterial agent due to their excellent cariogenic antibacterial activity when incorporated into orthodontic adhesive resin. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 31-39, 2018.

Enhanced osteoconductivity of sodium-substituted hydroxyapatite by system instability.

The effect of substituting sodium for calcium on enhanced osteoconductivity of hydroxyapatite was newly investigated. Sodium-substituted hydroxyapatite was synthesized by reacting calcium hydroxide and phosphoric acid with sodium nitrate followed by sintering. As a control, pure hydroxyapatite was prepared under identical conditions, but without the addition of sodium nitrate. Substitution of calcium with sodium in hydroxyapatite produced the structural vacancies for carbonate ion from phosphate site and hydrogen ion from hydroxide site of hydroxyapatite after sintering. The total system energy of sodium-substituted hydroxyapatite with structural defects calculated by ab initio methods based on quantum mechanics was much higher than that of hydroxyapatite, suggesting that the sodium-substituted hydroxyapatite was energetically less stable compared with hydroxyapatite. Indeed, sodium-substituted hydroxyapatite exhibited higher dissolution behavior of constituent elements of hydroxyapatite in simulated body fluid (SBF) and Tris-buffered deionized water compared with hydroxyapatite, which directly affected low-crystalline hydroxyl-carbonate apatite forming capacity by increasing the degree of apatite supersaturation in SBF. Actually, sodium-substituted hydroxyapatite exhibited markedly improved low-crystalline hydroxyl-carbonate apatite forming capacity in SBF and noticeably higher osteoconductivity 4 weeks after implantation in calvarial defects of New Zealand white rabbits compared with hydroxyapatite. In addition, there were no statistically significant differences between hydroxyapatite and sodium-substituted hydroxyapatite on cytotoxicity as determined by BCA assay. Taken together, these results indicate that sodium-substituted hydroxyapatite with structural defects has promising potential for use as a bone grafting material due to its enhanced osteoconductivity compared with hydroxyapatite.

Preparation of a novel anorganic bovine bone xenograft with enhanced bioactivity and osteoconductivity.

A novel anorganic bovine bone xenograft with enhanced bioactivity and osteoconductivity was prepared by an ion substitution method using sodium hypochlorite. Bovine bone granules were defatted, washed, and then soaked in sodium hypochlorite solution at room temperature. Subsequently, the granules were dried and then heat-treated at 1000°C with sodium hypochlorite. As a control, bovine bone granules were prepared with the same conditions but without sodium hypochlorite treatment. Phase, functional group, and elemental analyses by XRD, FTIR, and EPMA showed that the granules heat-treated without and with sodium hypochlorite were pure hydroxyapatite and sodium-chlorine-bearing hydroxyapatite, respectively. After soaking in simulated body fluid (SBF) for 1 week, low crystalline hydroxyl carbonate apatite fully covered the surface of sodium-chlorine-bearing hydroxyapatite, whereas it formed little on the hydroxyapatite surface. After soaking in SBF and deionized water, ICP-AES and IC analyses showed that the dissolutions of calcium, sodium, chlorine, and hydroxyl ions from sodium-chlorine-bearing hydroxyapatite notably increased compared with those from hydroxyapatite. This resultantly increased the ionic activity product of apatite in SBF and induced new formation of low crystalline hydroxyl carbonate apatite. The cytotoxicity test by BCA assay showed that there were no statistically significant differences between hydroxyapatite and sodium-chlorine-bearing hydroxyapatite. In addition, sodium-chlorine-bearing hydroxyapatite showed better osteoconductivity in the calvarial defects of New Zealand white rabbits within 4 weeks compared with that of hydroxyapatite. The results suggest that this novel anorganic bovine bone xenograft possesses encouraging potential for use as a bone grafting material due to better bioactivity and osteoconductivity than hydroxyapatite.