Rapid and area-specific coating of fluoride-incorporated apatite layers by a laser-assisted biomimetic process for tooth surface functionalization.

Surface functionalization of teeth with fluoride-incorporated apatite layers displays great potential in treatments and prevention of dental disorders. In this study, we used a sintered hydroxyapatite (sHA) substrate as a model material of teeth, and established a rapid and area-specific coating technique of fluoride-incorporated apatite layers by using a laser-assisted biomimetic (LAB) process. In this technique, a sHA substrate was irradiated on the surface with a Nd:YAG pulsed UV laser for 30 min in supersaturated calcium phosphate (CaP) solutions with various fluoride concentrations. The fluoride concentration in the CaP solution was varied to control morphology, crystalline structure, and fluoride content of the resulting layers. Without fluoride in the CaP solution, an octacalcium phosphate (OCP) layer with a flake-like structure was formed on the laser-irradiated surface of the substrate. The addition of fluoride (1000 µM and 3000 µM) to the CaP solution led to the formation of fluoride-incorporated apatite layers with an enamel-like needle-like nanostructure. The fluoride-incorporated apatite layers adhered firmly to the sHA surface and reduced acid dissolution of the sHA substrate by acting as a protective covering. Additionally, the layers released fluoride ions for more than 24 h, and exhibited antibacterial activity relative to a caries-causing bacterium, namely Streptococcus mutans. Thus, our LAB process can potentially act as a new tool for functionalization of tooth surfaces. STATEMENT OF SIGNIFICANCE: We used a sintered hydroxyapatite (sHA) substrate as a model material of teeth, and established a rapid and area-specific coating technique of fluoride-incorporated apatite layers on the sHA surface by using our laser-assisted biomimetic (LAB) process. In this process, pulsed laser was utilized to accelerate seeded crystal growth in supersaturated calcium phosphate solutions supplemented with NaF. The thus-fabricated fluoride-incorporated apatite layers consisted of enamel-like needle-like nanocrystals with c-axis orientation. These fluoride-incorporated apatite layers adhered firmly to the sHA surface, reduced acid dissolution of the sHA substrate by acting as a protective covering, and exhibited antibacterial activity against Streptococcus mutans through the fluoride release. Thus, our LAB process can potentially act as a new tool for functionalization of tooth surfaces.

Enhanced near band edge luminescence of Ti/ZnO nanorod heterostructures due to the surface diffusion of Ti.

Information on the mechanistic differences in the luminescence properties of Ti/ZnO nanorods (NRs) has been obtained through the preparation of heterostructures by (a) varying the thickness of Ti from 1 nm to 20 nm keeping the substrate temperature at 400 °C, (b) varying the substrate temperature from room temperature (RT) to 500 °C while keeping the metal thickness constant at 10 nm and (c) annealing the RT Ti sputtered NRs at temperatures of 400 °C and 500 °C. The photoluminescence (PL) spectra show that the near band edge luminescence of ZnO in the ultraviolet (UV) region is enhanced as the thickness of Ti increases up to 5 nm and, thereafter, it falls. Sputtering of Ti on ZnO NRs at RT does not cause any UV enhancement but when sputtered at and above 400 °C, the UV intensity is enhanced. Annealing of RT Ti sputtered NRs at and above 400 °C also results in the enhancement of the UV peak, although with a lesser magnitude. Analysis of the PL results, supported by X-ray diffraction, field emission scanning electron microscopy, elemental mapping, high resolution transmission electron microscopy, Fourier transform infrared spectroscopy and electrical I-V measurement results, show a clear indication that the surface diffusion of Ti causes a reduction in the surface defects.