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Development of dental composites with reactive fillers that promote precipitation of antibacterial-hydroxyapatite layers.

Abstract

The study aim was to develop light-curable, high strength dental composites that would release calcium phosphate and chlorhexidine (CHX) but additionally promote surface hydroxyapatite/CHX co-precipitation in simulated body fluid (SBF). 80wt.% urethane dimethacrylate based liquid was mixed with glass fillers containing 10wt.% CHX and 0, 10, 20 or 40wt.% reactive mono- and tricalcium phosphate (CaP). Surface hydroxyapatite layer thickness/coverage from SEM images, Ca/Si ratio from EDX and hydroxyapatite Raman peak intensities were all proportional to both time in SBF and CaP wt.% in the filler. Hydroxyapatite was, however, difficult to detect by XRD until 4weeks. XRD peak width and SEM images suggested this was due to the very small size (~10nm) of the hydroxyapatite crystallites. Precipitate mass at 12weeks was 22wt.% of the sample CaP total mass irrespective of CaP wt.% and up to 7wt.% of the specimen. Early diffusion controlled CHX release, assessed by UV spectrometry, was proportional to CaP and twice as fast in water compared with SBF. After 1week, CHX continued to diffuse into water but in SBF, became entrapped within the precipitating hydroxyapatite layer. At 12weeks CHX formed 5 to 15% of the HA layer with 10 to 40wt.% CaP respectively. Despite linear decline of strength and modulus in 4weeks from 160 to 101MPa and 4 to 2.4GPa, respectively, upon raising CaP content, all values were still within the range expected for commercial composites. The high strength, hydroxyapatite precipitation and surface antibacterial accumulation should reduce tooth restoration failure due to fracture, aid demineralised dentine repair and prevent subsurface carious disease respectively

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