Biomineralization is a dynamic, complex, lifelong process by which living organisms control precipitations of inorganic nanocrystals within organic matrices to form unique hybrid biological tissues, for example, enamel, dentin, cementum, and bone. Understanding the process of mineral deposition is important for the development of treatments for mineralization-related diseases and also for the innovation and development of scaffolds. This review provides a thorough overview of the up-to-date information on the theories describing the possible mechanisms and the factors implicated as agonists and antagonists of mineralization. Then, the role of calcium and phosphate ions in the maintenance of teeth and bone health is described. Throughout the life, teeth and bone are at risk of demineralization, with particular emphasis on teeth, due to their anatomical arrangement and location. Teeth are exposed to food, drink, and the microbiota of the mouth; therefore, they have developed a high resistance to localized demineralization that is unmatched by bone. The mechanisms by which demineralization–remineralization process occurs in both teeth and bone and the new therapies/technologies that reverse demineralization or boost remineralization are also scrupulously discussed. Technologies discussed include composites with nano- and micron-sized inorganic minerals that can mimic mechanical properties of the tooth and bone in addition to promoting more natural repair of surrounding tissues. Turning these new technologies to products and practices would improve health care worldwide.

Cure, volumetric changes and mechanical properties were assessed for new dental composites containing chlorhexidine (CHX) and reactive calcium phosphate-containing (CaP) to reduce recurrent caries. 20wt.% of light curable urethane dimethacrylate based liquid was mixed with 80wt.% glass filler containing 10wt.% CHX and 0-40wt.% CaP. Conversion versus depth with 20 or 40s light exposure was assessed by FTIR. Solidification depth and polymerization shrinkage were determined using ISO 4049 and 17304, respectively. Subsequent volume expansion and biaxial flexural strength and modulus change upon water immersion were determined over 4 weeks. Hydroxyapatite precipitation in simulated body fluid was assessed at 1 week. Conversion decreased linearly with both depth and CaP content. Average solidification depths were 4.5, 3.9, 3.3, 2.9 and 5.0 with 0, 10, 20, and 40% CaP and a commercial composite, Z250, respectively. Conversions at these depths were 53±2% for experimental materials but with Z250 only 32%. With Z250 more than 50% conversion was achieved only below 1.1mm. Shrinkage was 3% and 2.5% for experimental materials and Z250, respectively. Early water sorption increased linearly, whilst strength and modulus decreased exponentially to final values when plotted versus square root of time. Maximum volumetric expansion increased linearly with CaP rise and balanced shrinkage at 10-20wt.% CaP. Strength and modulus for Z250 decreased from 191 to 158MPa and 3.2 to 2.5GPa. Experimental composites initial strength and modulus decreased linearly from 169 to 139MPa and 5.8 to 3.8GPa with increasing CaP. Extrapolated final values decreased from 156 to 84MPa and 4.1 to 1.7GPa. All materials containing CaP promoted hydroxyapatite precipitation. The lower surface of composite restorations should both be solid and have greater than 50% conversion. The results, therefore, suggest the experimental composite may be placed in much thicker layers than Z250 and have reduced unbounded cytotoxic monomer. Experimental materials with 10-20wt.% additionally have volumetric expansion to compensate shrinkage, antibacterial and re-mineralizing components and competitive mechanical properties.

Investigation of polymerisation kinetics using ATR-FTIR systems is common in many dental studies. However, peak selection methods to calculate monomer-polymer conversion can vary, consequently affecting final results. Thus, the aim of this study is to experimentally confirm which method is less prone to systematic errors. Three commercial restorative materials were tested–Vertise Flow (VF), Constic and Activa Bioactive Restorative Kids. Firstly, Attenuated Total Reflectance Fourier Transform Infra-Red (ATR-FTIR) (Spectrum One, Perkin-Elmer, UK) spectra of monomers were acquired—10-methacryloyloxy decyl dihydrogen phosphate (10-MDP), bisphenol-A glycidyl dimethacrylate (Bis-GMA), 2-hydroxyethyl methacrylate (HEMA), triethyelene glycol dimethacrylate (TEGDMA) and urethane dimethacrylate (UDMA) to investigate proportionality of methacrylate peak heights versus concentration. Spectral changes upon light exposure of 2 mm discs of the restorative materials (irradiated for 20 s, LED curing unit 1100–1330 mW/cm²) were assessed to study polymerisation kinetics (n = 3), with continuous acquisition of spectra, before, during and after light exposure. Peak differences and degrees of conversion (D_C %) were calculated using 1320/1336, 1320/1350 and 1636/1648 cm^-1 as reaction/reference peaks. Inferential statistics included a MANOVA and within-subjects repeated measures ANOVA design (5% significance level). Proportionality of methacrylate peak height to concentration was confirmed, with the 1320/1352 cm^-1 peak combination showing the lowest coefficient of variation (8%). Difference spectra of the polymerisation reaction showed noise interference around the 1500–1800 cm^-1 region. Across the different materials, D_C % results are highly dependent upon peak selection (p<0.001), with higher variability associated to the 1636 cm^-1. Significant differences in the materials were only detected when the 1320 cm^-1 peak was used (p<0.05). Within the same materials, methods were significantly different for Constic and Activa (p<0.05). It is possible to conclude that the 1320 cm^-1 peak is more adequate to assess polymerisation of methacrylates and is therefore recommended.

To determine the effects of various monomers on conversion and cytocompatibility of dental composites and to improve these properties without detrimentally affecting mechanical properties, depth of cure and shrinkage. Composites containing urethane dimethacrylate (UDMA) or bisphenol A glycidyl methacrylate (Bis-GMA) with poly(propylene glycol) dimethacrylate (PPGDMA) or triethylene glycol dimethacrylate (TEGDMA) were characterized using the following techniques: conversion (FTIR at 1 and 4mm depths), depth of cure (BS EN ISO 4049:2009 and FTIR), shrinkage (BS EN ISO 17304:2013 and FTIR), strength and modulus (biaxial flexural test) and water sorption. Cytocompatibility of composites and their liquid phase components was assessed using three assays (resazurin, WST-8 and MTS). UDMA significantly improved conversion, BFS and depth of cure compared to Bis-GMA, without increasing shrinkage. UDMA was cytotoxic at lower concentrations than Bis-GMA, but extracts of Bis-GMA-containing composites were less cytocompatible than of those containing UDMA. PPGDMA improved conversion and depth of cure compared to TEGDMA, without detrimentally affecting shrinkage. TEGDMA was shown by all assays to be highly toxic. Resazurin, but not WST-8 and MTS, suggested that PPGDMA exhibited improved cytocompatibility compared to TEGDMA. The use of UDMA and PPGDMA results in composites with excellent conversion, depth of cure and mechanical properties, without increasing shrinkage. Composites containing UDMA appear to be slightly more cytocompatible than those containing Bis-GMA. These monomers may therefore improve the material properties of dental restorations, particularly bulk fill materials. The effect of diluent monomer on cytocompatibility requires further investigation.