PurposeThis study developed light cured dental composites with added monocalcium phosphate monohydrate (MCPM), tristrontium phosphate (TSrP) and antimicrobial polylysine (PLS). The aim was to produce composites that have enhanced water sorption induced expansion, can promote apatite precipitation and release polylysine.Materials and MethodsExperimental composite formulations consisted of light activated dimethacrylate monomers combined with 80 wt% powder. The powder phase contained a dental glass with and without PLS (2.5 wt%) and/or reactive phosphate fillers (15 wt% TSrP and 10 wt% MCPM). The commercial composite, Z250, was used as a control. Monomer conversion and calculated polymerization shrinkage were assessed using FTIR. Subsequent mass or volume changes in water versus simulated body fluid (SBF) were quantified using gravimetric studies. These were used, along with Raman and SEM, to assess apatite precipitation on the composite surface. PLS release was determined using UV spectroscopy. Furthermore, biaxial flexural strengths after 24 hours of SBF immersion were obtained.ResultsMonomer conversion of the composites decreased upon the addition of phosphate fillers (from 76 to 64%) but was always higher than that of Z250 (54%). Phosphate addition increased water sorption induced expansion from 2 to 4% helping to balance the calculated polymerization shrinkage of ~ 3.4%. Phosphate addition promoted apatite precipitation from SBF. Polylysine increased the apatite layer thickness from ~ 10 to 20 μm after 4 weeks. The novel composites showed a burst release of PLS (3.7%) followed by diffusion-controlled release irrespective of phosphate addition. PLS and phosphates decreased strength from 154 MPa on average by 17% and 18%, respectively. All formulations, however, had greater strength than the ISO 4049 requirement of > 80 MPa.ConclusionThe addition of MCPM with TSrP promoted hygroscopic expansion, and apatite formation. These properties are expected to help compensate polymerization shrinkage and help remineralize demineralized dentin. Polylysine can be released from the composites at early time. This may kill residual bacteria.

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.

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.

PurposeThe aim was to assess monomer conversion, dimensional stability, flexural strength / modulus, surface apatite precipitation and wear of mono / tri calcium phosphate (CaP) and polylysine (PLS)—containing dental composites. These were formulated using a new, high molecular weight, fluid monomer phase that requires no polymerisation activator.Materials and methodsUrethane and Polypropylene Glycol Dimethacrylates were combined with low levels of an adhesion promoting monomer and a light activated initiator. This liquid was mixed with a hybrid glass containing either 10 wt% CaP and 1 wt% PLS (F1) or 20 wt% CaP and 2 wt% PLS (F2). Powder to liquid mass ratio was 5:1. Commercial controls included Gradia Direct Posterior (GD) and Filtek Z250 (FZ). Monomer conversion and polymerisation shrinkage were calculated using Fourier Transform Infrared (FTIR). Subsequent volume increases in water over 7 weeks were determined using gravimetric studies. Biaxial flexural strength (BFS) / modulus (BFM) reduction and surface apatite precipitation upon 1 and 4 weeks immersion in water versus simulated body fluid (SBF) were assessed using a mechanical testing frame and scanning electron microscope (SEM). Mass / volume loss and surface roughness (Ra) following 7 weeks water immersion and subsequent accelerated tooth-brush abrasion were examined using gravimetric studies and profilometer.ResultsF1 and F2 exhibited much higher monomer conversion (72%) than FZ (54%) and low calculated polymerization shrinkage (2.2 vol%). Final hygroscopic expansions decreased in the order; F2 (3.5 vol%) > F1 (1.8 vol%) ~ Z250 (1.6 vol%) > Gradia (1.0 vol%). BFS and BFM were unaffected by storage medium type. Average BFS / BFM upon 4 weeks immersion reduced from 144 MPa / 8 GPa to 107 MPa / 5 GPa for F1 and 105 MPa / 6 GPa to 82 MPa / 4 GPa for F2. Much of this change was observed in the first week of immersion when water sorption rate was high. Surface apatite layers were incomplete at 1 week, but around 2 and 15 micron thick for F1 and F2 respectively following 4 weeks in SBF. Mass and volume loss following wear were equal. Average results for F1 (0.5%), F2 (0.7%), and FZ (0.5%) were comparable but lower than that of GD (1%). Ra, however, decreased in the order; F1 (15 μm) > F2 (11 μm) > GD (9 μm) > FZ (5 μm).ConclusionsHigh monomer conversion in combination with large monomer size and lack of amine activator should improve cytocompatibility of the new composites. High monomer molecular weight and powder content enables low polymerisation shrinkage despite high conversion. Increasing active filler provides enhanced swelling to balance shrinkage, which, in combination with greater surface apatite precipitation, may help seal gaps and reduce bacterial microleakage. High monomer conversion also ensures competitive mechanical / wear characteristics despite enhanced water sorption. Furthermore, increased active filler could help reduce surface roughness upon wear.

Continuing cariogenic bacterial growth demineralizing dentine beneath a composite filling is the most common cause of tooth restoration failure. Novel composites with antibacterial polylysine (PLS) (0, 4, 6, or 8 wt%) in its filler phase were therefore produced. Remineralising monocalcium phosphate was also included at double the PLS weight. Antibacterial studies involved set composite disc placement in 1% sucrose-supplemented broth containing Streptococcus mutans (UA159). Relative surface bacterial biofilm mass (n = 4) after 24 h was determined by crystal violet-binding. Live/dead bacteria and biofilm thickness (n = 3) were assessed using confocal laser scanning microscopy (CLSM). To understand results and model possible in vivo benefits, cumulative PLS release from discs into water (n = 3) was determined by a ninhydrin assay. Results showed biofilm mass and thickness decreased linearly by 28% and 33%, respectively, upon increasing PLS from 0% to 8%. With 4, 6, and 8 wt% PLS, respectively, biofilm dead bacterial percentages and PLS release at 24 h were 20%, 60%, and 80% and 85, 163, and 241 μg/disc. Furthermore, initial PLS release was proportional to the square root of time and levelled after 1, 2, and 3 months at 13%, 28%, and 42%. This suggested diffusion controlled release from water-exposed composite surface layers of 65, 140, and 210 μm thickness, respectively. In conclusion, increasing PLS release initially in any gaps under the restoration to kill residual bacteria or longer-term following composite/tooth interface damage might help prevent recurrent caries.