Filler characteristics of modern dental resin composites and their influence on physico-mechanical properties.

OBJECTIVE: The mechanical properties of dental resin-based composites (RBCs) are highly dependent on filler characteristics (size, content, geometry, composition). Most current commercial materials are marketed as "nanohybrids" (i.e. filler size <1µm). In the present study, filler characteristics of a selection of RBCs were described, aiming at identifying correlations with physico-mechanical properties and testing the relevance of the current classification. METHODS: Micron/sub-micron particles (> or <500nm) were isolated from 17 commercial RBCs and analyzed by laser diffractrometry and/or electron microscopy. Filler and silane content were evaluated by thermogravimetric analysis and a sedimentation technique. The flexural modulus (Eflex) and strength (σflex) and micro-hardness were determined by three-point bending or with a Vickers indenter, respectively. Sorption was also determined. All experiments were carried out after one week of incubation in water or 75/25 ethanol/water. RESULTS: Average size for micron-sized fillers was almost always higher than 1µm. Ranges for mechanical properties were: 3.775wt%) were associated with the highest mechanical properties (Eflex and σflex>12GPa and 130MPa, respectively) and lowest solvent sorption (∼0.3%). SIGNIFICANCE: Mechanical properties and filler characteristics significantly vary among modern RBCs and the current classification does not accurately illustrate either. Further, the chemical stability of RBCs differed, highlighting differences in resin and silane composition. Since Eflex and sorption were well correlated to the filler content, a simple and unambiguous classification based on such characteristic is suggested, with three levels (ultra-low fill, low-fill and compact resin composites).

Photopolymerization of highly filled dimethacrylate-based composites using Type I or Type II photoinitiators and varying co-monomer ratios.

OBJECTIVES: The use of a Type I photoinitiator (monoacylphosphine oxide, MAPO) was described as advantageous in a model formulation, as compared to the conventional Type II photoinitiator (Camphorquinone, CQ). The aim of the present work was to study the kinetics of polymerization of various composite mixtures (20-40-60-80 mol%) of bisphenol A glycidyl dimethacrylate/triethylene glycol dimethacrylate (BisGMA/TegDMA) containing either CQ or MAPO, based on real-time measurements and on the characterization of various post-cure characteristics. METHODS: Polymerization kinetics were monitored by Fourier-transform near-infrared spectroscopy (FT-NIRS) and dielectric analysis (DEA). A range of postcure properties was also investigated. RESULTS: FT-NIRS and DEA proved complementary to follow the fast kinetics observed with both systems. Autodecceleration occurred after ≈1 s irradiation for MAPO-composites and ≈5-10 s for CQ-composites. Conversion decreased with increasing initial viscosity for both photoinitiating systems. However despite shorter light exposure (3s for MAPO vs 20s for CQ-composites), MAPO-composites yielded higher conversions for all co-monomer mixtures, except at 20 mol% BisGMA, the less viscous material. MAPO systems were associated with increased amounts of trapped free radicals, improved flexural strength and modulus, and reduced free monomer release for all co-monomer ratios, except at 20 mol% BisGMA. SIGNIFICANCE: This work confirms the major influence of the initiation system both on the conversion and network cross-linking of highly-filled composites, and further highlights the advantages of using MAPO photoinitiating systems in highly-filled dimethacrylate-based composites provided that sufficient BisGMA content (>40 mol%) and adapted light spectrum are used.

Temozolomide-loaded photopolymerizable PEG-DMA-based hydrogel for the treatment of glioblastoma.

Glioblastoma is the most frequent primary malignant brain tumor in adults. Despite treatments including surgery, radiotherapy and chemotherapy by oral Temozolomide (TMZ), the prognosis of patients with glioblastoma remains very poor. We hypothesized that a polyethylene glycol dimethacrylate (PEG-DMA) injectable hydrogel would provide a sustained and local delivery of TMZ. The hydrogel photopolymerized rapidly (<2min) and presented a viscous modulus (≈10kPa). TMZ release kinetic presented two phases: a linear burst release of 45% of TMZ during the first 24h, followed by a logarithmic release of 20% over the first week. The in vivo tolerability study showed that the unloaded hydrogel did not induce apoptosis in mice brains nor increased microglial activation. In vivo, the anti-tumor efficacy of TMZ-hydrogel was evaluated on xenograft U87MG tumor-bearing nude mice. The tumor weight of mice treated with the photopolymerized TMZ hydrogel drastically decreased compared with all other groups. Higher apoptosis (located at the center of the tumor) was also observed. The present study demonstrates the potential of a photopolymerizable TMZ-loaded hydrogel to treat glioblastoma.

The effect of ultra-fast photopolymerisation of experimental composites on shrinkage stress, network formation and pulpal temperature rise.

OBJECTIVES: to complement our previous work by testing the null hypotheses that with short curing times and high DC, TPO-based resin composites would exhibit (1) higher polymerization stresses and consequently display (2) higher temperature rise and (3) higher flexural modulus, flexural strength and hardness, compared to a conventional CQ-based experimental composite. METHODS: Two experimental resin composites using either Lucirin-TPO or camphorquinone/DMAEMA as photoinitiators were prepared. Light curing was carried out using spectral outputs adapted to the absorption properties of each initiator. Different irradiation protocols were selected (0.5, 1, 3, 9 s at 500, 1000 and 2000 mW/cm(2) for Lucirin-TPO based composites and 20 or 40 s at 1000 mW/cm2 for Lucirin-TPO and camphorquinone-based composites). Degree of conversion (DC) was measured in real time by means of FT-NIR spectroscopy. Pulpal temperature rise (ΔT) was studied in a tooth model. Polymerization stress was monitored using the Bioman instrument. For cured specimens, flexural modulus and flexural strength were determined using a three point bending platform and Vickers hardness was determined with a microhardness indentor on samples prior to and after 24 h incubation in 75/25 ethanol/H2O. Premolars were restored with both materials and microleakage at the teeth/composite interfaces following restoration was assessed. RESULTS: Lucirin-TPO-based composites irradiated at radiant exposures of 3 J/cm(2) and more exhibited significantly higher DCs, associated with increased flexural moduli and hardness compared to CQ-based composites. For an ultra-short irradiation time of 1 s at 1000 mW/cm(2), TPO-composites displayed similar polymerization stresses compared to CQ-controls with yet a 25% increase for flexural modulus and 40% increase for hardness measured after EtOH/H2O sorption. Higher stress rates were however observed in all curing protocols compared to CQ-composites. Microleakage was similar between TPO and CQ-composites irradiated at 1000 mW/cm(2) for 3 and 20 s respectively, while a significant increase was observed for TPO-composites irradiated for 1 s. ΔT measured through a 0.6 mm thick dentin layer were all below 5.5°C; TPO-composites exhibited similar or lower values compared to controls. SIGNIFICANCE: The use of Lucirin-TPO in resin composites along with appropriate curing conditions may allow for a major reduction of irradiation time while improving mechanical properties. The amount of stress observed during polymerization in TPO-based composites can be similar to those using CQ and the cohesion at the restoration-tooth interface was not affected by short curing times. Contrary to other studies, we found that the temperatures increases measured during polymerization were all well below the 5.5°C threshold for the pulp.

Ultra-fast light-curing resin composite with increased conversion and reduced monomer elution.

OBJECTIVES: To test the null hypotheses that photoactive resin composites containing a Type I photoinitiator would exhibit reduced DC or increased monomer elution at substantially short curing times compared with materials based on a Type 2 ketone/amine system. METHODS: Two experimental resin composites were prepared, using either Lucirin-TPO or camphorquinone/DMAEMA. Specimens were light-cured using appropriate spectral emission that coincided with the absorption properties of each initiator using different irradiation protocols (0.5, 1, 3, 9s at 500, 1000 and 2000mW/cm(2) for Lucirin-TPO based composites and 20 or 40s at 1000mW/cm(2) for Lucirin-TPO and camphorquinone-based composites). Degree of conversion (DC) was measured by Raman spectroscopy, propagating radical concentrations were collected by means of electron paramagnetic resonance (EPR) and monomer leaching was characterized using high-performance liquid chromatography (HPLC). RESULTS: The null hypotheses were rejected, except for a single irradiation protocol (0.5s @ 500mW/cm(2)). Lucirin-TPO-based composites could cure 20 times faster and release at least 4 times less monomers in comparison to camphorquinone-based composites. At 1000mW/cm(2), and 1s irradiation time for curing times of 1s, Lucirin-TPO based composites displayed 10% higher DC. The difference in polymerization efficiency of Lucirin-TPO compared with camphorquinone-based resin composites were explained using EPR; the former showing a significantly greater yield of radicals which varied logarithmically with radiant exposure. SIGNIFICANCE: Lucirin-TPO is substantially more efficient at absorbing and converting photon energy when using a curing-light with an appropriate spectral emission and otherwise a limitation noted in several previous publications. At concentrations of 0.0134mol/L, Lucirin-TPO-based composites require a minimum light intensity of 1000mW/cm(2) and an exposure time of 1s to provide significantly improved DC and minimal elution compared with a conventional photoinitiator system. The use of a wide range of curing protocols in the current experiment has realized the significant potential of Lucirin-TPO and its impact for clinical applications, in replacement to materials using camphorquinone.