Effect of thickness on the degree of conversion of two bulk-fill and one conventional posterior resin-based composites at high irradiance and high temporal resolution.

OBJECTIVES: This study: 1) measures the effect of sample thickness and high irradiance on the depth-dependent time delay before photopolymerization reaction onset; 2) determines if exposure reciprocity exists; 3) measures the conversion rate at four irradiance levels; 4) determines the time, t0, at which the maximum DC rate is reached for two bulk-fill and one conventional posterior resin-based composites (RBCs). METHODS: Tetric PowerFill IVA shade (Ivoclar Vivadent) and Aura bulk-fill ultra universal restorative (SDI), and one conventional posterior resin-based composite (RBC), Heliomolar A3 (Ivoclar Vivadent), that were either 0.2 mm, 2 mm, or 4 mm thick were photocured using a modified Bluephase G4 (Ivoclar Vivadent) light-curing unit (LCU) that delivered a single emission band (wavelength centered at 449 nm). The same radiant exposure of 24 J/cm2 was delivered at irradiances ranging from 0.5 to 3 W/cm2 by adjusting the exposure time. PowerFill was also photocured for 3 s or 6 s using a Bluephase PowerCure LCU (Ivoclar Vivadent) on the 3 s mode setting. The degree of conversion (DC) was measured in real-time at a high temporal resolution at 30 °C using Attenuated Total Reflection (ATR) FTIR spectroscopy with a sampling rate of 13 DC data points per second. The DC data were analyzed using a phenomenological autocatalytic model. The RBC viscosity was measured at 21 °C and 30 °C. Light transmission through the RBC samples at 22 °C was monitored with time to calculate the extinction coefficients of the RBCs. RESULTS: The time delay before photopolymerization started increased as the RBC thickness increased and the irradiance decreased. An autocatalytic model described the DC data. The time t0 was less than 77 ms for the 0.2 mm thick samples of PowerFill irradiated using the highest irradiance of 3 W/cm2. Among the three RBCs for each sample thickness and irradiance level, the PowerFill had the smallest time t0. There was a time delay of 0.59 s and 1.25 s before the DC started to increase at the bottom of 4 mm thick samples for the PowerFill and Aura, respectively, when an irradiance of 1 W/cm2 was delivered. The time delay increased to 3.65 s for the Aura when an irradiance of 0.5 W/cm2 was delivered. The extinction coefficients near 449 nm were 0.78 mm-1, 0.76 mm-1, and 1.55 mm-1 during the first 2 s after the start of photocuring of PowerFill, Aura, and Heliomolar, respectively. Only PowerFill followed exposure reciprocity. At T = 30 °C, the viscosity was 3400, 17000, and 5200 Paˑs for PowerFill, Aura, and Heliomolar, respectively. SIGNIFICANCE: The time delay between when photopolymerization starts at the top and bottom of 2- or 4-mm thick RBC restorations may affect the structural integrity of the bond between the tooth and the bottom of the restoration. Only PowerFill followed exposure reciprocity between irradiance levels of 0.5 to 3 W/cm2. Exposure reciprocity did not occur for Aura or Heliomolar, neither of which are optimized for short light exposure or high irradiance conditions.

Synthesis, characterization and evaluation of azobenzene nanogels for their antibacterial properties in adhesive dentistry.

The presence of cariogenic bacteria within the prepared tooth cavity at the adhesive resin-dentin interface is detrimental to the long-term stability and function of composite restorations. Here, we report the synthesis and incorporation of methacrylated azobenzene nanogels within bisphenol A-glycidyl methacrylate/hydroxyethyl methacrylate/ethanol (B/H/E) adhesive resins and evaluate their ability to reduce the bacterial invasion of cariogenic Streptococcus mutans biofilms while preserving the mechanical strength and structural integrity of the critical interfacial connection between the restoration and the tooth. The azobenzene nanogel, with a hydrodynamic radius of < 2 nm and a molecular weight of 12,000 Da, was polymerized within B/H/E adhesive formulations at concentrations of 0.5 wt.%, 1.5 wt.%, and 2.5 wt.%. While the double-bond conversion, cytocompatibility, water solubility, and sorption of the adhesive networks were comparable, azobenzene nanogel networks showed improved hydrophobicity with a ≥ 25° increase in water contact angle. The polymerized adhesive surfaces formulated with azobenzene nanogels showed a 66% reduction in bacterial biofilms relative to the control while maintaining the mechanical properties and micro-tensile bond strength of the adhesive networks. The increased hydrophobicity and antibacterial activity are promising indicators that azobenzene nanogel additives have the potential to increase the durability and longevity of adhesive resins.

Nanogel-Facilitated In-Situ Delivery of a Cataract Inhibitor.

Cataracts are a leading cause of blindness worldwide. Surgical removal of cataracts is a safe and effective procedure to restore vision. However, a large number of patients later develop vision loss due to regrowth of lens cells and subsequent degradation of the visual axis leading to visual disability. This postsurgical complication, known as posterior capsular opacification (PCO), occurs in up to 30% of cataract patients and has no clinically proven pharmacological means of prevention. Despite the availability of many compounds capable of preventing early steps in PCO development, there is currently no effective means to deliver such therapies into the eye for a suitable duration. To model a solution to this unmet medical need, we fabricated acrylic substrates as intraocular lens (IOL) mimics scaled to place into the capsular bag of the mouse lens following a mock-cataract surgery. Substrates were coated with a hydrophilic crosslinked acrylate nanogel designed to elute Sorbinil, an aldose reductase inhibitor previously shown to suppress PCO. Insertion of the Sorbinil-eluting device into the lens capsule at the time of cataract surgery resulted in substantial prevention of cellular changes associated with PCO development. This model demonstrates that a cataract inhibitor can be delivered into the postsurgical lens capsule at therapeutic levels.

Photopolymerization kinetics of methyl methacrylate with reactive and inert nanogels.

The enhanced in situ photopolymerization kinetics of methyl methacrylate (MMA) to poly(methyl methacrylate) (PMMA) through the incorporation of both inert and reactive nanogel (NG) fillers under ambient conditions has been demonstrated. In addition to the polymerization kinetics, the physical and chemical properties of the prepolymeric NG were also utilized to tune the thermoplasticity and mechanical properties of the PMMA polymer network. The protocol followed in this study imparts superior MMA photopolymerization kinetics (≥ 60% double-bond conversion within 15 min for > 35 wt% nanogel loadings and ≥ 95% double-bond conversion in < 60 min for all NG concentrations) when compared with traditional polymerization mechanisms. PMMA remained a glassy material following the incorporation of both inert and reactive NG as demonstrated by the glass transition temperature (Tg) of the ultimate networks. Network linearity is uncompromised following incorporation of inert NG additives, thereby preserving the thermoplasticity of the PMMA network. As the non-functionalized, inert NG content increases, the maintenance of thermoplasticity occurs at the expense of mechanical properties (10× reduction of maximum strength at 25 wt% loading). These effects are less pronounced when reactive nanogels are employed (no significant reduction of maximum strength at 25 wt% loading with minimal crosslinking). The incorporation of NGs enable high chemical tunability within linear polymer networks. Given the wide range of monomers available for the synthesis of NGs, the methodology detailed in this study offers a scheme for the optimization of linear networks for specific targeted applications, hitherto deemed unrealistic under established polymerization protocols.