Limited cure depth is a drawback of light-activated composites. We hypothesize that curing light transmission and cure depth are influenced by monomer reactivity and filler/resin refractive index mismatch. Light transmission throughout cure was recorded for composites based on strontium (refractive index 1.51) or barium (refractive index 1.53) glass fillers. Fillers were mixed (70 wt%) with 4 bisphenol-A diglycidyl-ether-dimethacrylate (bis-GMA):triethylene glycol dimethacrylate (TEGDMA) formulations with refractive indices ranging from 1.4703 to 1.5370. Following polymerization, cure depth and pre- and post-cure translucency parameters were determined. Transmission changes and cure depths related to monomer reactivity and filler/resin refractive index mismatch with significant interaction. Composites became more opaque or translucent on curing. Optimizing filler/resin refractive index mismatch provides increased curing depth and assists shade-matching.

No abstract

Photochemical oxidation of near infrared (NIR) photosensitizers in the presence of diaryl iodonium salts bearing either bis(trifluoromethylsulfonyl)imide or hexafluorophosphate was investigated by exposure with NIR LEDs emitting either at 790 nm, 830 nm, 850 nm or 870 nm. Four different cyanines with barbituryl group at the meso position exhibit similar absorption in the NIR. These photosensitizers initiate in combination with diaryliodonium salts radical photopolymerization of dental composites with the focus to cure large thicknesses. Furthermore, the mixture comprising the cyanine and the iodonium salt was used to generate brown color in dental composites on demand. This required to understand the mechanism of dye decomposition in more detail applying exposure kinetics and a coupling of Ultra Performance Liquid Chromatography (UPLC) with mass spectrometry (MS) to analyze the photoproducts formed. Data showed cleavage of the polymethine chain at typical positions in case of the oxidized species. These were formed as result of electron transfer between the excited state of the photosensitizer and the iodonium salt. UPLC‐MS experiments additionally indicated a certain sensitivity of the system upon adding of acids and radicals generated by thermal treatment of azobisisobutyronitrile (AIBN). Thus, treatment of the photoinitiator composition led almost to the same products no matter the system was either exposed with NIR light or treated with acids or radicals generated by thermal decomposition of AIBN. These findings helped to understand the large curing depth of 14 mm upon NIR exposure at 850 nm and the brown color formed.

No abstract