Correlation between the beam profile from a curing light and the microhardness of four resins.

OBJECTIVE: To demonstrate the effect of localized irradiance and spectral distribution inhomogeneities of one LED-based dental light-curing unit (LCU) on the corresponding microhardness values at the top, and bottom surfaces of four dental resin-based composites (RBCs), which contained either camphorquinone (CQ) alone or a combination of CQ and monoacylphosphine oxide (TPO) as photoinitiators. METHODS: Localized irradiance beam profiles from a polywave LED-based LCU were recorded five times using a laser beam analyzer, without and with either a 400 nm or 460 nm narrow bandpass filter placed in front of the camera lens. Five specimens of each of the four RBCs (two containing CQ/TPO and two containing CQ-only) were exposed for 5-, 10-, or 30-s with the light guide directly on the top surface of the RBC. After 24 h, Knoop microhardness values were measured at 45 locations across the top and bottom surfaces of each specimen. Microhardness readings for each RBC surface and exposure time were correlated with localized patterns of the LCU beam profile, measured using the 400 nm and 460 nm bandpass filters. Spearman rank correlation was used to avoid relying on an assumption of a bivariate normal distribution for the KHN and irradiance. RESULTS: The local irradiance and spectral emission values were not uniformly distributed across the light tip. There was a strong significant positive correlation with the irradiance beam profile values from the LCU taken through bandpass filters and the microhardness maps of the RBC surfaces exposed for 5 and 10 s. The strength of this correlation decreased with increasing exposure time for the RBCs containing CQ only, and increased for the RBCs containing both CQ and TPO. CONCLUSIONS: Localized beam and spectral distributions across the tip end of the light guide strongly correlated with corresponding areas of microhardness in both the top and bottom surfaces among four RBCs with different photoinitiator contents. Significance: A light-curing unit with a highly inhomogeneous light output can adversely affect localized microhardness of resin-based composites and this may be a contributing factor for premature failure of a restoration.

Single and double ionization of the camphor molecule excited around the C 1s edge.

RATIONALE: An interesting class of volatile compounds, the monoterpenes, is present in some plants although their functions are not yet fully understood. We have studied the interaction of the camphor molecule with monochromatic high-energy photons (synchrotron radiation) using time-of-flight mass spectrometry and coincidence techniques. METHODS: A commercial sample of S-camphor was admitted into the vacuum chamber, without purification, through an inlet system. Monochromatic light with energy around the C 1s edge was generated by the TGM beamline at the Brazilian Synchrotron Facility. A Wiley-McLaren mass spectrometer was used to characterize and detect the ions formed by the camphor photoionization. The data analysis was supported by energy calculations. RESULTS: Although the fragmentation patterns were basically the same at 270 eV and 330 eV, it was observed that above the C 1s edge the contribution to the spectrum from lower mass/charge fragment ions increased, pointing to a higher degree of dissociation of the molecule. Projections of the PEPIPICO spectra demonstrated the existence of unstable doubly charged species. The Gibbs free energy was calculated using the Møller-Plesset perturbation theory (MP2) for the neutral, singly and doubly excited camphor molecule. CONCLUSIONS: Our PEPIPICO spectrum clearly demonstrated the formation of doubly ionic dissociative species. From a slope analysis, we propose a secondary decay after a deferred charge separation mechanism in which, after a few steps, the camphor dication dissociates into C2 H3 (+) and C3 H5 (+) . This is the main relaxation route observed at 270 eV and 330 eV. The large energy difference between the mono and the dication (of the order of 258.2 kcal/mol) may explain the experimentally observed absence of stable dications in the spectra, because their formation is disadvantaged energetically.

Polymerization kinetics and reactivity of alternative initiators systems for use in light-activated dental resins.

OBJECTIVES: The purpose of this study was to evaluate the reactivity and polymerization kinetics behavior of a model dental adhesive resin with water-soluble initiator systems. METHODS: A monomer blend based on Bis-GMA, TEGDMA and HEMA was used as a model dental adhesive resin, which was polymerized using a thioxanthone type (QTX) as a photoinitiator. Binary and ternary photoinitiator systems were formulated using 1mol% of each initiator. The co-initiators used in this study were ethyl 4-dimethylaminobenzoate (EDAB), diphenyliodonium hexafluorophosphate (DPIHFP), 1,3-diethyl-2-thiobarbituric acid (BARB), p-toluenesulfinic acid and sodium salt hydrate (SULF). Absorption spectra of the initiators were measured using a UV-Vis spectrophotometer, and the photon absorption energy (PAE) was calculated. The binary system camphorquinone (CQ)/amine was used as a reference group (control). Twelve groups were tested in triplicate. Fourier-transform infrared spectroscopy (FTIR) was used to investigate the polymerization reaction during the photoactivation period to obtain the degree of conversion (DC) and maximum polymerization rate (R(p)(max)) profile of the model resin. RESULTS: In the analyzed absorption profiles, the absorption spectrum of QTX is almost entirely localized in the UV region, whereas that of CQ is in the visible range. With respect to binary systems, CQ+EDAB exhibited higher DC and R(p)(max) values. In formulations that contained ternary initiator systems, the group CQ+QTX+EDAB was the only one of the investigated experimental groups that exhibited an R(p)(max) value greater than that of CQ+EDAB. The groups QTX+EDAB+DPIHFP and QTX+DPIHFP+SULF exhibited values similar to those of CQ+EDAB with respect to the final DC; however, they also exhibited lower reactivity. SIGNIFICANCE: Water-soluble initiator systems should be considered as alternatives to the widely used CQ/amine system in dentin adhesive formulations.

Effect of a non-thermal, atmospheric-pressure, plasma brush on conversion of model self-etch adhesive formulations compared to conventional photo-polymerization.

OBJECTIVE: To determine the effectiveness and efficiency of non-thermal, atmospheric plasmas for inducing polymerization of model dental self-etch adhesives. METHODS: The monomer mixtures used were bis-[2-(methacryloyloxy)ethyl] phosphate (2MP) and 2-hydroxyethyl methacrylate (HEMA), with mass ratios of 70/30, 50/50 and 30/70. Water was added to the above formulations: 10-30wt%. These monomer/water mixtures were treated steadily for 40s under a non-thermal atmospheric plasma brush working at temperatures from 32 to 35°C. For comparison, photo-initiators were added to the above formulations for photo-polymerization studies, which were light-cured for 40s. The degree of conversion (DC) of both the plasma- and light-cured samples was measured using FTIR spectroscopy with an attenuated total reflectance attachment. RESULTS: The non-thermal plasma brush was effective in inducing polymerization of the model self-etch adhesives. The presence of water did not negatively affect the DC of plasma-cured samples. Indeed, DC values slightly increased, with increasing water content in adhesives: from 58.3% to 68.7% when the water content increased from 10% to 30% in the adhesives with a 50/50 (2MP/HEMA) mass ratio. Conversion values of the plasma-cured groups were higher than those of light-cured samples with the same mass ratio and water content. Spectral differences between the plasma- and light-cured groups indicate subtle structural distinctions in the resultant polymer networks. SIGNIFICANCE: This research if the first to demonstrate that the non-thermal plasma brush induces polymerization of model adhesives under clinical settings by direct/indirect energy transfer. This device shows promise for polymerization of dental composite restorations having enhanced properties and performance.

Interaction of LED light with coinitiator-containing composite resins: effect of dual peaks.

OBJECTIVES: Recently the colour stability of composite resins has been an issue due to the emphasis on the aesthetics of restored teeth. The purpose of the present study was to investigate how dual-peak LED units affect the polymerization of coinitiator-containing composite resins. MATERIALS AND METHODS: Five composite resins [coinitiator-containing: Aelite LS Posterior (AL), Tetric EvoCeram (TE), and Vit-l-escence (VI); only CQ-containing: Grandio (GD) and Filtek Z350 (Z3)] were light cured using four different light-curing units (LCUs). Among them, Bluephase G2 (BP) and G-light (GL) were dual-peak LED LCUs. Microhardness, polymerization shrinkage, flexural, and compressive properties were measured. RESULTS: BP and GL had no consistent effect on the microhardness of AL, TE, and VI on the top and bottom surfaces of resin specimens. Among the specimens, AL and VI showed the least (9.86-10.41 µm) and greatest (17.58-19.21 µm) polymerization shrinkage, respectively. However, the effect of BP and GL on the shrinkage of specimens was not consistent. Among the specimens, GD showed the greatest flexural properties [strength (FS) and modulus (FM)] and TE showed the lowest flexural and compressive properties [strength (CS) and modulus (CM)]. In same resin product, maximum FS and CS differences due to the different LCUs were 10.3-21.0% and 3.6-9.2%, respectively. Furthermore, the influences of BP and GL on FS and CS were not consistent. CONCLUSION: The tested dual-peak LED LCUs had no consistent synergic effect on the polymerization of coinitiator-containing composite resins as compared with QTH and single-peak LED LCUs. CLINICAL SIGNIFICANCE: The dual-peak LED LCUs achieve a similar degree of polymerization in coinitiator-composite resins as QTH and single-peak LED LCUs did. Choice of LCU does not appear to be a determinant of the light curing of coinitiator-composite resins.

Comparison between two methods to evaluate temperature changes produced by composite light curing units and polymerization techniques.

AIM: This study evaluated the temperature change into the pulp chamber during the light curing of composite resin by direct (bovine tooth) and indirect (matrix) methods. METHODS: Direct method: fifty standardized cavities (2x2x2 mm) were prepared in bovine incisors, which were randomly assigned to evaluation of the temperature changes in the pulp chamber. Indirect method: temperature changes were evaluated through a dentine slice of 1.0 mm thickness in a elastomer cubic mold (2x2x2 mm). Filtek Z250 composite resin (3M/ESPE) was photo-activated using three light curing units: quartz-tungsten-halogen (QTH) by continuous, soft-start or intermittent light modulations; light emitting diode (LED); and plasma arc-curing (PAC). Ten groups (N.=10) were established according to technique evaluation and photo-activation methods. All experiments were carried out in a controlled environment (37 °C and 50 ± 10% relative humidity). The temperature changes were recorded using a digital thermometer attached to a type-K thermocouple in contact with the dentin slice (indirect method) or in contact with the axial wall (dentin) of pulp chamber (direct method). The results were submitted to ANOVA and Tukey's test (α=0.05). RESULTS: Temperature changes were statistically higher for the matrix indirect method (2.56 ºC) than bovine teeth direct method (1.17ºC). The change temperature was statistically higher for the PAC (1.77 ºC) when compared to other photo-activation modes in bovine teeth direct method. CONCLUSION: The two methods of temperature evaluation were different, however indirect method detected the higher temperature increase. Higher energy density arising from the light curing units and polymerization techniques promoted higher temperature increase.

Influence of different light sources on the conversion of composite resins.

AIMS: The purpose of this paper was to evaluate the influence of different light curing units on the conversion of four composite resins with different compositions (Durafill VS - Heraeus-Kulzer, Tetric Ceram - Ivoclar/Vivadent, Filtek Supreme XT - 3M ESPE e Aelite LS Packable - Bisco), using differential scanning calorimetry. MATERIALS AND METHODS: A stainless steel matrix was used to prepare 48 cylindrical composite test samples (n=6), measuring 3 mm in diameter and 1 mm in thickness. The samples were photoactivated using a halogen lamp (Optilux 500 - Demetron/Kerr) and three different generations of light-emitting diodes (LEDs) (LEC-470 I - MMOptics, Radii Plus - SDI and Ultra-Lume LED 5 - Ultradent). After removal of the matrix, each sample was weighed and hermetically sealed in an aluminum pan and analyzed. The amount of heat liberated by thermopolymerisation of residual monomers after photoactivation was measured in Joules/gram (J/g). The data were submitted to Analysis of Variance (ANOVA) test (P ≤ 0.002) and the Tukey test (P < 0.05). RESULTS: The Ultra-Lume LED 5 was superior on degree of conversion for all resins. The Radii Plus was equal to the Ultra-Lume LED 5, except for the resin Tetric Ceram , were the Optilux 500 was superior. The LEC-470 I was inferior for the conversion of all resins. CONCLUSION: The study proves the importance of the compatibility of the different photoinitiators in resin composites with the different light sources.

In vitro photosensitization initiated by camphorquinone and phenyl propanedione in dental polymeric materials.

Documentation is scarce on the photobiological effects of photoinitiators present in dental light curable materials. The aim of this study was to determine cellular effects of the photoinitiators camphorquinone (CQ) and phenyl propanedione (PPD) and to investigate whether these substances produced reactive oxygen species after low and high doses of optical radiation (between 0 and 17J/cm(2)). Rat salivary gland cells in vitro were exposed to visible blue light and/or UVA. Hematoporphyrin (HP), a photosensitizer used in medicine, and the UVA-filter 2-methoxy-4-hydroxy-benzophenone (B-3) were used as reference substances. It was found that PPD produced hydrogen peroxide, but not singlet oxygen, upon light irradiation. CQ produced neither hydrogen peroxide nor singlet oxygen. Cell death by necrosis and apoptosis was induced by irradiation in the presence of CQ, PPD and HP. Doses higher than 6J/cm(2) UVA and blue visible light from a source similar to clinically applied sources, induced apoptosis even in the absence of photosensitizers added. A reciprocity relationship was found between radiant exposure (at constant irradiance) and concentration of photoinitiators. In conclusion, the oral cells under investigation were light sensitive, and the sensitivity increased in presence of photoinitiators. PPD acted by mechanisms that included reactive oxygen species and CQ probably by formation of free radicals.

Evaluation of the photostability of different UV filter combinations in a sunscreen.

Development of photostable sunscreens is extremely important to preserve the UV protective capacity and to prevent the reactive intermediates of photounstable filter substances behaving as photo-oxidants when coming into direct contact with the skin. Thus, the objective of this study was to evaluate the photostability of four different UV filter combinations in a sunscreen by using HPLC analysis and spectrophotometry. The formulations that were investigated included four different UV filter combinations often used in SPF 15 sunscreens. The UV filter combinations were: octyl methoxycinnamate (OMC), benzophenone-3 (BP-3) and octyl salicylate (OS) (formulation 1); OMC, avobenzone (AVB) and 4-methylbenzilidene camphor (MBC) (formulation 2); OMC, BP-3 and octocrylene (OC) (formulation 3); OMC, AVB and OC (formulation 4). In the photostability studies, 40 mg of each formulation were spread onto a glass plate and left to dry before exposure to different UVA/UVB irradiation. Exposed samples were then immersed in isopropanol and the dried film dissolved ultrasonically. The filter components in the resulting solution were quantified by HPLC analysis with detection at 325 nm and by spectrophotometry. In this study, the four UV filter combinations showed different photostability profiles and the best one was formulation 3 (OMC, BP-3 and OC), followed by formulations 4, 1 and 2. In addition, OC improved the photostability of OMC, AVB and BP-3.

Radiomodifying effect of camphor on the spermatogonia of mice.

Camphor has been reported to exhibit radiomodifying properties for bacteria and solid tumours of mice. Therefore its radiomodifying effect was evaluated in the testis which is a less vascularised and hypoxic tissue. Young adult strain 'A' male mice were taken up for these studies. Camphor was administered at the rate of 0.1 mg/g body weight intraperitoneally and whole body irradiation was done after 45 minutes under normal aerated conditions. Doses of 0.5, 1.0 and 2.0 Gy were delivered to different groups with the help of 60Co gamma cell. Testicular germ cell renewal system which seems to be a very good model system for the study of chemical radiomodifier was used for this assay. Resting primary spermatocytes (RPS) were counted at different time intervals and comparison was made among different treatment groups and controls. It was observed that RPS counts significantly declined in radiation + camphor treated groups in comparison to radiation alone or control groups. Radiomodifying effect of camphor was significantly evident during the recovery period, i.e., on day 8 after 0.5 Gy irradiation and day 6 onward after 1.0 Gy and 2.0 Gy.