Influence of different concentrations of an iodonium salt on properties of amine-free resins.

OBJECTIVES: to evaluate the effect of different concentrations of an iodonium salt on the degree of conversion, polymerisation rate, flexural strength and modulus of an amine-free photopolymerizable resin system. METHODS: Two series of UDMA/TEGDMA resin mixtures (1:1 mass ratio) containing 0, 0.5, 1.0 or 2.0 mol% of bis(4-methyl phenyl)iodonium hexafluorophosphate(BPI): and 1 mol% camphorquinone (CQ) were evaluated. One of the series contained 2 mol% of the amine (2-(dimethylamino)ethyl methacrylate-DMAEMA), while the other series had only CQ and BPI as photoinitiators. Polymerisation kinetics and degree of conversion (DC) were evaluated by Fourier transform near-infrared spectroscopy (n = 3). Flexural strength (FS) and modulus (E) were evaluated by a three-point bending method (n = 12). Data were analysed by two-way ANOVA and Tukey's test. RESULTS: The system containing CQ + DMAEMA + BPI provided the highest DC and FS. Amine-free resins had similar E regardless of the presence of BPI. The resins containing CQ+DMAEMA with 1 and 2 mol% of BPI presented higher E compared with others. SIGNIFICANCE: Amine-containing resins reached statistically higher DC, rate of polymerisation and FS than amine-free systems. The use of higher BPI concentrations did not improve the properties of amine-free resins.

Physicochemical properties of dental resins formulated with amine-free photoinitiation systems.

OBJECTIVE: To assess the mechanical properties of two different dimethacrylate resin blends containing the photosensitizer camphorquinone (CQ) alone or in combination with one or more synergists including an amine and/or an iodonium. METHODS: Two co-monomer resin blends were formulated using Bis-GMA/TEGDMA and UDMA/TEGDMA, both at 1:1 mass ratio. Each resin blend was divided into four groups, comprising the following four photoinitiation systems: (1) CQ + 2-(dimethylamino)ethyl methacrylate (DMAEMA); (2) CQ + DMAEMA + bis(4-methyl phenyl)iodonium hexafluorophosphate (BPI); (3) CQ; and (4) CQ + BPI. Materials were evaluated for polymerisation kinetics, water sorption, solubility, flexural strength and modulus. RESULTS: BisGMA/TEGDMA with CQ showed minimal and insignificant degree of conversion and was not tested for water sorption/solubility and mechanical properties. The ternary system (i.e., CQ + DMAEMA + BPI), promoted the highest degree of conversion for each monomer blend. The resins containing amine had higher mechanical properties than the amine free. However, the UDMA amine free resins exhibited greater flexural strength and modulus than the corresponding amine free BisGMA resins. BisGMA/TEGDMA containing CQ + DMAEMA or CQ + BPI had significantly higher water sorption and solubility than the other groups. SIGNIFICANCE: Resins containing amine presented better properties than the amine-free systems. The addition of iodonium salt (BPI) improved the degree of conversion of the resins, even without an amine co-initiator. The amine-free initiator system (CQ + BPI) was more effective when used with UDMA versus BisGMA based-resins respectively.

Effect of diphenyliodonium hexafluorophosphate on the physical and chemical properties of ethanolic solvated resins containing camphorquinone and 1-phenyl-1,2-propanedione sensitizers as initiators.

OBJECTIVES: To evaluate the effects of the diphenyliodonium hexafluorophosphate (DPI) on the physical and mechanical properties of solvated dental adhesive resins containing camphorquinone (CQ) and/or 1-phenyl-1,2-propanedione (PPD) as initiators. METHODS: Model solvated resins containing bisphenol glycidyl methacrylate (BisGMA); triethyleneglycol dimethacrylate (TEGDMA); 1,3-glycerol dimethacrylate (GDMA); 2-hydroxyethyl methacrylate (HEMA); dimethylaminoethyl amine benzoate (EDAB) and ethanol were prepared. The resins were divided in 24 test groups according to the incorporated initiator systems (CQ-0.5 or 1mol%; PPD-0.5 or 1mol%; CQ+PPD-0.5 or 1mol%) as well the presence of DPI (0, 0.5 or 1mol%). Degree of conversion (using Fourier-transformed near infra-red spectroscopy), flexural strength and modulus by three point bending, cohesive strength and water sorption and solubility were measured. Data were statistically analyzed by one and two way ANOVA and Tukey's test (α=0.05). RESULTS: DPI increased the degree of conversion of all materials tested. Camphorquinone promoted higher degree of conversion than resins containing only PPD or CQ+PPD. Generally, the resins containing PPD+CQ with DPI presented higher flexural strength and modulus, cohesive strength, as well lower water sorption and solubility. SIGNIFICANCE: The use of PPD combined with CQ can increase the physical properties of the solvated resins. DPI improved the monomer conversion of all experimental materials and can positively modulate most of the physical properties of the solvated resins.

Mechanisms of setting reactions and interfacial behavior of a nano-filled resin-modified glass ionomer.

OBJECTIVES: In order to improve the short-comings of glass ionomers such as polishability and esthetics while preserving their excellent clinical bonding effectiveness, nanofiller technology has been introduced in a paste-paste resin-modified glass ionomer (nano-filled RMGI, Ketac Nano, KN, 3M ESPE). One objective of this study was to investigate if the introduction of nanotechnology had any significant effect on the setting reaction of the nanoionomer compared to a control RMGI, Vitremer (VM, 3M ESPE). Another objective was to determine the mechanism of bonding of KN in combination with its primer (KNP) to the tooth. METHODS: Fourier-Transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses were performed on KN and VM during the setting of the GIs. FTIR and XPS were also used to study the reaction of the primer of KN (KNP) with hydroxyapatite (HAP). Shear adhesion to dentin and enamel was measured with KN and compared with several RMGIs and one conventional glass ionomers (CGI). The interfaces were examined with scanning electron microscopy (SEM). RESULTS: FTIR data show that KN undergoes both acid-base and methacrylate setting reactions of classical RMGIs. XPS and FTIR studies of the interaction KNP with HAP shows the formation of calcium-polycarboxylate bond. Shear adhesion and failure mode of KN to enamel and dentin were similar to the other RMGIs and CGI. SEM images of KN with tooth structure showed a tight interface with a thin but distinct layer of 2-3 microns attributed to the primer. This was also observed for VM but not for the other three materials. CONCLUSIONS: KN showed two setting reactions expected in true RMGIs. The adhesion with dentin and enamel was similar to other glass-ionomers. The formation of calcium-polycarboxylate was also evident. This chemical bonding is a significant factor in the excellent long-term adhesion of these materials.

Stress relaxation via addition-fragmentation chain transfer in high T(g), high conversion methacrylate-based systems.

To reduce shrinkage stress which arises during the polymerization of crosslinked polymers, allyl sulfide functional groups were incorporated into methacrylate polymerizations to determine their effect on stress relaxation via addition-fragmentation chain transfer (AFCT). Additionally, stoichiometrically balanced thiol and allyl sulfide-containing norbornene monomers were incorporated into the methacrylate resin to maximize the overall functional group conversion and promote AFCT while also enhancing the polymer's mechanical properties. Shrinkage stress and reaction kinetics for each of the various functional groups were measured by tensometry and Fourier-transform infrared (FTIR) spectroscopy, respectively. The glass transition temperature (T(g)) and elastic moduli (E') were measured using dynamic mechanical analysis. When the allyl sulfide functional group was incorporated into dimethacrylates, the polymerization-induced shrinkage stress was not relieved as compared with analogous propyl sulfide-containing resins. These analogous propyl sulfide containing monomers are incapable of undergoing AFCT while having similar chemical structure and crosslink density to the allyl sulfide containing methacrylates. Here, a monomethacrylate monomer that also contains a cyclic allyl sulfide (PAS) was found to increase the crosslinking density nearly 20 times as compared to an analogous monomethacrylate in which the allyl sulfide was replaced with an ethyl sulfide. Despite the much higher crosslink density, the PAS formulation exhibited no concomitant increase in stress. Thiol-norbornene resins were copolymerized in PAS to promote AFCT as well as to synergistically combine the ring opening benefits associated with the thiol-ene reaction. AFCT resulted in a 63% reduction of polymerization stress and a 45°C enhancement of the glass transition temperature in the allyl sulfide-containing thiol-norbornene-methacrylate system compared with rubbery dimethacrylates. When compared with conventional glassy dimethacrylates, this combined system has less than 10% of the typical shrinkage stress level while having similarly excellent mechanical properties.

Novel dental restorative materials having low polymerization shrinkage stress via stress relaxation by addition-fragmentation chain transfer.

OBJECTIVES: To produce a reduced stress dental restorative material while simultaneously maintaining excellent mechanical properties, we have incorporated an allyl sulfide functional group into norbornene-methacrylate comonomer resins. We hypothesize that the addition-fragmentation chain transfer (AFCT) enabled by the presence of the allyl sulfide relieves stress in these methacrylate-based systems while retaining excellent mechanical properties owing to the high glass transition temperature of norbornene-containing resins. METHODS: An allyl sulfide-containing dinorbornene was stoichiometrically formulated with a ring-containing allyl sulfide-possessing methacrylate. To evaluate the stress relaxation effect as a function of the allyl sulfide concentration, a propyl sulfide-based dinorbornene, not capable of addition-fragmentation, was also formulated with the methacrylate monomer. Shrinkage stress, the glass transition temperature and the elastic modulus were all measured. The composite flexural strength and modulus were also measured. ANOVA (CI 95%) was conducted to determine differences between the means. RESULTS: Increasing the allyl sulfide content in the resin dramatically reduces the final stress in the norbornene-methacrylate systems. Both norbornene-methacrylate resins demonstrated almost zero stress (more than 96% stress reduction) compared with the conventional BisGMA/TEGDMA 70/30wt% control. Mechanical properties of the allyl sulfide-based dental composites were improved to the point of being statistically indistinguishable from the control BisGMA-TEGDMA by changing the molar ratio between the methacrylate and norbornene functionalities. SIGNIFICANCE: The allyl sulfide-containing norbornene-methacrylate networks possessed super-ambient T(g), and demonstrated significantly lower shrinkage stress when compared with the control (BisGMA/TEGDMA 70-30wt%). Although additional development remains, these low stress materials exhibit excellent mechanical properties which are appropriate for use as dental restorative materials.

Fluoride release and recharge behavior of a nano-filled resin-modified glass ionomer compared with that of other fluoride releasing materials.

PURPOSE: To compare the long-term fluoride release kinetics of a novel nano-filled two-paste resin-modified glass-ionomer (RMGI), Ketac Nano (KN) with that of two powder-liquid resin-modified glass-ionomers, Fuji II LC (FLC) and Vitremer (VT) and one conventional glass-ionomer, Fuji IX (FIX). METHODS: Fluoride release was measured in vitro using ion-selective electrodes. Kinetic analysis was done using regression analysis and compared with existing models for GIs and compomers. In a separate experiment the samples of KN and two conventional glass-ionomers, FIX and Ketac Molar (KM) were subjected to a treatment with external fluoride source (Oral-B Neutra-Foam) after 3 months of fluoride release and the recharge behavior studied for an additional 7-day period. RESULTS: The cumulative amount of fluoride released from KN, VT and FLC and the release profiles were statistically similar but greater than that for FIX at P < 0.05. All four materials, including KN, showed a burst of fluoride ions at shorter times (t) and an overall rate dependence on t1/2 typical for glass-ionomers. The coating of KN with its primer and of DY with its adhesive did not significantly alter the fluoride release behavior of the respective materials. The overall rate for KN was significantly higher than for the compomer DY. DY showed a linear rate of release vs. t and no burst effect as expected for compomers. The nanoionomer KN showed fluoride recharge behavior similar to the conventional glass ionomers FIX and KM. Thus, it was concluded that the new RMGI KN exhibits fluoride ion release behavior similar to typical conventional and RMGIs and that the primer does not impede the release of fluoride.