Interfacial Photo-Cross-Linking: Simple but Powerful Approach for Fabricating Capsule Polymer Particles with Tunable pH-Responsive Controlled Release Capability.

Herein, we describe capsule polymer particles with precisely controlled pH-responsive release properties prepared directly via the interfacial photo-cross-linking of spherical poly(2-diethylaminoethyl methacrylate-co-2-cinnamoylethyl methacrylate) (P(DEAEMA-CEMA)) particles. In the interfacial photo-cross-linking, photoreactive cinnamoyl groups in the polymer particles were cross-linked via [2π + 2π] cycloaddition reactions at the polymer/water interface, showing that the shell-cross-linked hollow polymer particles can be directly prepared from spherical polymer particles. The approach has fascinating advantages such as using minimal components, simplicity, and not requiring sacrificial template particles and toxic solvents. The following important observations are made: (I) encapsulated materials were stably retained in the capsule particles under neutral pH conditions; (II) encapsulated materials were released from the capsule particles under acidic pH conditions; (III) the release kinetics of encapsulated materials were controlled by the pH conditions; i.e., immediate and sustained release was achieved by varying the acidity of the aqueous media; (IV) the photoirradiation time did not significantly affect the release kinetics under different pH conditions; and (V) the pH-responsive release properties were regulated by changing the polymer composition in P(DEAEMA-CEMA). Furthermore, by exploiting the pH-responsiveness, capsule particles are successfully obtained via an all-aqueous process from spherical polymer particles. The advantages of the all-aqueous encapsulation process allowed the water-soluble biomacromolecules such as DNA and saccharides to be successfully encapsulated in the P(DEAEMA-CEMA) hollow particles. With this simple interfacial photo-cross-linking strategy, we envision the ready synthesis of sophisticated particulate materials for broad application in advanced research fields.

Shape-transformation of polymersomes from glassy and crosslinkable ABA triblock copolymers.

Recent developments in the field of polymer vesicles, i.e. polymersomes, have demonstrated that disrupting the equilibrium conditions of the milieu could lead to shape transformation into stable non-spherical morphologies, bringing on-demand shape control to reality and bearing great promise for cell mimicry and a variety of biomedical applications. Here, we studied the self-assembly behavior of glassy amphiphilic triblock copolymers, poly(ethylene glycol)-block-polystyrene-stat-poly(coumarin methacrylate)-block-poly(ethylene glycol) (PEG-b-P(S-stat-CMA)-b-PEG), and their response to various stimuli. By changing the respective molecular weights of both the hydrophobic P(S-stat-CMA) and the hydrophilic PEG blocks, we varied the hydrophobic volume fraction thereby accessing a range of morphologies from spherical and worm-like micelles, as well as polymersomes. For the latter, we observed that slow osmotic pressure changes induced by dialysis led to a decrease in size while rapid osmotic pressure changes by addition of a PEG fusogen led to morphological transformations into rod-like and tubular polymersomes. We also found out that chemically crosslinking the vesicles before inducing osmotic pressure changes led to the vesicles exhibiting hypotonic shock, atypical for glassy polymersomes. We believe that this approach combining the robustness of triblock copolymers and light-based transformations will help expand the toolbox to design ever more complex biomimetic constructs.

Polypyrrole and polyaniline nanocomposites with high photothermal conversion efficiency.

The simple and scalable synthesis of poly[2-(methacryloyloxy)ethyl phosphorylcholine] (PMPC)-coated conducting polymer (CP) nanocomposites is described. These functional nanocomposites exhibit tunable absorption in the near-infrared region with relatively high photothermal efficiencies. More importantly, their potential for bio-imaging and therapeutic treatment is proven by cellular uptake and cytotoxicity studies.

Novel Light-Responsive Hydrogels with Antimicrobial and Antifouling Capabilities.

Smart materials with both bactericidal and bacteria-resistant functions are promising for combating the infection concern of medical devices. Current work mostly utilizes hydrolysis to switch materials from antimicrobial to antifouling forms by incubating materials in aqueous solutions for hours to days. In this work, a new photoresponsive poly[2-((4,5-dimethoxy-2-nitrobenzyl)oxy)- N-(2-(methacryloyloxy)ethyl)- N, N-dimethyl-2-oxoethan-1-aminium] (polyCBNA) hydrogel was developed, incorporating the photolabile 4,5-dimethoxy-2-nitrobenzyl and cationic quaternary ammonium groups. The photolabile groups were readily cleaved from the hydrogel shortly upon UV irradiation at 365 nm (a long wavelength widely used for biomedical applications), leading to polymer surface charge switching from cationic to zwitterionic form. Protein adsorbed significantly on polyCBNA but easily desorbed from surfaces after UV irradiation. The cationic hydrogel as a precursor was shown to effectively kill the attached bacteria, and then quickly switched to zwitterionic antifouling form via photolysis, which released the attached bacteria from surfaces and prevented further bacterial attachment. Moreover, the adhered endothelial cells were easily detached from polyCBNA surfaces triggered by light, providing a facile and less destructive nonenzymatic approach to harvest cells. This smart photoresponsive polyCBNA polymer, with integrated antimicrobial and antifouling properties, holds great potential in biomedical applications such as self-sterilizing and self-cleaning coatings for implants, cell harvesting, and cell patterning.

Longevity of bond strength of resin cements to root dentine after radiation therapy.

AIM: To evaluate the bond strength and adhesive interface between several resin cements and root dentine immediately and 6 months after radiotherapy. METHODOLOGY: Sixty maxillary canines were selected and randomly assigned to two groups (n = 30): one group was not irradiated and the other one was subjected to a cumulative radiation dose of 60 Gy. The teeth were sectioned to obtain roots 16 mm long and the canals were prepared with the Reciproc system (R50) and filled using a lateral condensation technique with an epoxy resin sealer. Each group was divided into three subgroups (n = 10) according to the resin cement used for fibreglass fibre post cementation: RelyX-U200, Panavia-F2.0 and RelyX ARC. The posts were cemented in accordance with the manufacturer's recommendations. Three 1-mm-thick dentine slices were then obtained from each root third. The first two slices in the crown-apex direction of each third were selected for the push-out test. The failure mode after debonding was determined with a stereo microscope. The third slice from each root third was selected for scanning electron microscopy (SEM) analyses to examine the resin cement-dentine interface with 100, 1000, 2000 and 4000× magnification. Bond strength data were analysed by anova and Tukey's test (α = 0.05). RESULTS: Significantly lower bond strength (P < 0.0001) was obtained after irradiation compared to nonirradiated teeth. RelyX-U200 cemented fibre posts had the higher bond strength (15.17 ± 5.89) compared with RelyX ARC (P < 0.001) and Panavia-F2.0 (P < 0.001). The evaluation after 6 months revealed lower bond strength values compared to the immediate values (P < 0.001) for irradiated and nonirradiated teeth. Cohesive failures occurred in the irradiated dentine. SEM revealed fractures, microfractures and fewer collagen fibres in irradiated root dentine. RelyX-U200 and Panavia-F2.0 were associated with a juxtaposed interface of the cement with the radicular dentine in irradiated and nonirradiated teeth, and for RelyX ARC, hybrid layer formation and tags were observed in both irradiated and nonirradiated teeth. CONCLUSION: Radiation was associated with a decrease in the push-out bond strength and with lower resin cement/root dentine interface adaptation. Self-adhesive resin cement was a better alternative for fibre post cementation in teeth subjected to radiation therapy. The bond strength decreased after 6 months.

Delayed photo-activation and addition of thio-urethane: Impact on polymerization kinetics and stress of dual-cured resin cements.

OBJECTIVE: 1) to determine the moment during the redox polymerization reaction of dual cure cements at which to photo-activate the material in order to reduce the polymerization stress, and 2) to evaluate possible synergistic effects between adding chain transfer agents and delayed photo-activation. METHODS: The two pastes of an experimental dual-cure material were mixed, and the polymerization kinetics of the redox phase was followed. The moment when the material reached its maximum rate of redox polymerization (MRRP) of cement was determined. The degree of conversion (DC) and maximum rates of polymerization (Rpmax) were assessed for materials where: the photoactivation immediately followed material mixing, at MRRP, 1min before and 1min after MRRP. Thio-urethane (TU) additives were synthesized and added to the cement (20% wt), which was then cured under the same conditions. The polymerization kinetics was evaluated for both cements photo-activated immediately or at MRRP, followed by measurements of polymerization stress, flexural strength (FS) and elastic modulus (EM). Knoop hardness was measured before and after ethanol storage. RESULTS: Photo-activating the cement at or after MRRP reduced the Rpmax and the polymerization stress. Addition of TU promoted additional and more significant reduction, while not affecting the Rpmax. Greater hardness loss was observed for cements with TU, but the final hardness was similar for all experimental conditions. Addition of TU slightly reduced the EM and did not affect the FS. CONCLUSION: Delayed photo-activation and addition of TU significantly reduce the polymerization stress of dual-cured cements.

Photochemically Controlled Drug Dosing from a Polymeric Scaffold.

PURPOSE: To develop the first photoactive biomaterial coating capable of controlled drug dosing via inclusion of synthesised drug-3,5-dimethoxybenzoin (DMB) conjugates in a poly(2-methyoxyethyl acrylate) (pMEA) scaffold. METHODS: Flurbiprofen- and naproxen-DMB conjugates were prepared via esterification and characterised via NMR spectroscopy and mass spectrometry following chromatographic purification. Conjugate photolysis was investigated in acetonitrile solution and within the pMEA matrix following exposure to low-power 365 nm irradiation. Photo-liberation of drug from pMEA into phosphate buffered saline was monitored using UV-vis spectroscopy. RESULTS: The synthetic procedures yielded the desired drug conjugates with full supporting characterisation. Drug regeneration through photolysis of the synthesised conjugates was successful in both acetonitrile solution and within the pMEA scaffold upon UV irradiation. Conjugates were retained within the pMEA scaffold with exclusive drug liberation following irradiation and increased drug dose with increasing exposure. Multi-dosing capacity was demonstrated though the ability of successive irradiation periods to generate further bursts of drug. CONCLUSION: This study demonstrates the first application of photochemically controlled drug release from a biomaterial coating and the feasibility of using pMEA as a scaffold for housing the photoactive drug-DMB conjugates.

pH-degradable PVA-based nanogels via photo-crosslinking of thermo-preinduced nanoaggregates for controlled drug delivery.

pH-Degradable PVA nanogels, which are prepared by photo-crosslinking thermo-preinduced PVA nanoaggregates in water without any surfactants or toxic organic solvents, are used for intracellular PTX release and anticancer treatment. These nanogels fast degraded at mildly acidic conditions with a pH-triggered PTX release, and the degradation products are only native PVA and poly(hydroxyethyl acrylate) (PHEA) as well as acetaldehyde without any toxic byproducts. The nanogel sizes could be tailored by different temperatures during the crosslinking process. The results of confocal microscopy and flow cytometry revealed that smaller nanogels exhibited enhanced internalization with MCF-7 cells than the ones treated with larger nanogels, by which the smaller PTX-loaded nanogels induced a more significant cytotoxicity against MCF-7 cells. GRAPHIC ABSTRACT: pH-Degradable PVA nanogels can be prepared by photo-crosslinking of thermo-preinduced nanoaggregates with tailored nanogel sizes given their pH-triggered PTX release and fast acid-degradation into native PVA and cell-compatible poly(hydroxyethyl acrylate) (PHEA) as well as acetaldehyde.

Evaluation of Eudragit® Retard Polymers for the Microencapsulation of Alpha-Lipoic Acid.

BACKGROUND: Microencapsulation of natural antioxidants in polymeric systems represents a possible strategy for improving the oral bioavailability of compounds that are otherwise poorly soluble. OBJECTIVE: α-lipoic acid (ALA) was microencapsulated with polymethacrylate polymers (blends at various ratios of Eudragit® RS100 and RL100 resins). METHOD: Microspheres were produced by solvent displacement of an ethanol cosolution of ALA and polymers; the microsuspensions were then freeze-dried, using trehalose as a cryoprotector. Microspheres were characterized in the solid state for micromeritic properties and drug loading, as well as by infrared spectroscopy, powder X-ray diffractometry and differential scanning calorimetry. The antioxidant activity of free and encapsulated ALA was assessed by the 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. RESULTS: In vitro release studies, performed in simulated gastric (pH 1.2) and intestinal fluid (pH 6.8), showed that, depending on polymer composition and drug-to-polymer ratio, ALA release can be slowed down, compared to the dissolution pattern of the free drug. Solid-state characterization confirmed the chemical stability of ALA in the microspheres, suggesting that ALA did not develop strong interactions with the polymer and was present in an amorphous or a disordered-crystalline state within the polymer network. As indicated by the DPPH assay, the microencapsulation of ALA in Eudragit® Retard matrices did not alter its antioxidant activity. CONCLUSION: ALA was effectively encapsulated in Eudragit® Retard matrices, showing a chemical stability up to 6 months at room conditions and at 40°C. Moreover, since the drug maintained its antioxidant activity in vitro, the potential application of these microparticulate systems for oral administration would deserve further studies.

Curcumin-Eudragit® E PO solid dispersion: A simple and potent method to solve the problems of curcumin.

Using a simple solution mixing method, curcumin was dispersed in the matrix of Eudragit® E PO polymer. Water solubility of curcumin in curcumin-Eudragit® E PO solid dispersion (Cur@EPO) was greatly increased. Based on the results of several tests, curcumin was demonstrated to exist in the polymer matrix in amorphous state. The interaction between curcumin and the polymer was investigated through Fourier transform infrared spectroscopy and (1)H NMR which implied that OH group of curcumin and carbonyl group of the polymer involved in the H bonding formation. Cur@EPO also provided protection function for curcumin as verified by the pH challenge and UV irradiation test. The pH value influenced curcumin release profile in which sustained release pattern was revealed. Additionally, in vitro transdermal test was conducted to assess the potential of Cur@EPO as a vehicle to deliver curcumin through this alternative administration route.

Curing behaviour of high-viscosity bulk-fill composites.

OBJECTIVES: This study aimed to assess the effect of curing conditions--exposure time, mode, energy density, and exposure distance--on the mechanical properties of high-viscosity bulk-fill resin-based composites (RBCs) measured at simulated clinical relevant filling depths. METHODS: Three high-viscosity bulk-fill RBCs were investigated by assessing the variation in micromechanical properties in 200µm steps (Vickers hardness [HV] and indentation modulus [E]) within simulated 6-mm deep fillings (n=5) polymerized under 16 different curing conditions. The exposure duration was 5, 20, and 40s in the standard power mode; 3, 4, and 8s in the high power mode; and 3 and 6s in the plasma mode; the exposure distance was 0 and 7mm. Energy density ranged from 2.63 to 47.03J/cm(2). Measurements were performed after 24h of storage in distilled water at 37°C. The depth of cure (DOC) was calculated as the 80% hardness drop-off. RESULTS: The results were compared using one- and multiple-way ANOVAs and Tukey's HSD post hoc test (α=0.05). The effect of the parameter material was significant and strong on all measured properties (p<0.05, partial eta-squared ηP(2)=0.492 for E, 0.562 for HV, and 0.087 for DOC). Energy density exerted the strongest influence on the measured properties in all materials, whereas the influence of the exposure distance was strong on DOC, low on E and not significant on HV. The high-viscosity bulk-fill RBCs respond heterogeneously to variations in curing conditions. CONCLUSIONS: A lower energy density limit was identified, allowing for a 4mm material bulk placement (5.88J/cm(2) for EvoCeram Bulk Fill, 7.0J/cm(2) for x-tra fil, and 23.51J/cm(2) for SonicFill). This limit increased to 47.03J/cm(2) for a 5mm bulk placement, as claimed for SonicFill. To maintain mechanical properties in depth, however, an energy density of at least 23.51J/cm(2) is recommended for EvoCeram Bulk Fill and x-tra fil and 47.03J/cm(2) for SonicFill, respectively. This energy density should be achieved at moderate irradiance and increased curing time. CLINICAL SIGNIFICANCE: An exposure time of 20s at moderate irradiance is recommended for all materials for a 4 mm bulk placement.

Residual HEMA and TEGDMA release and cytotoxicity evaluation of resin-modified glass ionomer cement and compomers cured with different light sources.

The purpose of this study was first to evaluate the elution of 2-hydroxyethyl methacrylate (HEMA) and triethylene glycol dimethacrylate (TEGDMA) monomers from resin-modified glass ionomer cement (RMGIC) and compomers cured with halogen and light-emitting diode (LED) light-curing units (LCUs). The effect of cured materials on the viability of L929 fibroblast cells was also evaluated. One RMGIC (Ketac N100) and two compomers (Dyract Extra and Twinkystar) were tested. Materials were prepared in teflon disks and light-cured with LED or halogen LCUs. The residual monomers of resin materials in solution were identified using high-performance liquid chromatography. The fibroblast cells' viability was analyzed using MTT assay. The type of LCU did not have a significant effect on the elution of HEMA and TEGDMA. A greater amount of HEMA than TEGMDA was eluted. The amount of TEGDMA eluted from Twinkystar was greater than Dyract Extra (P < 0.05) when cured with a halogen LCU. All material-LCU combinations decreased the fibroblast cells' viability more than the control group (P < 0.01), except for Dyract Extra cured with a halogen LCU (P > 0.05). Curing with the LED LCU decreased the cells' viability more than curing with the halogen LCU for compomers. For Ketac N100, the halogen LCU decreased the cells' viability more than the LED LCU.

The effect of time between handling and photoactivation on self-adhesive resin cement properties.

PURPOSE: To evaluate the degree of conversion, absorption, and solubility in water of self-adhesive resin cements subjected to different time intervals between material preparation and the photoactivation procedure. MATERIALS AND METHODS: Two dual self-adhesive resin cements were tested: RelyX Unicem and SmartCem2. The degree of conversion as a function of time was evaluated by Fourier-transformed infrared spectroscopy using the attenuated total reflectance technique. Three time intervals between handling and photoactivation were applied: Group 1 = immediately; Group 2 = a 1-minute interval; Group 3 = a 4-minute interval. All specimens were irradiated with a light-emitting diode source for 40 seconds. Thirty discs of each cement (1 mm thick × 6 mm diameter, n = 10) were prepared for the absorption and solubility tests. These specimens were stored in distilled water at 37°C for 90 days. The results were subjected to ANOVA with two factors (material and activation time intervals) and Tukey's test (95% significance). RESULTS: The 4-minute interval significantly reduced the degree of conversion of SmartCem2 (30.6% ± 8.3%). No other significant changes were observed for the degree of conversion; however, the time intervals before photoactivation interfered significantly in the water absorption of the RelyX Unicem specimens but not the SmartCem2 specimens. The time intervals did not affect the solubility of either cement. In all cases, SmartCem2 had higher solubility than RelyX Unicem. CONCLUSION: The time interval between handling and photoactivation significantly influenced the degree of conversion and water sorption of the resin-based cements. In general, one can say that the self-adhesive resin cements should be photoactivated as soon as possible after the material handling process.

Effect of artificial aging on the bond durability of fissure sealants.

PURPOSE: To evaluate the effect of artificial aging on the bond durability of fissure sealants in vitro. MATERIALS AND METHODS: Twenty bovine incisors received 4 different sealant treatments and were divided into four groups: 1. Ultraseal XT plus (UX); 2. Enamel Loc (EL); 3. 35% phosphoric acid plus Enamel Loc (PEL); 4. Adper Prompt L-Pop plus Clinpro (PPC). Beam-shaped specimens were prepared and randomly divided into three subgroups. One subgroup underwent the microtensile bond strength (µTBS) test after 24-h storage in 37°C water. The other two subgroups were also subjected to the microtensile bond strength test after 5000 and 10,000 thermal cycles, respectively. Another twelve intact human third molars were sealed using 1 of 3 methods and were divided into 3 groups of 4 each: 1. Ultraseal XT plus; 2. Adper Prompt L-Pop plus Clinpro; and 3. Enamel Loc. Two specimens from each group were immersed in a 50% silver nitrate solution for 24 h, followed by exposure to fluorescent light for 8 h, before being scanned in a micro-CT (microcomputer tomography) machine. The other two were handled in the same way after undergoing 10,000 thermal cycles. The CT images obtained were evaluated. RESULTS: All samples from the EL group were broken during preparation, so no µTBS results were available. After 5000 thermal cycles, the bond strengths of the three other groups (UX, PEL, PPC) decreased significantly (p < 0.05). Longer thermocycling (10,000 cycles) resulted in more decreases in µTBS for group PEL and PPC, while the strength of the UX group remained relatively unchanged. After thermocycling, considerable silver penetration could be seen at the sealant/enamel interface of the EL group in micro-CT images. CONCLUSIONS: The etch-and-rinse procedure for sealant application promotes higher bond strength under artificial aging. Micro-CT, a nondestructive analytical tool, may be used to evaluate the sealant/enamel interface effectively.

Preheating of resin-based flowable materials in a microwave device: a promising approach to increasing hardness and softening resistance under cariogenic challenge.

This study aimed to evaluate whether preheated resin-based flowable restoratives would show increased hardness and softening susceptibility after an early cariogenic challenge. Fluroshield- Yellowed, Bioseal, Wave, Master Flow, Fluroshield-White, Conseal F, Filtek Z350 Flow, and Opallis Flow were tested. Preheating was performed using a microwave device. Five specimens of each preheated or room temperature material (n = 5) were fabricated. Hardness was assessed before and after a cariogenic challenge. The analysis was done by two-way analysis of variance (ANOVA) with repeated measures (cariogenic challenge) and Tukey's test for multiple comparisons (

Electroresponsive polymer-carbon nanotube hydrogel hybrids for pulsatile drug delivery in vivo.

Drug release triggered by an external non-invasive stimulus is of great interest for the development of new drug delivery systems. The preparation of an electroresponsive multiwalled carbon nanotube/poly(methylacrylic acid) (MWNT/PMAA)-based hybrid material is reported. The hydrogel hybrids achieve a controlled drug release upon the ON/OFF application of an electric field, giving rise to in vitro and in vivo pulsatile release profiles.

Effect of curing unit and adhesive system on marginal adaptation of composite restorations.

This study sought to evaluate how a curing unit and adhesive system affected the marginal adaptation of resin composite restorations. Class V cavities were prepared in bovine teeth with a gingival margin in dentin and an incisal margin in enamel. The cavities were restored with a micro-hybrid resin composite using one of four adhesives: Single Bond 2, Prime & Bond NT, Clearfil SE Bond, Xeno IV. The light-activations were performed using a quartz-tungsten-halogen (QTH) lamp or a second-generation light-emitting diode (LED). Restorations were finished and polished and epoxy replicas were prepared. Marginal adaptation was analyzed by using scanning electronic microscopy (magnification 500X). The widest gaps in each margin were recorded, and data were submitted to Kruskal-Wallis, Mann-Whitney, and Wilcoxon tests (α = 0.05). Differences between the adhesives were observed only when the dentin margins were evaluated: Clearfil SE Bond demonstrated better marginal adaptation than Prime & Bond NT or Single Bond 2 (which demonstrated the widest gaps in the dentin margin). The type of curing unit only affected the results for Xeno IV when the enamel margin was analyzed; the LED lamp promoted smaller gaps than the QTH lamp.

Effect of immediate and delayed light activation on the mechanical properties and degree of conversion in dual-cured resin cements.

We evaluated the effect of activation mode (immediate or delayed light activation vs. no light activation) on diametral tensile strength (DTS), elastic modulus, ultimate tensile strength (UTS), and degree of conversion (DC) in dual-cured resin cements. Three resin cements were evaluated: Enforce, RelyX ARC, and Panavia F. The mixed cements were inserted into circular molds for the DTS test and into dumbbell-shaped molds for the UTS test. Inside the molds, the cements were light-activated either immediately or after 5 min (delayed light activation). If no light activation was performed, the materials were protected from light exposure (control). The DTS and UTS tests were performed until fracture. The elastic modulus was calculated using data from the DTS test, and DC was evaluated 24 h after manipulation using near-infrared spectroscopy. Data for each variable were individually analyzed by two-way ANOVA and the post-hoc Tukey test (α = 0.05). Regarding DTS, activation mode influenced only Panavia Fspecimens, which had the lowest DTS values in the absence of light activation. Activation mode did not influence the elastic modulus or UTS of any resin cement evaluated. Immediate light activation yielded higher DC values as compared with the absence of light activation.

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.

Simultaneous determination of polymerization shrinkage, exotherm and thermal expansion coefficient for dental resin-composites.

OBJECTIVES: To measure shrinkage strain, exotherm, and coefficient of thermal expansion (CTE), simultaneously for a set of representative resin-composites. METHODS: Six commercially available resin-composites with different filler loadings were selected. A modified bonded-disk instrument that includes temperature-monitoring apparatus was used to measure simultaneously: shrinkage strain, exotherm, and CTE. Shrinkage strain and temperature of disk specimens (n=3/materials) were monitored for 1h after irradiation for 20s at 1200mW/cm(2) (energy density=24J/cm(2)). Disks were irradiated for a second time 60min after the first irradiation. Axial expansion strain and temperature were monitored for 3min. Exotherm was obtained from differences between temperature rise during 1st and 2nd irradiations. CTE was calculated from disk axial expansion due to irradiation heat (ΔL) and rise in temperature (ΔT) during the second irradiation. RESULTS: The final shrinkage strain values ranged from 1.7% to 2.34%, exotherm values ranged from 4.66 to 9.43°C, and CTE ranged from 18.44 to 24.63 (10(-6)/°C). Negative correlations were found between filler loading and shrinkage strain, exotherm, and CTE. Positive correlation was apparent between shrinkage strain and CTE. SIGNIFICANCE: The modified bonded-disk instrument could be used to measure simultaneously shrinkage strain, exotherm, and CTE of resin-composites.