The quality of first-year dental students' cognitive structures and the factors that influence it.

INTRODUCTION: In health professions education, it is widely recognised that concept mapping helps students organise their knowledge. This study aimed to investigate the quality of first-year dental students' cognitive structures and the factors that influence it. Two approaches (qualitative and descriptive) to analysing student concept maps are described in this article. The qualitative approach emphasises the distinct morphologies (structures) that are considered to indicate the level of understanding. The descriptive approach provides information on the content's richness in terms of concepts and key concepts. MATERIALS AND METHODS: A total of 31 first-year dental students participated in this study. In an introductory session, students drew their first concept map (CM) using Cmaptools software. Then, students created and submitted individualised CMs for four course topics. Qualitative and descriptive approaches to analysing concept maps are valuable because they highlight what students have learned and how they organise and structure knowledge through CMs. To determine students' cognitive structures and explore the evolution of their representations over the four course topics, two examiners analysed the CMs' morphology and content. RESULTS: Students presented various cognitive structures for the same topic. The quality of concept maps seemed to be influenced by the topic, as well as by familiarisation with making CM. CONCLUSION: Concept mapping revealed the organisation of students' knowledge. This study explored the structural (morphology) and content analyses of CMs. The quality of the CMs seems to be affected by the nature of the topic.

The Effect of Expiration Date on Mechanical Properties of Resin Composites.

OBJECTIVE: The aim of this in vitro study is to evaluate the effect of expiration date on some mechanical properties of resin composites after controlled storage of syringes and compules in a refrigerator at 4°C. MATERIALS AND METHODS: Specimens were tested at 7 days after storage in distilled water at room temperature. The investigated properties are the static modulus of elasticity, the flexural strength, and the Vickers microhardness. Same batches of restorative materials were examined at baseline (at least 1 year before their expiration date) and 1 year after they expired. RESULTS: Paired t-test is used to compare the results between the two groups using StatView software (version 5.0) SAS Campus Drive Cary, North Carolina, USA. Except for the flexural strength, no statistical differences were found between the mechanical properties of the expired and the unexpired group. CONCLUSION: The 1-year expiry date did not seem to affect the investigated mechanical properties.

Evaluation of Emdogain® antimicrobial effectiveness against biofilms containing the keystone pathogen Porphyromonas gingivalis.

This study aimed to evaluate the antimicrobial activity of Emdogain® (EMD) against biofilms containing the periopathogen Porphyromonas gingivalis. A brain-Heart infusion broth inoculated with S. gordonii and P. gingivalis was perfused (7-d, anaerobiosis) through a closed circuit containing two Robbins devices as to form biofilms. The latter were then treated for 2 min with various antimicrobials (Chlorhexidine (CHX) 0.2%, Povidone iodine (PVI) 5%, PVI 10%, essential oils (EO), EO ZeroTM or EMD) (n=8) and cell densities were calculated and compared. In the present in vitro model, Emdogain® was not statistically effective (p>0.05) in killing biofilm bacteria unlike the other tested molecules.

Filler characteristics of modern dental resin composites and their influence on physico-mechanical properties.

OBJECTIVE: The mechanical properties of dental resin-based composites (RBCs) are highly dependent on filler characteristics (size, content, geometry, composition). Most current commercial materials are marketed as "nanohybrids" (i.e. filler size <1µm). In the present study, filler characteristics of a selection of RBCs were described, aiming at identifying correlations with physico-mechanical properties and testing the relevance of the current classification. METHODS: Micron/sub-micron particles (> or <500nm) were isolated from 17 commercial RBCs and analyzed by laser diffractrometry and/or electron microscopy. Filler and silane content were evaluated by thermogravimetric analysis and a sedimentation technique. The flexural modulus (Eflex) and strength (σflex) and micro-hardness were determined by three-point bending or with a Vickers indenter, respectively. Sorption was also determined. All experiments were carried out after one week of incubation in water or 75/25 ethanol/water. RESULTS: Average size for micron-sized fillers was almost always higher than 1µm. Ranges for mechanical properties were: 3.775wt%) were associated with the highest mechanical properties (Eflex and σflex>12GPa and 130MPa, respectively) and lowest solvent sorption (∼0.3%). SIGNIFICANCE: Mechanical properties and filler characteristics significantly vary among modern RBCs and the current classification does not accurately illustrate either. Further, the chemical stability of RBCs differed, highlighting differences in resin and silane composition. Since Eflex and sorption were well correlated to the filler content, a simple and unambiguous classification based on such characteristic is suggested, with three levels (ultra-low fill, low-fill and compact resin composites).

Photopolymerization of highly filled dimethacrylate-based composites using Type I or Type II photoinitiators and varying co-monomer ratios.

OBJECTIVES: The use of a Type I photoinitiator (monoacylphosphine oxide, MAPO) was described as advantageous in a model formulation, as compared to the conventional Type II photoinitiator (Camphorquinone, CQ). The aim of the present work was to study the kinetics of polymerization of various composite mixtures (20-40-60-80 mol%) of bisphenol A glycidyl dimethacrylate/triethylene glycol dimethacrylate (BisGMA/TegDMA) containing either CQ or MAPO, based on real-time measurements and on the characterization of various post-cure characteristics. METHODS: Polymerization kinetics were monitored by Fourier-transform near-infrared spectroscopy (FT-NIRS) and dielectric analysis (DEA). A range of postcure properties was also investigated. RESULTS: FT-NIRS and DEA proved complementary to follow the fast kinetics observed with both systems. Autodecceleration occurred after ≈1 s irradiation for MAPO-composites and ≈5-10 s for CQ-composites. Conversion decreased with increasing initial viscosity for both photoinitiating systems. However despite shorter light exposure (3s for MAPO vs 20s for CQ-composites), MAPO-composites yielded higher conversions for all co-monomer mixtures, except at 20 mol% BisGMA, the less viscous material. MAPO systems were associated with increased amounts of trapped free radicals, improved flexural strength and modulus, and reduced free monomer release for all co-monomer ratios, except at 20 mol% BisGMA. SIGNIFICANCE: This work confirms the major influence of the initiation system both on the conversion and network cross-linking of highly-filled composites, and further highlights the advantages of using MAPO photoinitiating systems in highly-filled dimethacrylate-based composites provided that sufficient BisGMA content (>40 mol%) and adapted light spectrum are used.

Tooth Retrospective Dosimetry Using Electron Paramagnetic Resonance: Influence of Irradiated Dental Composites.

In the aftermath of a major radiological accident, the medical management of overexposed individuals will rely on the determination of the dose of ionizing radiations absorbed by the victims. Because people in the general population do not possess conventional dosimeters, after the fact dose reconstruction methods are needed. Free radicals are induced by radiations in the tooth enamel of victims, in direct proportion to dose, and can be quantified using Electron Paramagnetic Resonance (EPR) spectrometry, a technique that was demonstrated to be very appropriate for mass triage. The presence of dimethacrylate based restorations on teeth can interfere with the dosimetric signal from the enamel, as free radicals could also be induced in the various composites used. The aim of the present study was to screen irradiated composites for a possible radiation-induced EPR signal, to characterize it, and evaluate a possible interference with the dosimetric signal of the enamel. We investigated the most common commercial composites, and experimental compositions, for a possible class effect. The effect of the dose was studied between 10 Gy and 100 Gy using high sensitivity X-band spectrometer. The influence of this radiation-induced signal from the composite on the dosimetric signal of the enamel was also investigated using a clinical L-Band EPR spectrometer, specifically developed in the EPR center at Dartmouth College. In X-band, a radiation-induced signal was observed for high doses (25-100 Gy); it was rapidly decaying, and not detected after only 24 h post irradiation. At 10 Gy, the signal was in most cases not measurable in the commercial composites tested, with the exception of 3 composites showing a significant intensity. In L-band study, only one irradiated commercial composite influenced significantly the dosimetric signal of the tooth, with an overestimation about 30%. In conclusion, the presence of the radiation-induced signal from dental composites should not significantly influence the dosimetry for early dose assessment.

The effect of ultra-fast photopolymerisation of experimental composites on shrinkage stress, network formation and pulpal temperature rise.

OBJECTIVES: to complement our previous work by testing the null hypotheses that with short curing times and high DC, TPO-based resin composites would exhibit (1) higher polymerization stresses and consequently display (2) higher temperature rise and (3) higher flexural modulus, flexural strength and hardness, compared to a conventional CQ-based experimental composite. METHODS: Two experimental resin composites using either Lucirin-TPO or camphorquinone/DMAEMA as photoinitiators were prepared. Light curing was carried out using spectral outputs adapted to the absorption properties of each initiator. Different irradiation protocols were selected (0.5, 1, 3, 9 s at 500, 1000 and 2000 mW/cm(2) for Lucirin-TPO based composites and 20 or 40 s at 1000 mW/cm2 for Lucirin-TPO and camphorquinone-based composites). Degree of conversion (DC) was measured in real time by means of FT-NIR spectroscopy. Pulpal temperature rise (ΔT) was studied in a tooth model. Polymerization stress was monitored using the Bioman instrument. For cured specimens, flexural modulus and flexural strength were determined using a three point bending platform and Vickers hardness was determined with a microhardness indentor on samples prior to and after 24 h incubation in 75/25 ethanol/H2O. Premolars were restored with both materials and microleakage at the teeth/composite interfaces following restoration was assessed. RESULTS: Lucirin-TPO-based composites irradiated at radiant exposures of 3 J/cm(2) and more exhibited significantly higher DCs, associated with increased flexural moduli and hardness compared to CQ-based composites. For an ultra-short irradiation time of 1 s at 1000 mW/cm(2), TPO-composites displayed similar polymerization stresses compared to CQ-controls with yet a 25% increase for flexural modulus and 40% increase for hardness measured after EtOH/H2O sorption. Higher stress rates were however observed in all curing protocols compared to CQ-composites. Microleakage was similar between TPO and CQ-composites irradiated at 1000 mW/cm(2) for 3 and 20 s respectively, while a significant increase was observed for TPO-composites irradiated for 1 s. ΔT measured through a 0.6 mm thick dentin layer were all below 5.5°C; TPO-composites exhibited similar or lower values compared to controls. SIGNIFICANCE: The use of Lucirin-TPO in resin composites along with appropriate curing conditions may allow for a major reduction of irradiation time while improving mechanical properties. The amount of stress observed during polymerization in TPO-based composites can be similar to those using CQ and the cohesion at the restoration-tooth interface was not affected by short curing times. Contrary to other studies, we found that the temperatures increases measured during polymerization were all well below the 5.5°C threshold for the pulp.

Physico-mechanical characteristics of commercially available bulk-fill composites.

OBJECTIVES: Bulk-fill composites have emerged, arguably, as a new "class" of resin-based composites, which are claimed to enable restoration in thick layers, up to 4mm. The objective of this work was to compare, under optimal curing conditions, the physico-mechanical properties of most currently available bulk-fill composites to those of two conventional composite materials chosen as references, one highly filled and one flowable "nano-hybrid" composite. METHODS: Tetric EvoCeram Bulk Fill (Ivoclar-Vivadent), Venus Bulk Fill (Heraeus-Kulzer), SDR (Dentsply), X-tra Fil (VOCO), X-tra Base (VOCO), Sonic Fill (Kerr), Filtek Bulk Fill (3M-Espe), Xenius (GC) were compared to the two reference materials. The materials were light-cured for 40s in a 2mm×2mm×25mm Teflon mould. Degree of conversion was measured by Raman spectroscopy, Elastic modulus and flexural strength were evaluated by three point bending, surface hardness using Vickers microindentation before and after 24h ethanol storage, and filler weight content by thermogravimetric analysis. The ratio of surface hardness before and after ethanol storage was considered as an evaluation of polymer softening. Data were analyzed by one-way ANOVA and post hoc Tukey's test (p=0.05). RESULTS: The mechanical properties of the bulk-fill composites were mostly lower compared with the conventional high viscosity material, and, at best, comparable to the conventional flowable composite. Linear correlations of the mechanical properties investigated were poor with degree of conversion (0.090.8). Softening in ethanol revealed differences in polymer network density between material types. CONCLUSION: The reduction of time and improvement of convenience associated with bulk-fill materials is a clear advantage of this particular material class. However, a compromise with mechanical properties compared with more conventional commercially-available nano-hybrid materials was demonstrated by the present work. SIGNIFICANCE: Given the lower mechanical properties of most bulk-fill materials compared to a highly filled nano-hybrid composite, their use for restorations under high occlusal load is subject to caution. Further, the swelling behaviour of some of the bulk-fill materials may be a reason for concern, which highlights the critical requirement for a veneering material, not only to improve aesthetic quality of the translucent material, but to reduce the impact of degradation.

Ultra-fast light-curing resin composite with increased conversion and reduced monomer elution.

OBJECTIVES: To test the null hypotheses that photoactive resin composites containing a Type I photoinitiator would exhibit reduced DC or increased monomer elution at substantially short curing times compared with materials based on a Type 2 ketone/amine system. METHODS: Two experimental resin composites were prepared, using either Lucirin-TPO or camphorquinone/DMAEMA. Specimens were light-cured using appropriate spectral emission that coincided with the absorption properties of each initiator using different irradiation protocols (0.5, 1, 3, 9s at 500, 1000 and 2000mW/cm(2) for Lucirin-TPO based composites and 20 or 40s at 1000mW/cm(2) for Lucirin-TPO and camphorquinone-based composites). Degree of conversion (DC) was measured by Raman spectroscopy, propagating radical concentrations were collected by means of electron paramagnetic resonance (EPR) and monomer leaching was characterized using high-performance liquid chromatography (HPLC). RESULTS: The null hypotheses were rejected, except for a single irradiation protocol (0.5s @ 500mW/cm(2)). Lucirin-TPO-based composites could cure 20 times faster and release at least 4 times less monomers in comparison to camphorquinone-based composites. At 1000mW/cm(2), and 1s irradiation time for curing times of 1s, Lucirin-TPO based composites displayed 10% higher DC. The difference in polymerization efficiency of Lucirin-TPO compared with camphorquinone-based resin composites were explained using EPR; the former showing a significantly greater yield of radicals which varied logarithmically with radiant exposure. SIGNIFICANCE: Lucirin-TPO is substantially more efficient at absorbing and converting photon energy when using a curing-light with an appropriate spectral emission and otherwise a limitation noted in several previous publications. At concentrations of 0.0134mol/L, Lucirin-TPO-based composites require a minimum light intensity of 1000mW/cm(2) and an exposure time of 1s to provide significantly improved DC and minimal elution compared with a conventional photoinitiator system. The use of a wide range of curing protocols in the current experiment has realized the significant potential of Lucirin-TPO and its impact for clinical applications, in replacement to materials using camphorquinone.

Influence of free radicals signal from dental resins on the radio-induced signal in teeth in EPR retrospective dosimetry.

In case of radiological accident, retrospective dosimetry is needed to reconstruct the absorbed dose of overexposed individuals not wearing personal dosimeters at the onset of the incident. In such a situation, emergency mass triage will be required. In this context, it has been shown that Electron Paramagnetic Resonance (EPR) spectroscopy would be a rapid and sensitive method, on the field deployable system, allowing dose evaluation of a great number of people in a short time period. This methodology uses tooth enamel as a natural dosimeter. Ionising radiations create stable free radicals in the enamel, in a dose dependent manner, which can be detected by EPR directly in the mouth with an appropriate resonator. Teeth are often subject to restorations, currently made of synthetic dimethacrylate-based photopolymerizable composites. It is known that some dental composites give an EPR signal which is likely to interfere with the dosimetric signal from the enamel. So far, no information was available about the occurrence of this signal in the various composites available on the market, the magnitude of the signal compared to the dosimetric signal, nor its evolution with time. In this study, we conducted a systematic characterization of the signal (intensity, kinetics, interference with dosimetric signal) on 19 most widely used composites for tooth restoration, and on 14 experimental resins made with the most characteristic monomers found in commercial composites. Although a strong EPR signal was observed in every material, a rapid decay of the signal was noted. Six months after the polymerization, the signal was negligible in most composites compared to a 3 Gy dosimetric signal in a tooth. In some cases, a stable atypical signal was observed, which was still interfering with the dosimetric signal.

Progress in dimethacrylate-based dental composite technology and curing efficiency.

OBJECTIVES: This work aims to review the key factors affecting the polymerization efficiency of light-activated resin-based composites. The different properties and methods used to evaluate polymerization efficiency will also be critically appraised with focus on the developments in dental photopolymer technology and how recent advances have attempted to improve the shortcomings of contemporary resin composites. METHODS: Apart from the classical literature on the subject, the review focused in particular on papers published since 2009. The literature research was performed in Scopus with the terms "dental resin OR dimethacrylate". The list was screened and all papers relevant to the objectives of this work were included. RESULTS: Though new monomer technologies have been developed and some of them already introduced to the dental market, dimethacrylate-based composites still currently represent the vast majority of commercially available materials for direct restoration. The photopolymerization of resin-based composites has been the subject of numerous publications, which have highlighted the major impact of the setting process on material properties and quality of the final restoration. Many factors affect the polymerization efficiency, be they intrinsic; photoinitiator type and concentration, viscosity (co-monomer composition and ratio, filler content) and optical properties, or extrinsic; light type and spectrum, irradiation parameters (radiant energy, time and irradiance), curing modes, temperature and light guide tip positioning. SIGNIFICANCE: : This review further highlights the apparent need for a more informative approach by manufacturers to relay appropriate information in order for dentists to optimize material properties of resin composites used in daily practice.

Spectral spatial electron paramagnetic resonance imaging as a tool to study photoactive dimethacrylate-based dental resins.

Photopolymerizable dimethacrylate-based dental resins, which are widely used in the current routine dental practice, show a very strong EPR signal. This signal has already been studied by EPR spectroscopy, but not by EPR imaging. The spectrum is quite complex due to hyperfine splitting and to the presence of two radical species, which is a priori not favorable to EPR imaging. In this work, the robustness of EPR imaging was investigated, both in the spatial and spectral-spatial modes, to characterize this type of material using small resin samples. The images produced using standard deconvolution and filtered backprojection procedure did not display any noticeable artifact. They also reflected the expected density of free radicals in two types of resin, photopolymerized with two different light irradiances. Moreover, the spectral-spatial imaging mode provided a complete spectrum for each pixel, which enabled to delineate the different distributions of the two radical species inside the samples. EPR imaging offered a different information compared to the usual degree of conversion measured by Raman spectrometry. These results suggest that EPR imaging could be used as a complementary tool to further characterize the dimethacrylate-based resins used in dental practice or for other applications.

New insight into the "depth of cure" of dimethacrylate-based dental composites.

OBJECTIVES: To demonstrate that determination of the depth of cure of resin-based composites needs to take into account the depth at which the transition between glassy and rubbery states of the resin matrix occurs. METHODS: A commercially available nano-hybrid composite (Grandio) in a thick layer was light cured from one side for 10 or 40 s. Samples were analyzed by Vickers indentation, Raman spectroscopy, atomic force microscopy, electron paramagnetic imaging and differential scanning calorimetry to measure the evolution of the following properties with depth: microhardness, degree of conversion, elastic modulus of the resin matrix, trapped free radical concentration and glass transition temperature. These measurements were compared to the composite thickness remaining after scraping off the uncured, soft composite. RESULTS: There was a progressive decrease in the degree of conversion and microhardness with depth as both properties still exhibited 80% of their upper surface values at 4 and 3.8 mm, respectively, for 10 s samples, and 5.6 and 4.8 mm, respectively, for 40 s samples. In contrast, there was a rapid decrease in elastic modulus at around 2.4 mm for the 10 s samples and 3.0 mm for the 40 s samples. A similar decrease was observed for concentrations of propagating radicals at 2 mm, but not for concentrations of allylic radicals, which decreased progressively. Whereas the upper composite layers presented a glass transition temperature - for 10 s, 55°C (±4) at 1 mm, 56.3°C (±2.3) at 2 mm; for 40 s, 62.3°C (±0.6) at 1 mm, 62°C (±1) at 2 mm, 62°C (±1.7) at 3 mm - the deeper layers did not display any glass transition. The thickness remaining after scraping off the soft composite was 7.01 (±0.07 mm) for 10 s samples and 9.48 (±0.22 mm) for 40 s samples. SIGNIFICANCE: Appropriate methods show that the organic matrix of resin-based composite shifts from a glassy to a gel state at a certain depth. Hence, we propose a new definition for the "depth of cure" as the depth at which the resin matrix switches from a glassy to a rubbery state. Properties currently used to evaluate depth of cure (microhardness, degree of conversion or scraping methods) fail to detect this transition, which results in overestimation of the depth of cure.

Physical, mechanical and rheological characterization of resin-based pit and fissure sealants compared to flowable resin composites.

OBJECTIVES: The purpose of this study was to compare the mechanical and rheological properties of resin-based pit and fissure sealants to flowable resin composites in order to define clinical indications based on these properties. METHODS: Eight flowable resin composites (Admira Flow, Filtek Supreme XT Flow, FlowLine, Grandio Flow, Point-4 Flowable, Premise Flowable, Revolution Formula 2, X-Flow) and four resin-based pit and fissure sealants (Clinpro, Delton FS(+), Estiseal F, Guardian Seal) were used in this study. Their filler weight content was measured by thermogravimetric analysis. Mechanical properties were measured: dynamic and static moduli of elasticity, flexural strength and Vickers microhardness. Rheological measurements were performed using a dynamic oscillation rheometer. RESULTS: Flowable resin composites have by far better mechanical properties than pit and fissure sealants, except for Delton FS(+). All the materials tested are non-Newtonian, shear thinning fluids. They all showed elasticity even at the lowest frequencies but elasticity differs pretty much from one material to another. SIGNIFICANCE: Resin-based pit and fissure sealants seem appropriate for preventive pit and fissure sealing. For enlarged fissures, it can be assumed that flowable resin composites with low elasticity at low frequency are more appropriate.

Pulpal-temperature rise and polymerization efficiency of LED curing lights.

This paper assesses the effects of light characteristics and irradiation time on the Vickers microhardness (VH) of a dual-photoinitiator commercial composite and on temperature increase in the pulp chamber (deltaT). Four recent light-emitting diodes (LEDs)--bluephaseG2 (BG2), bluephase16i (B16i), G-Light (G) and Freelight2 (F2)--and one control halogen light (XL3000-X) were tested on two shades of Tetric EvoCeram (A2 and Bleach XL), whose respective commercial formulations differed based on their concentration of camphorquinone and lucirin TPO. Three different irradiation times were applied--10, 20 and 40 seconds-and VH was measured on the upper and lower surfaces of 2-mm thick samples. The deltaT was measured by using a K-type thermocouple inserted into the pulp chamber of a molar that had been prepared to obtain a 2-mm thickness of dentin. The measurements were made either during polymerization of a 2 mm composite (Shade A2 or Bleach) or with an empty mold. The data were analyzed with the two-way ANOVA (p < 0.05) test. For shade A2, all but one irradiation condition (F2-10 seconds, lower surface) generated VH values that were statistically equal to or better than the standard chosen for this study (X-40 seconds). For Bleach shade, the VH values obtained with G and BG2-20 and 40 seconds were statistically comparable to X-40 seconds for both the upper and lower surfaces. This was not the case with either G and BG2-10 seconds or for all the procedures with other LCUs for which a VH of at least one of the surfaces was significantly lower than the reference. The results also highlight differences between the two material shades, whether the upper or lower surface is considered. Regarding temperature measurements for shade A2, B16i-20-40 seconds, BG2-40 seconds and G-40 seconds induced significantly higher deltaTs (3.98, 5.98, 5.21 and 4.95, respectively) than X-40 seconds (3.09). For Bleach shade, B16i-20 and 40 seconds, F2-20 and 40 seconds, BG2-40 seconds and G-40 seconds generated deltaTs significantly higher than the control values (2.70, 4.05, 3.03, 4.58, 2.74 and 2.44, respectively). The deltaT values obtained with uncovered tooth were generally higher than those obtained with a 2-mm layer of composite. In conclusion, this research emphasizes that a perfect correspondence between light and material spectra is of prime concern, both to insure optimal polymerization and to limit heating in the pulp chamber. Some reduction in curing time is possible, but only within certain limits.

Hydroxyl radical release from dental resins: electron paramagnetic resonance evidence.

It is well known that polymeric free radicals remain trapped inside dental resins for a long time after photopolymerization. Moreover, although these high molecular mass compounds have very limited mobility, there is evidence to suggest that they disappear progressively over time. The purpose of this study was to provide new experimental data to help understand this phenomenon. To determine whether low molecular mass free radicals are released by dental composites stored in hydrophilic media, we used electron paramagnetic resonance spectroscopy to perform spin-trapping experiments on experimental and commercial samples stored in ethanol. Under these conditions, ethoxy radicals were produced. Further experiments demonstrated that (1) hydroxyl radicals were released from the methacrylated resin and (2) they reacted with ethanol molecules to produce "secondary" ethoxy free radicals. In addition to the well-known monomer toxicity of methacrylated resins, we may have identified a new source of concern for these biomaterials.

Influence of curing protocol on selected properties of light-curing polymers: degree of conversion, volume contraction, elastic modulus, and glass transition temperature.

OBJECTIVES: The purpose of this study was to investigate the effect of light-curing protocol on degree of conversion (DC), volume contraction (C), elastic modulus (E), and glass transition temperature (T(g)) as measured on a model polymer. It was a further aim to correlate the measured values with each other. METHODS: Different light-curing protocols were used in order to investigate the influence of energy density (ED), power density (PD), and mode of cure on the properties. The modes of cure were continuous, pulse-delay, and stepped irradiation. DC was measured by Raman micro-spectroscopy. C was determined by pycnometry and a density column. E was measured by a dynamic mechanical analyzer (DMA), and T(g) was measured by differential scanning calorimetry (DSC). Data were submitted to two- and three-way ANOVA, and linear regression analyses. RESULTS: ED, PD, and mode of cure influenced DC, C, E, and T(g) of the polymer. A significant positive correlation was found between ED and DC (r=0.58), ED and E (r=0.51), and ED and T(g) (r=0.44). Taken together, ED and PD were significantly related to DC and E. The regression coefficient was positive for ED and negative for PD. Significant positive correlations were detected between DC and C (r=0.54), DC and E (r=0.61), and DC and T(g) (r=0.53). Comparisons between continuous and pulse-delay modes of cure showed significant influence of mode of cure: pulse-delay curing resulted in decreased DC, decreased C, and decreased T(g). Influence of mode of cure, when comparing continuous and step modes of cure, was more ambiguous. SIGNIFICANCE: A complex relationship exists between curing protocol, microstructure of the resin and the investigated properties. The overall performance of a composite is thus indirectly affected by the curing protocol adopted, and the desired reduction of C may be in fact a consequence of the decrease in DC.

Kinetic study of free radicals trapped in dental resins stored in different environments.

In this work, we used electron paramagnetic resonance to follow the decrease kinetics of free radicals trapped in an experimental resin (ER) and in a commercial composite (Charisma (Ch)) stored under different conditions (in air at 25 and 37 degrees C; in argon, oxygen and water at 25 degrees C). During the first day, the decay was fast (0-24h-rate of decay of allylic radical: 1700-1000a.u. for Ch, 1700-1500a.u. for ER) and the storage conditions had no influence on the kinetics. This phase was ascribed to a post-polymerization phenomenon. From 1day to 1month, the rate of decay depended on the storage environment. In argon, free radicals were quite stable (1day to 1month-rate of decay of allylic radical: 1200-1000a.u. for Ch, 1400-1200a.u. for ER). For the other storage environments, in ER, the rate of decay was higher in water than in oxygen and in air (1day to 1month-rate of decay of allyl radical: 1400a.u. to 100, 500 and 800a.u., respectively). In Ch, free radicals faded quicker than in ER, as undetectable levels were reached before 1month, which attests to the influence of fillers on radical decrease kinetics. Heating experiments were also performed, and free radical concentrations decreased faster at higher temperatures, especially above the glass transition temperature. In conclusion, ambient oxygen is mainly involved in the termination process of free radicals. Therefore, conditions influencing oxygen diffusion have an impact on radical kinetics as well.

Softening and elution of monomers in ethanol.

OBJECTIVES: The purpose of this study was to investigate the effect of light-curing protocol on softening and elution of monomers in ethanol as measured on a model polymer. It was a further aim to correlate the measured values with previously reported data on degree of conversion and glass transition temperature for the same polymer and curing protocols. METHODS: Different light-curing protocols were used in order to investigate the influence of energy density, power density, and mode of cure on the properties of a model polymer. The modes of cure were continuous, pulse-delay, and stepped irradiation of the specimens. Wallace hardness was used to determine the softening of the polymer after storage in ethanol for 24h. Elution of monomers from the polymer was assessed after 7 days in ethanol by means of high-pressure liquid chromatography (HPLC). Data were submitted to two- and three-way analysis of variance (ANOVA), Newman-Keuls' multiple comparison test, and linear regression analysis. RESULTS: Energy density, power density, and mode of cure of the polymer influenced the softening and elution of monomers in ethanol. As energy density increased, softening and elution in ethanol decreased. At same energy density, the influence of power density varied with the mode of cure. When compared to the continuous mode of cure, and at same energy density, pulse-delay irradiation resulted in polymers that in general were more susceptible to softening, but eluted monomers to a lower extent. Less elution was also found with step-cured polymers. Significant, negative correlations were detected between softening and elution in ethanol, respectively, and degree of conversion and between softening and elution in ethanol, respectively, and glass transition temperature. SIGNIFICANCE: A complex relationship exists between curing protocol and the properties selected for investigation. The effect of different combinations of exposure periods and power densities are important to understanding how the curing protocol affects the properties of polymer-based materials.

Rheological properties of experimental Bis-GMA/TEGDMA flowable resin composites with various macrofiller/microfiller ratio.

OBJECTIVES: The purpose of this study was to investigate the rheological behavior of resin composites and to evaluate the influence of each component, organic as well as inorganic, on their viscoelastic properties by testing model experimental formulations. METHODS: Several unfilled mixtures of 2,2-bis-[4-(methacryloxy-2-hydroxy-propoxy)-phenyl]-propane (Bis-GMA) and triethylene glycol dimethacrylate (TEGDMA) were prepared as well as experimental flowable resin composites using a Bis-GMA/TEGDMA 50/50 wt% mixture as organic fraction filled at 60% in weight with varying ratios of silanated barium glass (1 microm) and partially hydrophobic fumed silica (0.1 microm). Their rheological properties were investigated using dynamic oscillatory rheometers. Transmission electron microscopy (TEM) was also performed to investigate the spatial organization of the filler particles. RESULTS: Unfilled Bis-GMA/TEGDMA mixtures all showed a Newtonian behavior. The experimental flowable resin composites were non-Newtonian, shear-thinning fluids. As the quantity of microfiller increased, the viscosity increased and the shear-thinning behavior increased as well. In addition, the experimental composites showed thixotropy, i.e. their viscosity is a function of time after deformation. All these properties were not specifically linked to the creation and destruction of a visible network between inorganic particles, as no difference could be seen between particles' spatial organization at the equilibrium rest state or immediately after deformation. SIGNIFICANCE: The complex viscoelastic properties of resin composites are due to interactions between microfiller and monomer molecules. Modifying the chemical and physical properties of the particles' surface could possibly improve their flow properties and thus their clinical handling performances.