Solid-State Experimental and Theoretical Investigation of the Ammonium Salt of Croconate Violet, a Pseudo-Oxocarbon Ion

The present work describes the crystal structure, vibrational spectra, and theoretical calculations of ammonium salts of 3,5-bis-(dicyanomethylene)cyclopentane-1,2,4-trionate, (NH(4))(2)(C(11)N(4)O(3)) [(NH(4))(2)CV], also known as ammonium croconate violet. This compound crystallizes in triclinic P (1) over bar and contains two water molecules per unit formula. The crystal packing is stabilized by hydrogen bonds involving water molecules and ammonium cations, giving rise to a 3D polymeric arrangement. In this structure, a pi-stacking interaction is not observed, as the smaller centroid-centroid distance is 4.35 angstrom. Ab initio electronic structure calculations under periodic boundary conditions were performed to predict vibrational and electronic properties. The vibrational analysis was used to assist the assignments of the Raman and infrared bands. The solid structure was optimized and characterized as a minimum in the potential-energy surface. The stabilizing intermolecular hydrogen bonds in the crystal Structure were characterized by difference charge-density analysis. The analysis of the density of states of (NH(4))(2)CV gives an energy gap of 1.4 eV with a significant contribution of carbon and nitrogen 2p states for valence and conduction bands.

Sol-gel preparation of near-infrared broadband emitting Er(3+)-doped SiO(2)-Ta(2)O(5) nanocomposite films

This article reports a study on the preparation, densification process, and structural and optical properties of SiO(2)-Ta(2)O(5) nanocomposite films obtained by the sol-gel process. The films were doped with Er(3+) and the Si:Ta molar ratio was 90:10. Values of refractive index, thickness and vibrational modes in terms of the number of layers and thermal annealing time are described for the films. The densification process is accompanied by OH group elimination, increase in the refractive index, and changes in film thickness. Full densification of the film is acquired after 90 min of annealing at 900 degrees C. The onset of crystallization and devitrification, with the growth of Ta(2)O(5) nanocrystals occurs with film densification, evidenced by high-resolution transmission electron microscopy. The Er(3+)-doped nanocomposite annealed at 900 degrees C consists of Ta(2)O(5) nanoparticles, with sizes around 2 nm, dispersed in the SiO(2) amorphous phase. The main emission peak of the film is detected at around 1532 nm, which can be assigned to the (4)I(13/2)->(4)I(15/2) transition of the Er(3+) ions present in the nanocomposites. This band has a full width at half medium of 64 nm, and the lifetime measured for the (4)I(13/2) levels is 5.4 ms, which is broader compared to those of other silicate systems. In conclusion, the films obtained in this work are excellent candidates for use as active planar waveguide. (C) 2010 Elsevier B.V. All rights reserved.

Er(3+)-doped silica-hafnia films for optical waveguides and spherical resonators

In this paper we present some result on sol-gel derived silica-hafnia systems. In particular we focus on fabrication, morphological and spectroscopic assessment of Er(3+)-activated thin films. Two examples of silica-hafnia-derived waveguiding glass ceramics, prepared by top-down and bottom-up techniques are reported, and the main optical properties are discussed. Finally, some properties of activated microspherical resonators, having a silica core, obtained by melting the end of a telecom fiber, coated with an Er(3+)-doped 70SiO(2)-30HfO(2) film, are presented. (C) 2009 Elsevier B.V. All rights reserved.

Composite pre-heating: Effects on marginal adaptation, degree of conversion and mechanical properties

Objectives. This study evaluated the effect of composite pre-polymerization temperature and energy density on the marginal adaptation (MA), degree of conversion (DC), flexural strength (FS), and polymer cross-linking (PCL) of a resin composite (Filtek Z350, 3M/ESPE). Methods. For MA, class V cavities (4mmx2mmx2mm) were prepared in 40 bovine incisors. The adhesive system Adper Single Bond 2 (3M/ESPE) was applied. Before being placed in the cavities, the resin composite was either kept at room-temperature (25 degrees C) or previously pre-heated to 68 degrees C in the Calset (TM) device (AdDent Inc., Danbury, CT, USA). The composite was then light polymerized for 20 or 40s at 600mW/cm(2) (12 or 24 J/cm(2), respectively). The percentage of gaps was analyzed by scanning electron microscopy, after sectioning the restorations and preparing epoxy resin replicas. DC (n = 3) was obtained by FT-Raman spectroscopy on irradiated and non-irradiated composite surfaces. FS (n = 10) was measured by the three-point-bending test. KHN (n = 6) was measured after 24h dry storage and again after immersion in 100% ethanol solution for 24 h, to calculate PCL density. Data were analyzed by appropriate statistical analyses. Results. The pre-heated composite showed better MA than the room-temperature groups. A higher number of gaps were observed in the room-temperature groups, irrespective of the energy density, mainly in the axial wall (p < 0.05). Composite pre-heating and energy density did not affect the DC, FS and PCL (p > 0.05). Significance. Pre-heating the composite prior to light polymerization similar in a clinical situation did not alter the mechanical properties and monomer conversion of the composite, but provided enhanced composite adaptation to cavity walls. (C) 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Contraction stress related to composite inorganic content

Objectives. The role of inorganic content on physical properties of resin composites is well known. However, its influence on polymerization stress development has not been established. The aim of this investigation was to evaluate the influence of inorganic fraction on polymerization stress and its determinants, namely, volumetric shrinkage, elastic modulus and degree of conversion. Methods. Eight experimental composites containing 1:1 BisGMA (bisphenylglycidyl dimethacrylate): TEGDMA (triethylene glycol dimethacrylate) (in mol) and barium glass at increasing concentrations from 25 to 60 vol.% (5% increments) were tested. Stress was determined in a universal test machine using acrylic as bonding substrate. Nominal polymerization stress was obtained diving the maximum load by the cross-surface area. Shrinkage was measured using a water picnometer. Elastic modulus was obtained by three-point flexural test. Degree of conversion was determined by FT-Raman spectroscopy. Results. Polymerization stress and shrinkage showed inverse relationships with filler content (R(2) = 0.965 and R(2) = 0.966, respectively). Elastic modulus presented a direct correlation with inorganic content (R(2) = 0.984). Degree of conversion did not vary significantly. Polymerization stress showed a strong direct correlation with shrinkage (R(2) = 0.982) and inverse with elastic modulus (R(2) = 0.966). Significance. High inorganic contents were associated with low polymerization stress values, which can be explained by the reduced volumetric shrinkage presented by heavily filled composites. (C) 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Bis-GMA co-polymerizations: Influence on conversion, flexural properties, fracture toughness and susceptibility to ethanol degradation of experimental composites

Objectives. The aim of this study was to evaluate the influence of monomer content on fracture toughness (K(Ic)) before and after ethanol solution storage, flexural properties and degree of conversion (DC) of bisphenol A glycidyl methacrylate (Bis-GMA) co-polymers. Methods. Five formulations were tested, containing Bis-GMA (B) combined with TEGDMA (T), UDMA (U) or Bis-EMA (E), as follows (in mol%): 30B:70T; 30B:35T:35U; 30B:70U; 30B:35T:35E; 30B:70E. Bimodal filler was introduced at 80 wt%. Single-edge notched beams for fracture toughness (FT, 25 mm x 5 mm x 2.5 mm, a/w = 0.5, n = 20) and 10 mm x 2 mm x 1 mm beams for flexural strength (FS) and modulus (FM) determination (10 mm x 2 mm x 1 mm, n = 10) were built and then stored in distilled water for 24 h at 37 degrees C. All FS/FM beams and half of the FT specimens were immediately submitted to three-point bending test. The remaining FT specimens were stored in a 75%ethanol/25%water (v/v) solution for 3 months prior to testing. DC was determined with FT-Raman spectroscopy in fragments of both FT and FS/FM specimens at 24 h. Data were submitted to one-way ANOVA/Tukey test (alpha = 5%). Results. The 30B:70T composite presented the highest K(Ic) value (in MPa m(1/2)) at 24 h (1.3 +/- 0.4), statistically similar to 30B:35T:35U and 30B:70U, while 30B:70E presented the lowest value (0.5 +/- 0.1). After ethanol storage, reductions in K(Ic) ranged from 33 to 72%. The 30B:70E material presented the lowest reduction in FT and 30B:70U, the highest. DC was similar among groups (69-73%), except for 30B:70U (52 +/- 4%, p < 0.001). 30B:70U and 30B:35T:35U presented the highest FS (125 +/- 21 and 122 +/- 14 MPa, respectively), statistically different from 30B:70T or 30B:70E (92 +/- 20 and 94 +/- 16 MPa, respectively). Composites containing UDMA or Bis-EMA associated with Bis-GMA presented similar FM, statistically lower than 30B:35T:35U. Significance. Composites formulated with Bis-GMA:TEGDMA:UDMA presented the best compromise between conversion and mechanical properties. (C) 2009 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Influence of BisGMA, TEGDMA, and BisEMA contents on viscosity, conversion, and flexural strength of experimental resins and composites

Different monomer structures lead to different physical and mechanical properties for both the monomers and the polymers. The objective of this study was to determine the influence of the bisphenylglycidyl dimethacrylate (BisGMA) concentration (33, 50 or 66 mol%) and the co-monomer content [triethylene glycol dimethacrylate (TEGDMA), ethoxylated bisphenol-A dimethacrylate (BisEMA), or both in equal parts] on viscosity (eta), degree of conversion (DC), and flexural strength (FS). eta was measured using a viscometer, DC was obtained by Fourier transfer Raman (FT-Raman) spectroscopy, and FS was determined by three-point bending. At 50 and 66% BisGMA, increases in eta were observed following the partial and total substitution of TEGDMA by BisEMA. For 33% BisGMA, eta increased significantly only when no TEGDMA was present. The DC was influenced by BisGMA content and co-monomer type. Mixtures containing 66% BisGMA showed a lower DC compared with mixtures containing other concentrations of BisGMA. The BisEMA mixtures had a lower DC compared with the TEGDMA mixtures. The FS was influenced by co-monomer content only. BisEMA mixtures presented a statistically lower FS, followed by TEGDMA + BisEMA mixtures, and then by TEGDMA mixtures. Partial or total replacement of TEGDMA by BisEMA increased eta, which was associated with the observed decreases in DC and FS. Although the BisGMA content influenced the DC, it did not affect the FS results.

Influence of Photoactivation Protocol and Light Guide Distance on Conversion and Microleakage of Composite Restorations

Purpose: To evaluate the effect of light guide distance and the different photoactivation methods on the degree of conversion (DC) and microleakage of a composite. Methods and Materials: Three photoactivation protocols (600mW/cm(2) x 40 seconds; 400 mW/cm(2) x 60 seconds or 200 mW/cm(2) x 20 seconds, followed by 500 mW/cm(2) X 40 seconds) and three distances from the light source (0, 3 or 7 mm) were tested. Cylindrical specimens (5 nun diameter; 2 mm tall; n=3) were prepared for the DC test (FT-Raman). Class V cavities were made in 90 bovine incisors to conduct the microleakage test. The specimens were conditioned for 15 seconds with phosphoric acid (37%), followed by application of the adhesive system Prime & Bond NT (Dentsply/Caulk). The preparations were restored in bulk. The specimens were stored for 24 hours in distilled water (37 degrees C) before being submitted to the silvernitrate microleakage protocol. The restorations were sectioned and analyzed under 25x magnification. Results: Statistical analyses (two-way ANOVAs and Tukey test, alpha=0.05) found significance only for the factor distance (p=0.015) at the top of the composite for the DC test. Conversion was statistically lower for the 7 mm groups compared to the 0 and 3 mm groups, which were equivalent to each other. At the bottom of the specimens, none of the factors or interactions was significant (p<0.05). The Kruskal-Wallis test showed that, in general, the soft-start method led to lower microleakage scores when compared to the continuous modes, mainly when associated with a distancing of 7 mm (p<0.01). With the exception of specimens irradiated with 400mW/cm(2) that did not demonstrate variations on scores for the distances tested, higher microleakage was observed for shorter distances from the light source. Conclusions: Soft-start methods may reduce microleakage when the light guide distancing provides a low level of irradiance, which also causes a discrete reduction in the DC.

Contraction stress determinants in dimethacrylate composites

The influence of composite organic content on polymerization stress development remains unclear. It was hypothesized that stress was directly related to differences in degree of conversion, volumetric shrinkage, elastic modulus, and maximum rate of polymerization encountered in composites containing different BisGMA (bisphenylglycidyl dimethacrylate) concentrations and TEGDMA ( triethylene glycol dimethacrylate) and/or BisEMA ( ethoxylated bisphenol-A dimethacrylate) as co-monomers. Stress was determined in a tensilometer. Volumetric shrinkage was measured with a mercury dilatometer. Elastic modulus was obtained by flexural test. We used fragments of flexural specimens to determine degree of conversion by FT-Raman spectroscopy. Reaction rate was determined by differential scanning calorimetry. Composites with lower BisGMA content and those containing TEGDMA showed higher stress, conversion, shrinkage, and elastic modulus. Polymerization rate did not vary significantly, except for the lower value of the 66% TEGDMA composite. We used linear regressions to evaluate the association between polymerization stress and conversion (R-2 = 0.905), shrinkage ( R-2 = 0.825), and modulus ( R-2 = 0.623).

Early and 24-hour bond strength and degree of conversion of etch-and-rinse and self-etch adhesives

Purpose: To evaluate early and 24-hour microtensile bond strength (mu TBS) and the degree of conversion (DC) of one representative adhesive system from each of the four current bonding approaches. Methods: 40 human molars were sectioned occluso-gingivally into two halves. Resin composite was bonded incrementally to flat, mid-coronal dentin, using the adhesives Adper Scotchbond MP (MP); Adper Scotchbond 2 (SB); Clearfil SE Bond (SE); and Adper Prompt L-Pop (LP) according to the respective manufacturer`s instructions (n= 10). One half was immediately sectioned into sticks and subjected to mu TBS test. As the sectioning process took approximately 1 hour, the results were designated as 1-hour bond strengths. The other half was stored in distilled water at 37 degrees C for 24 hours before being sectioned and tested. The DC of these systems was measured using Fourier Transform-Raman spectroscopy in three periods: immediately, 1 and 24 hours after polymerization. Data were analyzed with ANOVA and Tukey`s tests. Results: There were no significant differences between the 1-hour and 24-hour bond strengths (P> 0.05), or among the DC measured immediately, 1 hour and 24 hours after polymerization (P> 0.05). However, significant differences were observed among adhesives (P< 0.05). mu TBS values obtained, in MPa (1 hour/24 hour), were: SB (48.6 + 1.3/48.4 + 3.5) = SE (51.9 + 4.7/53.3 +/- 2.9) > MP (35.3 +/- 10.9/38.6 + 6.7) > LP (25.5 + 1.1/26.0 + 1.5). The DC, in percentage (immediately/1 hour/24 hour), were: SE (81/82/87) > MP (79/77/81) > SB (60/63/65) > LP (39/37/42).

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. 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. (C) 2009 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.