Thermal analysis and structural investigation of different dental composite resins

The structural and thermal properties of three different dental composite resins, Filtek (TM) Supreme XT, Filtek (TM) Z-250 and TPHA (R)(3) were investigated in this study. The internal structures of uncured and cured resins with blue light-emitting diodes (LEDs) were examined by Micro-Raman spectroscopy. Thermal analysis techniques as DSC, TG and DTG methods were used to investigate the temperature characteristics, as glass transition (T (g) ), degradation, and the thermal stability of the resins. The results showed that the TPHA (R)(3) and Filtek (TM) Supreme XT presented very similar T (g) values, 48 and 50A degrees C, respectively, while the Filtek (TM) Z-250 composite resin presented a higher one, 58A degrees C. AFM microscope was utilized in order to analyze the sample morphologies, which possess different fillers. The composed resin Filtek (TM) Z-250 has a well interconnected more homogeneous morphology, suggesting a better degree of conversion correlated to the glass phase transition temperature. The modes of vibration of interest in the resin were investigated using Raman spectroscopy. It was possible to observe the bands representative for the C=C (1630 cm(-1)) and C=O(1700 cm(-1)) vibrations were studied with respect to their compositions and polymerization. It was observed that the Filtek (TM) Z -250 resin presents the best result related to the thermal properties and polymerization after light curing among the other resins.

Synthesis optimization, structural evolution and optical properties of Y(0.9)Er(0.1)Al(3)(BO(3))(4) nanopowders obtained by soft chemistry methods

This paper describes the structural evolution of Y(0.9)Er(0.1)Al(3)(BO(3))(4) nanopowders using two soft chemistry routes, the sol-gel and the polymeric precursor methods. Differential scanning calorimetry, differential thermal analyses, thermogravimetric analyses, X-ray diffraction, Fourier-transform infrared, and Raman spectroscopy techniques have been used to study the chemical reactions between 700 and 1200 degrees C temperature range. From both methods the Y(0.9)Er(0.1)Al(3)(BO(3))(4) (Er:YAB) solid solution was obtained almost pure when the powdered samples were heat treated at 1150 degrees C. Based on the results, a schematic phase formation diagram of Er:YAB crystalline solid solution was proposed for powders from each method. The Er:YAB solid solution could be optimized by adding a small amount of boron oxide in excess to the Er:YAB nominal composition. The nanoparticles are obtained around 210 nm. Photoluminescence emission spectrum of the Er:YAB nanocrystalline powders was measured on the infrared region and the Stark components of the (4)I(13/2) and (4)I(15/2) levels were determined. Finally, for the first time the Raman spectrum of Y(0.9)Er(0.1)Al(3)(BO(3))(4) crystalline phase is also presented. (C) 2008 Elsevier Masson SAS. All rights reserved.

Observation of persistent photoconductivity in vanadyl phthalocyanine

Persistent photoconductivity (PPC) in vanadyl phthalocyanine (VOPc) organic light-emitting diodes was investigated using photoconductive time response, photocurrent-voltage characteristics and charge extraction in linearly increasing voltage (CELIV) measurements. The experiments were performed in phase 1 (amorphous) and in phase 2 (crystalline) samples obtained by the physical vapour deposition (PVD) technique over ITO/glass electrodes with an Al covering electrode. The results indicated a photoconductivity with a long decay time in phase 1 VOPc described by a stretched exponential relaxation. The device showed a rectifying behaviour and the mobility of holes was measured by CELIV, following a dispersive model. In crystalline samples the PPC effect was not observed and the dominant mechanism of transport of holes was hopping in a Gaussian density of states.

Enhanced visualization of histological samples with an adjustable RGB contrast system with application for tissue used in photodynamic therapy

The analysis of histological sections has long been a valuable tool in the pathological studies. The interpretation of tissue conditions, however, relies directly on visual evaluation of tissue slides, which may be difficult to interpret because of poor contrast or poor color differentiation. The Chromatic Contrast Visualization System (CCV) combines an optical microscope with electronically controlled light-emitting diodes (LEDs) in order to generate adjustable intensities of RGB channels for sample illumination. While most image enhancement techniques rely on software post-processing of an image acquired under standard illumination conditions, CCV produces real-time variations in the color composition of the light source itself. The possibility of covering the entire RGB chromatic range, combined with the optical properties of the different tissues, allows for a substantial enhancement in image details. Traditional image acquisition methods do not exploit these visual enhancements which results in poorer visual distinction among tissue structures. Photodynamic therapy (PDT) procedures are of increasing interest in the treatment of several forms of cancer. This study uses histological slides of rat liver samples that were induced to necrosis after being exposed to PDT. Results show that visualization of tissue structures could be improved by changing colors and intensities of the microscope light source. PDT-necrosed tissue samples are better differentiated when illuminated with different color wavelengths, leading to an improved differentiation of cells in the necrosis area. Due to the potential benefits it can bring to interpretation and diagnosis, further research in this field could make CCV an attractive technique for medical applications.

In vitro effect of low-level laser on odontoblast-like cells

The aim of this study was to evaluate the metabolism of odontoblast-like MDPC-23 cells subjected to direct LLL irradiation. The cells were seeded (20,000 cells/well) in 24-well plates and incubated for 24 hours at 37 degrees C. After this period, the culture medium (DMEM) was replaced by fresh DMEM supplemented with 2 or 5% (stress induction by nutritional deficit) or 10% fetal bovine serum (FBS). The cells were exposed to laser doses of 2, 4, 10, 15 and 25 J/cm(2) from a near infrared InGaAsP diode laser prototype (LASERTable; 780 +/- 3 nm, 40 mW). One control group (sham irradiation) was established for each experimental condition (laser dose x FBS supplementation). Three and 72 hours after the last irradiation, cells were analyzed with respect to metabolism, morphology, total protein expression and alkaline phosphatase (ALP) activity. Higher metabolism and total protein expression were observed 72 hours after the last irradiation at the doses of 15 and 25 J/cm(2) (Mann-Whitney; p<0.05). Higher ALP activity was obtained with 5% FBS when the cells were irradiated with doses of 2 and 10 J/cm(2). For the dose of 25 J/cm(2), the highest ALP activity was observed with 10% FBS. It was concluded that the LLLT parameters used in this study stimulated the metabolic activity of the MDPC-23 cells, especially at the doses of 15 and 25 J/cm(2).

Increased Viability of Odontoblast-Like Cells Subjected to Low-Level Laser Irradiation

Studies have shown that the increase of cell metabolism depends on the low level laser therapy (LLLT) parameters used to irradiate the cells. However, the optimal laser dose to up-regulate pulp cell activity remains unknown. Consequently, the aim of this study was to evaluate the metabolic response of odontoblast-like cells (MDPC-23) exposed to different LLLT doses. Cells at 20000 cells/cm(2) were seeded in 24-well plates using plain culture medium (DMEM) and were incubated in a humidified incubator with 5% CO(2) at 37 degrees C. After 24 h, the culture medium was replaced by fresh DMEM supplemented with 5% (stress by nutritional deficit) or 10% fetal bovine serum (FBS). The cells were exposed to different laser doses from a near infrared diode laser prototype designed to provide a uniform irradiation of the wells. The experimental groups were: G1: 1.5 J/cm(2) + 5% FBS; G2: 1.5 J/cm(2) + 10% FBS; G3: 5 J/cm(2) + 5% FBS; G4: 5 J/cm(2) + 10% FBS; G5: 19 J/cm(2) + 5% FBS; G6: 19 J/cm(2) + 10% FBS. LLLT was performed in 3 consecutive irradiation cycles with a 24-hour interval. Non-irradiated cells cultured in DMEM supplemented with either 5 or 10% FBS served as control groups. The analysis of the metabolic response was performed by the MTT assay 3 h after the last irradiation. G1 presented an increase in SDH enzyme activity and differed significantly (Mann-Whitney test, p < 0.05) from the other groups. Analysis by scanning electron microscopy showed normal cell morphology in all groups. Under the tested conditions, LLLT stimulated the metabolic activity of MDPC-23 cultured in DMEM supplemented with 5% FBS and exposed to a laser dose of 1.5 J/cm(2). These findings are relevant for further studies on the action of near infrared lasers on cells with odontoblast phenotype.

Mixing alternating copolymers containing fluorenyl groups with phospholipids to obtain Langmuir and Langmuir-Blodgett films

The control of molecular architectures may be essential to optimize materials properties for producing luminescent devices from polymers, especially in the blue region of the spectrum. In this Article, we report on the fabrication of Langmuir-Blodgett (LB) films of polyfluorene copolymers mixed with the phospholipid dimyristoyl phosphatidic acid (DMPA). The copolymers poly(9.9-dioetylfluorene)-co-phenylene (copolymer I) and poly(9,9-dioctylfluorene)-co-quaterphenylene) (copolymer 2) were synthesized via Suzuki reaction. Copolymer I could not form a monolayer on its own, but it yielded stable films when mixed with DMPA. In contrast, Langmuir monolayers could be formed from either the neat copolymer 2 or when mixed with DMPA. The surface pressure and surface potential measurements, in addition to Brewster angle microscopy, indicated that DMPA provided a suitable matrix for copolymer I to form a stable Langmuir film, amenable to transfer as LB films, while enhancing the ability of copolymer 2 to form LB films with enhanced emission, as indicated by fluorescence spectroscopy. Because a high emission was obtained with the mixed LB films and since the molecular-level interactions between the film components can be tuned by changing the experimental conditions to allow For further optimization, one may envisage applications of these films in optical devices such as organic light-emitting diodes (OLEDs).

A Multitechnique Study of Structure and Dynamics of Polyfluorene Cast Films and the Influence on Their Photoluminescence

This article describes the microstructure and dynamics in the solid state of polyfluorene-based polymers, poly(9,)-dioctylfluorenyl-2,7-diyl) (PFO), a semicrystalline polymer, and poly [(9,9-dioctyl- 2,7-divinylene-fluorenylene)-alt-co-{2-methoxy-5-(2-ethyl-hexyloxy)- 1,4-phenylene vinylene}, a copolymer with mesomorphic phase properties. These Structures were determined by wide-angle X-ray scattering (WAXS) measurements, Assuming a packing model for the copolymer structure, where the planes of the phenyl rings are stacked and separated by an average distance of similar to 4.5 angstrom and laterally spaced by about similar to 16 angstrom, we followed the evolution of these distances as a function of temperature using WAXS and associated the changes observed to the polymer relaxation processes identified by dynamical mechanical thermal analysis. Specific molecular motions were studied by solid-state nuclear magnetic resonance. The onset of the side-chain motion at about 213 K (beta-relaxation) produced a small increase in the lateral spacing and in the stacking distance of the phenyl rings in them aggregated Structures, Besides, at about 383 K (alpha-relaxation) there occurs a significant increase in the amplitude of the torsion motion in the backbone, producing a greater increase in the stacking distance of the phenyl rings. Similar results were observed in the semicrystalline phase of PFO, but in this case the presence of the crystalline structure affects considerably the overall dynamics, which tends to be more hindered. Put together, Our data explain many features of the temperature dependence of the photoluminescence of these two polymers.

De-aggregation of polyfluorene derivative by blending with a series of poly(alkyl methacrylate)s with varying sidegroup sizes

A polyfluorene derivative of the PPV, poly(9,9`-n-dihexyl-2,7-fluorenedilvinylene-alt-1,4-phenylenevinylene), with a strong tendency to aggregation was blended with several members of a series composed by poly(alkyl methacrylate)s with the following substituents in the ester position: methyl, ethyl, isopropyl, isobutyl, n-butyl, and cyclohexyl. The de-aggregation effect in blends was studied by steady-state photoluminescence spectroscopy using several blend compositions. The efficiency of each dispersing phase was discussed in terms of the polymer miscibility, controlled by interaction parameters between the polyfluorene and every poly(alkyl methacrylate)s, here described using Hilde-brand solubility parameters. (c) 2009 Elsevier Ltd. All rights reserved.

Temperature dependence of molecular dynamics and supramolecular aggregation in MEH-PPV films: A solid-state NMR, X-ray and fluorescence spectroscopy study

This article presents an investigation of the temperature induced modification in the microstructure and dynamics of poly[2-methoxy-5-(2`-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) cast films using Wide-Angle X-ray Scattering (WAXS), solid-state Nuclear Magnetic Resonance (NMR), and Fluorescence Spectroscopy (PL). MEH-PPV chain motions were characterized as a function of temperature by NMR. The results indicated that the solvent used to cast the films influences the activation energy of the side-chain motions. This was concluded from the comparison of the activation energy of the toluene cast film, E(a) = (54 +/- 8) kJ/mol, and chloroform cast film, E(a) = (69 +/- 5) kJ/mol, and could be attributed to the higher side-chain packing provided by chloroform, that preferentially solvates the side chain in contrast to toluene that solvates mainly the backbone. Concerning the backbone mobility, it was observed that the torsional motions in the MEH-PPV have average amplitude of similar to 10 degrees at 300 K, which was found to be independent of the solvent used to cast the films. In order to correlate the molecular dynamics processes with the changes in the microstructure of the polymer, in situ WAXS experiments as a function of temperature were performed and revealed that the interchain spacing in the MEH-PPV molecular aggregates increases as a function of temperature, particularly at temperatures where molecular relaxations occur. It was also observed that the WAXS peak associated with the bilayer spacing becomes narrower and its intensity increases whereas the peak associated with the inter-backbone planes reduces its intensity for higher temperatures. This last result Could be interpreted as a decrease in the number of aggregates and the reduction of the interchain species during the MEH-PPV relaxation processes. These WAXS results were correlated with PL spectra modifications observed upon temperature treatments. (C) 2008 Elsevier Ltd. All rights reserved.

Absorption and emission properties of LBL PPV films deposited on ITO electrodes

In this work we studied the properties of absorption and emission line shape of layer-by-layer (LBL) poly(p-phenylene vinylene) (PPV) on indium-tin oxide (ITO) electrode. To minimize the PPV thermal conversion effects during the polymer processing, we used a less aggressive leaving group in the precursor polymer; minimizing electrode degradation. LBL ITO/PPV films showed the same absorption and emission line shape compared with LBL PPV films deposited on non-metallic substrates (glass). With this analysis we indirectly observe the decrease in the ITO degradation. Atomic force microscopy (AFM) technique was used to analyze quantitatively the microscopic morphology of the film surface. Results indicated that the substrate topology is not affected, to a large extent, by the use of dodecylbenzensulfonate (DBS) ion. (C) 2008 Elsevier B.V. All rights reserved.

Tryptophan oxidation by singlet molecular oxygen [O-2 ((1)Delta(g))]: Mechanistic studies using O-18-labeled hydroperoxides, mass spectrometry, and light emission measurements

Proteins have been considered important targets for reactive oxygen species. Indeed, tryptophan (W) has been shown to be a highly susceptible amino acid to many oxidizing agents, including singlet molecular oxygen [O-2 ((1)Delta(g))]. In this study, two cis- and trans-tryptophan hydroperoxide (WOOH) isomers were completely characterized by HPLC/mass spectrometry and NMR analyses as the major W-oxidation photoproducts. These photoproducts underwent thermal decay into the corresponding alcohols. Additionally, WOOHs were shown to decompose under heating or basification, leading to the formation of N-formylkynurenine (FMK). Using O-18-labeled hydroperoxides ((WOOH)-O-18-O-18), it was possible to confirm the formation of two oxygen-labeled FMK molecules derived from (WOOH)-O-18-O-18 decomposition. This result demonstrates that both oxygen atoms in FMK are derived from the hydroperoxide group. In addition, these reactions are chemiluminescent (CL), indicating a dioxetane cleavage pathway. This mechanism was confirmed since the CL spectrum of the WOOH decomposition matched the FMK fluorescence spectrum, unequivocally identifying FMK as the emitting species.

Langmuir Films of Petroleum at the Air-Water Interface

Understanding the behavior of petroleum films at the air/water interface is crucial for dealing with oil sticks and reducing the damages to the environment, which has normally been attempted with studies of Langmuir films made of fractions of petroleum. However, the properties of films from whole petroleum samples may differ considerably from those of individual fractions, Using surface pressure and surface potential measurements and Brewster angle and fluorescence microscopy, we show that petroleum forms it nonhomogeneous Langmuir film at the air-water interface. The surface pressure isotherms for petroleum Langmuir films exhibit gas (G), liquid-expanded (LE), and liquid-condensed phases, with almost no hysteresis in the compression-decompression cycles. Domains formed upon compression from the G to the LE phase were accompanied by an increase in fluorescence intensity with excitation at 400-440 nm owing to an increase in the surface density of the chromophores in the petroleum film. The surface pressure and the fluorescence microscopy data pointed to self-assembling domains into a pseudophase in thermo-dynamic equilibrium with other less emitting petroleum components. This hypothesis was supported by Brewster angle microscopy images, whereby the appearance of water domains even at high surface pressures confirms the tendency of petroleum to stabilize emulsion systems. The results presented here suggest that, for understanding the interaction with water, it may be more appropriate to use the whole petroleum samples rather than its fractions.

Novel electroluminescent devices containing Eu(3+)-(2-acyl-1,3-indandionate) complexes with TPPO ligand

Fabrication and electroluminescent properties of devices containing europium complexes of general formula [Eu(ACIND)(3)(TPPO)(2)], where ACIND, 2-acyl-1,3-indandionate ligands: and TPPO, triphenylphosphine oxide. as emitter layers are discussed. The double-layer devices based on these complexes present the following configurations: device 1: ITO/TPD/[Eu(AlND)(3)(TPPO)(2)]/Al: device 2: ITO/TPD/[Eu(ISOV-IND)(3)(TPPO)(2)]/Al and device 3: ITO/TPD/[Eu(BIND)(3)(TPPO)(2)]/Al, where AlND, 2-acetyl-1,3-indandionate; ISOVIND, 2-isovaleryl-1,3-indandionate; and BIND, 2-benzoyl-1,3-indandionate, respectively. These devices exhibited photo and electroluminescent emissions. An important characteristic presented by devices is that their electroluminescent (EL) spectra, in the region of (5)D(0) -> (7)F(J) (J = 0, 1, 2, 3 and 4) transitions of Eu(3+) ion, show profiles that are different from photoluminescent (PL) ones. In addition to narrow bands arising from intraconfigurational-4f(6) transitions, devices 1 and 2 also exhibited a broad band with maximum at around 500 nm which is assigned to electrophosphorescence from the indandionate ligands. On the other hand, EL spectra of device 3 present only narrow bands from (5)D(0) -> (7)F(J) transitions. [Eu(ACIND)(3)(TPPO)(2)] complexes are promising candidates to prepare efficient organic light-emitting devices (OLEDs) when compared with those containing Eu(3+)-complexes of aliphatic beta-diketonate anions. (C) 2009 Elsevier B.V. All rights reserved.

On the energy transfer from a polymer host to the rhenium(I) complex in OLEDs

Photoluminescence and electroluminescence of PVK films doped with fac-[ClRe(CO)(3)(bpy)], bpy=2,2`-bipyridine, are investigated. Photoluminescence spectra of spin-coated PVK films (lambda(exc)=290 nm) exhibit a broad band centered at 405 nm. As the concentration of dopant increases, the polymer emission is quenched and a band at 555 nm appears (isosbestic point at 475 nm). In OLEDs with ITO/PEDOT:PSS/PVK/butylPBD/Al architecture doped with fac-[ClRe(CO)(3)(bpy)], the polymer host emission is completely quenched even at the lowest concentration of dopant. The electroluminescence spectra of the devices show that there is an efficient energy transfer from the host to the dopant, which exhibits a very intense emission at 580 nm. (C) 2009 Elsevier B.V. All rights reserved.