Synthesis of poly(styrene-co-methyl methacrylate)-based ionomers and their Langmuir and Langmuir-Blodgett (LB) film formation

Poly(styrene-co-methyl methacrylate) (PS-PMMA) ionomers with several degrees of sulfonation were synthesized and characterized by infrared, UV-vis, and NMR spectroscopies, elemental analysis, and differential scanning calorimetry (DSC). Stable Langmuir films could be produced with PS-PMMA with 3 and 6 mol % of sulfonation, while PS-PMMA 8% exhibited material loss to the water subphase, probably due to its higher solubility. Surface pressure and surface potential isotherms with PS-PMMA 3% spread onto salt-containing subphases pointed to a film behavior characteristic of the polyelectrolyte effect, where charge repulsion governs the film properties. The Langmuir-Blodgett films of this ionomer were successfully transferred onto various substrates, as confirmed by UV-vis and FTIR spectroscopies. Using cycling voltammetry, we show that LB films from PS-PMMA 3% can be applied in selective sensing of dopamine, even in the presence of interferents such as ascorbic acid.

Effect of methyl methacrylate monomer on bond strength of denture base resin to acrylic teeth

Bond failures at the acrylic teeth and denture base resin interface are still a common clinical problem in prosthodontics. The effect of methyl methacrylate (MMA) monomer on the bond strength of three types of denture base resins (Acron MC, Lucitone 550 and QC-20) to two types of acrylic teeth (Biotone and Trilux) was evaluated. Twenty specimens were produced for each denture base resin/acrylic tooth combination and were randomly divided into control (acrylic teeth received no surface treatment) and experimental groups (MMA was applied to the surface of the acrylic teeth for 180 s) and were submitted to shear tests (1 mm/mm). Data (MPa) were analyzed using three-way ANOVA/Student's test (alpha = 0.05). MMA increased the bond strength of Lucitone denture base resins and decreased the bond strength of QC-20. No difference was detected for the bond strength of Acron MC base resin after treatment with MMA. (C) 2008 Elsevier Ltd. All rights reserved.

Effect of incorporation of 2-tert-butylaminoethyl methacrylate on flexural strength of a denture base acrylic resin

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Staining methods applied to glycol methacrylate embedded tissue sections

The use of glycol methacrylate (GMA) avoids some technical artifacts, which are usually observed in paraffin-embedded sections, providing good morphological resolution. on the other hand, weak staining have been mentioned during the use of different methods in plastic sections. In the present study, changes in the histological staining procedures have been assayed during the use of staining and histochemical methods in different GMA-embedded tissues.Samples of tongue, submandibular and sublingual glands, cartilage, portions of respiratory tract and nervous ganglion were fixed in 4% formaldehyde and embedded in glycol methacrylate. The sections of tongue and nervous ganglion were stained by H&E. Picrosirius, Toluidine Blue and Sudan Black B methods were applied, respectively, for identification of collagen fibers in submandibular gland, sulfated glycosaminoglycans in cartilage (metachromasia) and myelin lipids in nervous ganglion. Periodic Acid-Schiff (PAS) method was used for detection of glycoconjugates in submandibular gland and cartilage while AB/PAS combined methods were applied for detection of mucins in the respiratory tract. In addition, a combination of Alcian Blue (AB) and Picrosirius methods was also assayed in the sublingual gland sections.The GMA-embedded tissue sections showed an optimal morphological integrity and were favorable to the staining methods employed in the present study. In the sections of tongue and nervous ganglion, a good contrast of basophilic and acidophilic structures was obtained by H&E. An intense eosinophilia was observed either in the striated muscle fibers or in the myelin sheaths in which the lipids were preserved and revealed by Sudan Black B. In the cartilage matrix, a strong metachromasia was revealed by Toluidine Blue in the negatively-charged glycosaminoglycans. In the chondrocytes, glycogen granules were intensely positive to PAS method. Extracellular glycoproteins were also PAS positive in the basal membrane and in the region occupied by the lamina externa and reticular fibers surrounding each smooth muscle cells of the blood vessels. In the epithelial cells of the respiratory tract, acid and neutral mucins were histochemically detected by AB and PAS methods, respectively. Moreover, granules containing acid and neutral mucins were revealed in purple by AB and PAS concomitantly. In the sublingual gland sections, a distinct affinity of acid mucins by AB (in turquoise-blue) and collagen fibers by Picrosirius (in red) was obtained when these methods were combined. Although some routine dyes used in paraffin sections have showed a weak stain in historesin sections, our results showed that different dyes could be applied in GMA sections if modified staining procedures were assayed. Therefore, appropriate staining contrast and, thus, detection of one or different substances in a same section can be acquired in association to the good morphological resolution provided by GMA. (C) 2003 Elsevier Ltd. All rights reserved.

Persistence of endodontic methacrylate-based cement residues on dentin adhesive surface treated with different chemical removal protocols

The aim of this study was to evaluate the persistence of methacrylate-based cement residues on the dentin, after dentin surface cleaning with ethanol or acetone, with or without previous application of a dentin adhesive. Forty bovine crown fragments were obtained and the dentin surface was washed with 1.0 mL of 2.5% sodium hypochlorite (NaOCl), followed by 0.1 mL of 17% ethylenediaminetetraacetic acid application for 3 min, and final irrigation with 2.5% NaOCl. The specimens were air dried and resin-based cement was rubbed onto the dentine surface with a microbrush applicator. In 20 specimens, previously to cement, a dentin adhesive was applied in all surfaces. After 15 min, the surface was scrubbed with a cotton pellet and moistened with ethanol or acetone, compounding the following groups: G199.5% ethanol and G2acetone, without previous use of dentin adhesive; G399.5% ethanol and G4acetone, with previous use of dentin adhesive. The dentin surface was scrubbed until the cement residues could not be visually detected. Sections were then processed for scanning electron microscopy and evaluated at 500x magnification and scores were attributed to each image according to the area covered by residual sealer, and data were subjected to KruskalWallis at 5% significance. The lower residue presence was observed in G3 (P = 0.005). All surface presented cement residues when acetone was used as cleaning solution (P = 0.0005). The cleaning solutions were unable to completely remove the cement residues from both surfaces. The ethanol used after previous application of the dentin adhesive promoted the lower presence of residues.

Synthesis, characterization and solution properties of amphiphilic N-isopropylacrylamide-poly(ethylene glycol)-dodecyl methacrylate thermosensitive polymers

Terpolymers of N-isopropylacrylamide, dodecyl methacrylate (DOMA) and poly(ethylene glycol) (PEG) methacrylate, were synthesized by random copolymerization, and the composition was controlled to achieve systems having different thermosensitivities. H-1 NMR spectra and gel permeation chromatography (GPC) were employed to characterize the different samples obtained. The solution properties were studied by employing spectrophotometry, fluorescence, and dynamic light scattering techniques. The chemical compositions in the final terpolymers are close to those in the feed. The polymers exhibited cloud point temperatures (T-es) varying from 17 to 52 degrees C. Micropolarity studies using I-1/I-3 ratio of the vibronic bands of pyrene show the formation of amphiphilic aggregates capable of incorporating hydrophobic drugs as the polymer concentration is increased. The critical aggregation concentration (CAC) increases from 3.6 x 10(-3) to 1 x 10(-2) g/l with the PEG content varying from 5 to 35 mol%. Anisotropy measurements confirm the results obtained by pyrene fluorescence and show that the aggregates resulting from intermolecular interactions present different organizations. The hydrodynamic diameters (Dh) of the aggregates determined by dynamic light scattering (DLS) vary from 40 to 150 nm depending on the terpolymer composition. The T-cs and Dh values decreased with the ionic strength, and this behavior was attributed to the dehydration of the polymeric micelles. The capacity of solubilization of the aggregates was evaluated by employing pyrene, and the obtained results confirm the ability to incorporate hydrophobic molecules. (c) 2005 Elsevier B.V All rights reserved.

The Interaction Between N-Isopropylacrylamide-Acrylic Acid-Ethyl Methacrylate Thermosensitive Polymers and Cationic Surfactants

The interaction between cationic surfactants and isopropylacrylamide-acrylic acid-ethyl methacrylate (IPA:AA:EMA) terpolymers has been investigated using steady-state fluorescence and spectrophotometric measurements to assess the effect of the polymer composition on the aggregation process and terpolymers' thermosensitivities. Micropolarity studies using pyrene show that the interaction of cationic surfactants with IPA:AA:EMA terpolymers occurs at surfactant concentrations much smaller than that observed for the pure surfactant in aqueous solution. The critical aggregation concentration (CAC) values decrease with both the hydrocarbon length of the surfactant and the content of ethyl methacrylate. These results were interpreted as a manifestation of the increasing contribution of attractive hydrophobic and electrostatic forces between negatively charged polymer chains and positively charged surfactant molecules. The increase of ethyl methacrylate in the copolymers lowers the CAC due to the larger hydrophobic character of the polymer backbone. The cloud point determination reveals that the lower critical solution temperatures (LCST) depend strongly on the copolymer composition and surfactant nature. The binding of surfactants molecules to the polymer chain screens the electrostatic repulsion between the carboxylic groups inducing a conformational transition and the dehydration of the polymer chain.

Effect of cerium (IV) ions on the anticorrosion properties of siloxane-poly(methyl methacrylate) based film applied on tin coated steel

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Highly corrosion resistant siloxane-polymethyl methacrylate hybrid coatings

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Polymerization of photocurable commercial dental methacrylate-based composites - Photocalorimetry study

Due to their excellent aesthetics, photopolymers have been extensively used in several dentistry applications. However, several problems are reported, e.g. low mechanical and abrasion resistance, shrinkage during polymerization, etc. Properties of the final restorations are intrinsically related to the polymerization stage, which can be conveniently studied by photocalorimetry. In the present work the polymerization reaction and the filler content of different photocurable commercial dental methacrylate-based composites were studied by means of photocalorimetry and thermogravimetry, respectively. The results show that the values of curing rate, the heat of polymerization and the filler content vary significantly from one composite to another.

Fluorescence study of the interaction between metal ions and methyl methacrylate methacrylic acid copolymers in aqueous solutions: thallium(I), calcium(II), and terbium(III)

The binding of the cations thallium(I), calcium(II) and terbium(III) to methyl methacrylate-methacrylic acid copolymers with different fractions of acid groups (x) has been studied in aqueous solution at, various pH values using the fluorescence of covalently bonded 9-vinyl anthracene as a probe. In all cases, the extent of binding increases as a function of the charge of the polymer with either increasing fraction of carboxylic acids or of pH. However, differences are observed in the behavior of the three cations, With Tl(I), quenching of the anthracene group fluorescence is observed. indicating that the thallium(I) approaches the probe and suggesting that the alkylanthracene is probably in a relatively polar region. Binding constants have been determined from anthracene quenching data and from studies with the fluorescent-probe sodium pyrenetetrasulfonate, Good agreement is obtained between the two methods, and values for the binding constants increase from 250 to 950 M-1 as x increases from 0.39 to 1. It is suggested that the cation is held in the polyelectrolyte domain, partly by Debye-Huckel effects and partly by more specific interactions. Stronger binding is found with calcium(II) and terbium(III), and in this case increases in fluorescence intensity are observed on complexation due to the anthracene group being in a more hydrophobic region, probably as a result of conformational changes in the polymer chain. In the former case the stoichiometry of the interaction was determined from the fluorescence data to involve two carboxylate groups bound per calcium. Association constants were found using murexide as an indicator of free calcium to vary from 8400 to 37 000 M-1 as x increases from 0.39 to 1. It is suggested that in this case specific calcium(II)-carboxylate interactions contribute to the binding. With terbium(III), a greater increase in the probe fluorescence intensity was observed than with calcium, and it is suggested that the interaction with the polymer is even stronger, leading to a more pronounced conformational change in the polymer. It is proposed that the terbium(III) interacts with sis carboxylic groups on the polymer chain, with three being coordinated and three attracted by electrostatic interactions.

Thermal diffusivity analysis of doped poly(methyl-methacrylate) with electron donor and acceptor molecules

A computer-assisted method for analysing photoacoustic spectra has been developed in the Windows(TM) environment with the use of an easy graphical interface, the computer simulation was carried out with the aim of using the entire expression of the Rosencwaig-Gersho theory, thus permitting multiple applications. The simulation was applied to a system that mimics the electron transfer process in which the concentration of octaethylporphin donor molecules was constant whereas the concentration of duroquinone and 2,3-dichloro-5,6-dicyano-1, l-benzoquinone acceptor molecules varied. The increment of the acceptor concentration influenced the photoacoustic amplitude and phase signals. In the phase signal a significant shift to smaller values was observed, denoting a faster heat generation. The analysis of the photoacoustic signal enabled the determination of the thermal diffusivity, the result obtained through the simulation was about (7 +/- 1) x 10(-7) m(2) s(-1) indicating that changes in the photoacoustic phase signals were due to the electron transfer process rather than changes in the thermal properties of the sample.

Chromophore relaxation in a side-chain methacrylate copolymer functionalized with 4-[N-ethyl-N-(2-hydroxyethyl)]amino-2 '-chloro-4 '-nitroazobenzene

A side-chain methacrylate copolymer functionalized with the nonlinear optical chromophore 4-[N-ethyl-N-(2-hydroxyethyl)]amino-2'-chloro-4'-nitroazobenzene, disperse red-13, was prepared and characterized. The chromophore relaxation was investigated measuring the decay of the electrooptic coefficient r(13) and the complex dielectric constant at different temperatures. Results obtained below and above T-g were analyzed using the Kohlrausch-Williams-Watts(KWW) equation, through the study of the temperature dependence of the KWW parameters. Above T-g the relaxation time experimental data were fitted to the Williams-Landel-Ferry (WLF) equation and its parameters determined. Chromophore relaxation leading to the decrease of electrooptic properties was found associated with a primary alpha relaxation. The obtained WLF equation parameters were introduced into the Adam-Gibbs-Tool-Narayanaswamy-Moynihan equation, and the overall relaxation time temperature dependence was successfully obtained in terms of the fictive temperature, accounting for the sample thermal treatment and allowing optimized thermal treatment to be found. The copolymer KWW stretching parameter at the glass transition temperature lies close to the limit value for short-range interactions, i.e., 0.6, suggesting that the chromophore group is participating in primary a relaxation.

Spectroscopic properties of polycarbonate and poly(methyl methacrylate) blends doped with Europium(III) acetylacetonate

Spectroscopic properties of blends formed by bisphenol-A polycarbonate (PC) and poly(methyl methacrylate) (PMMA) doped with Europium (III) acetylacetonate [Eu(acac)(3)], have been studied by photoacoustic spectroscopy (PAS) and photoluminescent (PL) spectroscopy. Emission and excitation spectra, excited state decay times, and quantum efficiency have been evaluated as well. PAS studies evidenced chemical interactions between the Europium complex and the PC/PMMA blend, which presented typical percolation threshold behavior regarding the Eu3+ content. PL spectra evidenced the photoluminescence of the Eu3+ incorporated into the blend. Photoluminescence property enhancement was observed for the composite in comparison with the precursor compound. Optimized emission quantum efficiency was observed for the 60/40 blend doped with 2% and 4% Europium (III) acetylacetonate. (c) 2005 Elsevier B.V. All rights reserved.