Regimes of conformational transitions of a diblock polyampholyte

The conformational properties of symmetric flexible diblock polyampholytes are investigated by scaling theory and molecular dynamics simulations. The electrostatically driven coil-globule transition of a symmetric diblock polyampholyte is found to consist of three regimes identified with increasing electrostatic interaction strength. In the first (folding) regime the electrostatic attraction causes the chain to fold through the overlap of the two blocks, while each block is slightly stretched by self-repulsion. The second (weak association or scrambled egg) regime is the classical collapse of the chain into a globule dominated by the fluctuation-induced attractions between oppositely charged sections of the chain. The structure of the formed globule can be represented as a dense packing of the charged chain sections (electrostatic attraction blobs). The third (strong association or ion binding) regime starts with direct binding of oppositely charged monomers (dipole formation), followed by a cascade of multipole formation (quadrupole, hexapole, octupole, etc.), leading to multiplets analogous to those found in ionomers. The existence of the multiplet cascade has also been confirmed in the simulations of solutions of short polymers with only one single charge (either positive or negative) in the middle of each chain. We use scaling theory to estimate the average chain size and the electrostatic correlation length as functions of the chain length, strength of electrostatic interactions, charge fraction, and solvent quality. The theoretically predicted scaling laws of these conformational properties are in very good agreement with our simulation results.

Effect of ion concentration of ionomer in electron injection layer of polymer light-emitting devices

Polymer light-emitting devices (PLEDs) with poly(2-methoxy-5-hexyloxy)-p-phenylenevinylene (OC1OC6-PPV) as the emissive layer were studied with an electron injection layer of ionomers consisting of copolymers of styrene and methylmethacrylate (PS/PMMA) with 3, 6 and 8 mol% degree of sulfonation. The ionomers were able to form very thin films over the emissive layer, with less than 30 nm. Additionally, the presence of ion pairs of ionomer suppresses the tendency toward dewetting of the thin film of ionomer (similar to 10 nm) which can cause malfunction of the device. The effect of the ionomers was investigated as a function of the ion content. The devices performance, characterized by their current density and luminance intensity versus voltage, showed a remarkable increase with the ionomer layer up to 6 mol% of ionic groups, decreasing after that for the 8 mol% ionomer device. The study of the impedance spectroscopy in the frequency range from 0.1 to 10(6) Hz showed that the injection phenomena dominate over the transport in the electroluminescent polymer bulk. (c) 2006 Elsevier B.V. All rights reserved.

Retention of oral microorganisms on conventional and resin-modified glass-ionomer cements

A cárie secundária representa problema de saúde pública e socioeconômico no mundo. A restauração de dentes acometidos por cárie pode criar condições favoráveis à proliferação microbiana na superfície do material restaurador ou na interface dente/restauração, criando ambiente propício para o estabelecimento de cárie secundária. O objetivo deste estudo foi avaliar a capacidade de retenção de placa bacteriana em cimentos de ionômero de vidro convencionais (Chelon-Fil e Vidrion R) e modificados por resina (Vitremer e Fuji II LC) e de resina composta híbrida (Z100), utilizada como controle. Nos testes de retenção de microrganismos, in situ, 12 voluntários utilizaram, por 7 dias, placa de Hawley contendo corpos-de-prova de todos os materiais. A seguir, os corpos-de-prova foram transferidos para tubos contendo 2,0 ml de Ringer-PRAS e os microrganismos presentes em sua superfície foram cultivados em placa com ágar-sangue e ágar Mitis Salivarius Bacitracina, os quais foram incubados, a 37ºC, em anaerobiose (90% N2, 10% CO2), por 10 e 2 dias, respectivamente. Os ionômeros modificados por resina retiveram quantidade de bactérias similar àquela mostrada pela resina testada. Os ionômeros modificados por resina também apresentaram menor número de estreptococos do grupo mutans do que a resina e os cimentos ionoméricos convencionais. Os ionômeros de vidro convencionais apresentaram menor número de estreptococos do grupo mutans que a resina, sendo que essa diferença não foi estatisticamente significativa.

Fluoride release by restorative materials before and after a topical application of fluoride gel

The release of fluoride from restorative materials (Vitremer, Ketac-Fil, Fuji II LC and Freedom) was evaluated during two 15-day periods, before and after a topical application of acidulated phosphate fluoride gel (APF). For each material, 6 specimens were made, which were immersed in 2 ml of deionized water. The fluoride concentration dosages in the solutions were read at intervals of 24 hours for 15 days. After this period, the specimens of each material received treatment with APF gel for 4 minutes and the fluoride released was analyzed at 24-hour intervals during the following 15 days. The analysis of variance and the Tukey test (p < 0.05) showed that the total mean fluoride released during the initial 15 days was greater for Vitremer and Ketac-Fil and lower for Fuji II LC and Freedom; and in the final 15 days there was a difference in release readings, with the greatest value for Vitremer, followed by Fuji II LC, Ketac-Fil and Freedom. The comparison of the results between the 1st day and the 16th day (after gel application) showed a greater fluoride release on the 16th day for Vitremer, Fuji II LC and Freedom and was equal for Ketac-Fil. Although all the materials evaluated gained fluoride with the application of APF, the data suggest that the resin-modified ionomers are more efficient in releasing fluoride to the medium than the other materials.

Inhibitory activity of glass-ionomer cements on cariogenic bacteria

This study evaluated the antibacterial activity of the glass-ionomer cements Vitrebond (3M ESPE), Ketac Molar (3M ESPE) and Fuji IX (GC America) against S mutans, S sobrinus, L acidophilus and A viscosus, using the agar diffusion test. Inocula were obtained by the seed of indicators cultures in BHI broth incubated at 37°C for 24 hours. Base layers containing 15 mL of BHI agar and 300 μL of each bacteria suspension were prepared in Petri dishes. Six wells measuring 4 mm in diameter were made in each plate and completely filled with one of the testing materials. A 0.2% chlorhexidine solution applied in round filter papers was used as control. Tests were performed 12 times for each material and bacteria strain. After incubation of the plates at 37°C for 24 hours, the zones of bacterial growth inhibition around the wells were measured. Overall, the results showed the following sequence of antibacterial activity: Vitrebond (despite the activation mode) > 0.2% chlorhexidine > Ketac Molar > Fuji IX, according to Kruskal-Wallis and Mann-Whitney statistical tests. This study confirmed significant antibacterial activity for two conventional glass-ionomers and one resin-modified glass-ionomer material. The resin-modified glass-ionomer cement Vitrebond, regardless of the activation mode, presented the best antibacterial activity against S mutans and S sobrinus. The antibacterial activity against A viscosus for Vitrebond was similar to 0.2% chlorhexidine, while light activation reduced its antibacterial activity against L acidophilus. ©Operative Dentistry, 2005.

Effect of curing regime on the cytotoxicity of resin-modified glass-ionomer lining cements applied to an odontoblast-cell line

Objective: The aim of this in vitro study was to evaluate the cytotoxicity of resin-modified glass-ionomer lining cements submitted to different curing regimes and applied to an immortalized odontoblast-cell line (MDPC-23). Methods: Forty round-shaped specimens of each experimental material (Fuji Lining LC and Vitrebond) were prepared. They were light-cured for the manufacturers' recommended time (MRT = 30 s), under-cured (0.5 MRT = 15 s), over-cured (1.5 MRT = 45 s) or allowed to dark cure (0 MRT). Sterilized filter papers soaked with either 5 μL of PBS or HEMA were used as negative and positive control, respectively. After placing the specimens individually in wells of 24-well dishes, odontoblast-like cells MDPC-23 (30,000 cells/cm2) were plated in each well and incubated for 72 h in a humidified incubator at 37 °C with 5% CO2 and 95% air. The cytotoxicity was evaluated by the cell metabolism (MTT assay) and cell morphology (SEM). Results: Fuji Lining LC was less cytotoxic than Vitrebond (p < 0.05) in all the experimental conditions. However, the cytotoxicity of Fuji Lining LC was noticeably increased in the absence of light-curing while the same was not observed for Vitrebond. The length of light-curing (15, 30 or 45 s) did not influence the toxicity of both lining materials when they were applied on the odontoblast-cell line MDPC-23. Significance: The light-activation plays an important role in reducing the cytotoxicity of Fuji Lining LC. Following the manufacturer' recommendation regarding the light-curing regime may prevent toxic effect to the pulp cells. © 2005 Academy of Dental Materials.

In vitro surface roughness of different glass ionomer cements indicated for ART restorations

Aim: The aim of this in vitro study was to evaluate the surface roughness of three glass ionomer cements (GICs) indicated for ART restorations. Methods: Ten cylindrical specimens of three commercial glass ionomers cements (Vidrion R - S.S. White, Maxxion R - FGM and Vitromolar DFL) were prepared (n=30) without surface finishing or protection. Twenty-four hours after preparation, the surface roughness measurements were obtained as the mean of three readings of the surface of each specimen by profilometry. The roughness values (Ra, μm) were subjected to one-way ANOVA and Tukey's test (p<0.05). Results: No statistically significant differences were observed between Vidrion R (0.18 ± 0.05) and Vitromolar (0.21 ± 0.05), whereas Maxxion R presented significantly higher roughness values than those of the other materials. Conclusions: It may be concluded that characteristics of particle size and composition of the different GICs affected their surface roughness 24 h after preparation.

Desgaste e rugosidade superficial de um cimento de ionômero de vidro nanoparticulado

To compare the abrasion wear resistance and superficial roughness of different glass ionomer cements used as restorative materials, focusing on a new nanoparticulate material. Material and Method: Three glass ionomer cements were evaluated: Ketac Molar, Ketac N100 and Vitremer (3M ESPE, St. Paul, MN, USA), as well as the Filtek Z350 (3M ESPE, St. Paul, MN, USA). For each material were fabricated circular specimens (n=12), respecting the handling mode specified by the manufacturer, which were polished with sandpaper disks of decreasing grit. The wear was determined by the amount of mass (M) lost after brushing (10,000 cycles) and the roughness (Ra) using a surface roughness tester. The difference between the Minitial and Mfinal (ΔM) as well as beroughness of aesthetic restorative materials: an in vitro comparison. SADJ. 2001; 56(7): 316-20. 11. Yip HK, Peng D, Smales RJ. Effects of APF gel on the physical structure of compomers and glass ionomer cements. Oper. Dent. 2001; 26(3): 231-8. 12. Ma T, Johnson GH, Gordon GE. Effects of chemical disinfectants on the surface characteristics and color of denture resins. J Prosthet Dent 1997; 77(2): 197-204. 13. International organization for standardization. Technical specification 14569-1. Dental Materials – guidance on testing of wear resistance – PART I: wear by tooth brushing. Switzerland: ISO; 1999. 14. Bollen CML, Lambrechts P, Quirynen M. Comparison of surface roughness of oral hard materials to the threshold surface roughness for bacterial plaque retention: a review of the literature. Dent Mater.1997; 13(4): 258-9. 15. Kielbassa AM, Gillmann C, Zantner H, Meyer-Lueckel H, Hellwig E, Schulte-Mönting J. Profilometric and microradiographic studies on the effects of toothpaste and acidic gel abrasivity on sound and demineralized bovine dental enamel. Caries Res. 2005; 39(5): 380-6. 16. Tanoue N, Matsumara H, Atsuta M. Wear and surface roughness of current prosthetic composites after toothbrush/dentifrice abrasion. J Prosthet Dent. 2000; 84(1): 93-7. 17. Heath JR, Wilson HJ. Abrasion of restorative materials by toothpaste. J Oral Rehabil. 1976; 3(2): 121-38. 18. Frazier KB, Rueggeberg FA, Mettenburg DJ. Comparasion of wearresistance of class V restorative materials. J Esthet Dent. 1998; 10(6): 309-14. 19. Momoi Y, Hirosakil K, Kohmol A, McCabe JF. In vitro toothebrushdentifrrice abrasion of resin-modified glass ionomers. Dent Mater. 1997; 13(2): 82-8. 20. Turssi CP, Magalhães CS, Serra MC, Rodrigues Jr.AL. Surface roughness assessment of resin-based materials during brushing preceded by pHcycling simulations. Oper Dent. 2001; 26(6): 576-84. 21. Wang L, Cefaly DF, Dos Santos JL, Dos Santos JR, Lauris JR, Mondelli RF, et al. In vitro interactions between lactic acid solution and art glassionomer cements. J Appl Oral Sci. 2009; 17(4): 274-9. 22. Carvalho FG, Fucio SB, Paula AB, Correr GM, Sinhoreti MA, PuppinRontani RM. Child toothbrush abrasion effect on ionomeric materials. J Dent Child (Chic). 2008; 75(2): 112-6. 23. Coutinho E, Cardoso MV, De Munck J, Neves AA, Van Landuyt KL, Poitevin A, et al. Bonding effectiveness and interfacial characterization of a nano-filled resin-modified glass-ionomer. Dent Mater. 2009; 25(11): 1347-57. tween Rainitial and Rafinal (ΔRa) were also used for statistical analysis (α=0.05). Results: Except for the composite, significant loss of mass was observed for all glass ionomer cements and the ΔM was comparable for all of them. Significant increase in roughness was observed only for Vitremer and Ketac N100. At the end of the brushing cycle, just Vitremer presented surface roughness greater than the composite resin. Conclusion: All glass ionomer cements showed significant weight loss after 10,000 cycles of brushing. However, only Vitremer showed an increase of roughness greater than the Z350 resin, while the nanoparticulate cement Ketac N100 showed a smooth surface comparable to the composite.

Incorporação de nanopartículas de óxido de zinco a um cimento de ionômero de vidro por meio da calcinação: avaliação de propriedades mecânicas e físicas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Mass transport in polymers

The study of mass transport in polymeric membranes has grown in importance due to its potential application in many processes such as separation of gases and vapors, packaging, controlled drug release. The diffusion of a low molecular weight species in a polymer is often accompanied by other phenomena like swelling, reactions, stresses, that have not been investigated in all their aspects yet. Furthermore, novel materials have been developed that include inorganic fillers, reactive functional groups or ions, that make the scenery even more complicated. The present work focused on the experimental study of systems where the diffusion is accompanied by other processes; suitable models were also developed to describe the particular circumstances in order to understand the underlying concepts and be able to design the performances of the material. The effect of solvent-induced deformation in polymeric films during sorption processes was studied since the dilation, especially in constrained membranes, can cause the development of stresses and therefore early failures of the material. The bending beam technique was used to test the effects of the dilation and the stress induced in the polymer by penetrant diffusion. A model based on the laminate theory was developed that accounts for the swelling and is able to predict the stress that raise in the material. The addition of inorganic fillers affects the transport properties of polymeric films. Mixed matrix membranes based on fluorinated, high free volume matrices show attractive performances for separation purposes but there is a need for deeper investigation of the selectivity properties towards gases and vapors. A new procedure based on the NELF model was tested on the experimental data; it allows to predict solubility of every penetrant on the basis of data for one vapor. The method has proved to be useful also for the determination of the diffusion coefficient and for an estimation of the permeability in the composite materials. Oxygen scavenging systems can overcome lack of barrier properties in common polymers that forbids their application in sensitive applications as food packaging. The final goal of obtaining a membrane almost impermeable to oxygen leads to experimental times out of reach. Hence, a simple model was developed in order to describe the transport of oxygen in a membrane with also reactive groups and analyze the experimental data collected on SBS copolymers that show attractive scavenging capacity. Furthermore, a model for predicting the oxygen barrier behavior of a film formed as a blend of OSP in a common packaging material was built, considering particles capable of reactions with oxygen embedded in a non-reactive matrix. Perfluorosulphonic acid ionomers (PFSI) are capturing attention due to a high thermal and chemical resistance coupled with very peculiar transport properties, that make them appropriate to be used in fuel cells. The possible effect of different formation procedure was studied together with the swelling due to water sorption since both water uptake and dilation can dramatically affect the fuel cells performances. The water diffusion and sorption was studied with a FTIR-ATR spectrometer that can give deeper information on the bonds between water molecules and the sulphonic hydrophilic groups and, therefore, on the microstructure of the hydrated ionomer.

Flüssigkristalline Ionomere zum Aufbau von Multischichtstrukturen

Die vorliegende Arbeit beschäftigt sich mit der Synthese und Charakterisierung von nematischen und smektischen LC-Polyestern, die mit ionischen Gruppen funktionalisiert wurden. Als ionische Gruppen wurden Phosphonsäure-salze und Phosphonium- oder Ammoniumgruppen verwendet. Je nach Polymerrückgrat erhält man LC-Ionomere, bei denen die ionischen Gruppen entweder an das Mesogen oder an den Hauptkettenspacer gebunden sind. Diese LC-Ionomere können zusammen mit amorphen Polyelektrolyten oder anorganischen Schichtmineralien für den Multischichtaufbau durch alternierende Adsorption von Polykation und Polyanion aus der Lösung verwendet werden (Methode von G. Decher). Die Multischichtbildung konnte mittels UV-Spektroskopie, IR-Spektroskopie, Kontaktwinkel-Messungen, Röntgenreflexionsmessungen und Oberflächen Plasmonen-Spektroskopie verfolgt werden. Die Subschichten sind zwischen 25 und 55 Å dick und hängen z.B. von der Polarität des Lösungsmittels ab. Erste cis-trans Isomerisierungen und Photoorientierungs-Versuche wurden durchgeführt.

Ionomere zum Aufbau funktioneller Oberflächen

Im ersten Teil der Arbeit wurden Ionomere durch aufeinanderfolgende polymeranaloge Reaktionen eines Reaktivesterpolymers mit verschiedenen primären bzw. sekundären Aminen synthetisiert. Polarisationsmikroskopische Untersuchungen zeigten, dass diese Ionomere sowohl über thermotrope als auch über lyotrope flüssigkristalline Eigenschaften verfügen. Anschließend wurden mit der 'self-assembly'-Methode Multischichtfilme aus den Ionomeren und hochgeladenen Polyelektrolyten sowie aus entgegengesetzt geladenen Ionomeren aufgebaut. Bei Röntgen-reflexionsmessungen an den Multischichtfilmen konnten winkelabhängige Modulationen der Strahlungsintensität beobachtet werden. Es ist zu vermuten, dass es sich bei diesen Modulationen um Überlagerungen von Kiessig-Ringen und Bragg-Peaks handelt, was ein Indiz dafür ist, dass regel-mäßige Subschichten in den Filmen existieren. Das Konzept der polymeranalogen Reaktionen eines Reaktivesterpolymers mit verschiedenen primären Aminen wurde außerdem dazu benutzt, Polymere zur Modifikation von Cadmiumselenid-Nanokristallen herzustellen. Hierbei konnte zum einen gezeigt werden, dass Nanokristalle direkt mit aminogruppenhaltigen Polymeren modifiziert werden können, zum anderen ist es auch möglich kationische Ionomere auf Nanokristallen mit Mercaptoessigsäure-Liganden zu adsorbieren. Im letzten Teil der Arbeit wurden ionische triazinhaltige Polymere hergestellt und elektrochemisch charakterisiert. Die hergestellten Polymere sind sehr leicht reduzierbar. Anschließend wurden aus den triazinhaltigen Polymeren und entgegengesetzt geladenen Polyelektrolyten ebenfalls Multischichtfilme hergestellt.

Solid-state NMR investigation of phosphonic acid based proton conducting materials

In this work, new promising proton conducting fuel cell membrane materials were characterized in terms of their structure and dynamic properties using solid-state nuclear magnetic resonance (NMR) spectroscopy and X-ray diffraction. Structurally different, phosphonic acid (PA) containing materials were systematically evaluated for possible high-temperature operation (e.g. at T>100°C). Notably, 1H, 2H and 31P magic angle spinning (MAS) NMR provided insight into local connectivities and dynamics of the hydrogen bonded network, while packing arrangements were identified by means of heteronuclear dipolar recoupling techniques.rnThe first part of this work introduced rather crystalline, low molecular weight ionomers for proton conducting membranes, where six different geometries such as line, triangle, screw, tetrahedron, square and hexagon, were investigated. The hexagon was identified as the most promising geometry with high-temperature bulk proton conductivities in the range of 10-3 Scm-1 at a relative humidity of 50%. However, 2H NMR and TGA-MS data suggest that the bulk proton transport is mainly due to the presence of crystal water. Single crystal X-ray data revealed that in the tetrahedron phosphonic acids form tetrameric clusters isolating the mobile protons while the phosphonic acids in the hexagon form zigzag-type pathways through the sample.rnThe second part of this work demonstrates how acid-base pairing and the choice of appropriate spacers may influence proton conduction. Different ratios of statistical copolymers of poly (vinylphosphonic acid) and poly (4-vinylpyridine) were measured to derive information about the local structure and chemical changes. Though anhydrous proton conductivities of all statistical copolymers are rather poor, the conductivity increases to 10-2 S cm-1 when exposing the sample to relative humidity of 80%. In contrast to PVPA, anhydride formation of phosphonic acids in the copolymer is not reversible even when exposing the sample to a relative humidity of 100%.rnIn addition, the influence of both spacers and degree of backbone crystallinity on bulk proton conductivity was investigated. Unlike in systems such as poly benzimidazole (PBI), spacers were inserted between the protogenic groups along the backbone. It was found that dilution of the protogenic groups decreases the conductivity, but compared to PVPA, similar apparent activation energies for local motions were obtained from both variable temperature 1H NMR and impedance spectroscopy data. These observations suggest the formation of phosphonic acid clusters with high degrees of local proton motion, where only a fraction of motions contribute to the observable bulk proton conductivity. Additionally, it was shown that gradual changes of the spacer length lead to different morphologies.rnIn summary, applying advanced solid-state NMR and X-ray analysis, structural and dynamic phenomena in proton conducting materials were identified on a molecular level. The results were discussed with respect to different proton conduction mechanisms and may contribute to a more rational design or improvement of proton conducting membranes.rn

Adhesión de ionómeros vítreos convencionales a dentina tratada con distintas sustancias

El objetivo de este trabajo fue evaluar la fuerza adhesiva de los ionómeros vítreos convencionales a la dentina tratada con ácido fosfórico, con ácido poliacrílico y con solución de hipoclorito de sodio. Los ensayos se realizaron sobre dentina de premolares extraídos por razones ortodóncicas o periodontales, los cuales se asignaron al azar en tres grupos de 10 elementos cada uno. A cada grupo se le practicó un tratamiento distinto (descalcificación, desproteinización o eliminación del barro dentinario). Sobre cada espécimen se le adhirió un cilindro de ionómero vítreo convencional preparado según las especificaciones de su fabricante. Posteriormente las muestras fueron sometidas a fuerzas de cargas de corte utilizando una máquina de ensayos universal (Instron). Los resultados obtenidos fueron sometidos a análisis de ANOVA de una entrada y a post test de comparación múltiple de Tukey. Por lo que puede expresarse que no hubo diferencia estadísticamente significativa (p>0,05) en la fuerza adhesiva de los ionómeros vítreos que fueron adheridos a dentina con tratamiento de ácido poliacrílico, y los que fueron adheridos a dentina con tratamiento de descalcificación (acción del ácido fosfórico). Se encontró diferencia estadísticamente significativa en las muestras adheridas a dentina tratadas con poliacrílico y ácido fosfórico (p<0.01 y p<0.05 respectivamente), con respecto a las que fueron tratadas con hipoclorito.