<p> Over the past decade, the development of surface-initiated living polymerization methods has brought a breakthrough to surface modification owing to their control ability. Surface-initiated atom transfer radical polymerization (si-ATRP), as the most popular one, has been widely employed to give novel polymer structures and functionalities to various surfaces for the purposes of tailoring surface properties, introducing new functions, or preparing so-called "smart surfaces", which can respond to external stimuli such as solvent type, pH, temperature, electric and magnetic fields etc. In this thesis, the mechanistic study of the si-ATRP was first carried out through modeling to gain good understanding of si-ATRP. Si-ATRP was then employed to prepare different types of polymer brushes to produce "smart surfaces". </p> <p> The kinetic model was developed using the method of moment. Combined with experimental data, a quantitative analysis was carried out for the si-ATRP mechanism. All information of grafted polymer chains, including active chain concentration, radical concentration, chain length, polydispersity, was illustrated. A new radical termination mechanism, termed as migration-termination, was proposed for si-ATRP. </p> <p> Si-ATRP was then employed to graft poly(oligo(ethylene glycol) methacrylate) (POEGMA) block poly(methyl methacrylate) (PMMA) brushes on silicon wafer surfaces. Simple solvent treatment gave nanoscale patterns via the phase segregation of POEGMA and PMMA segments. Various patterns including spherical aggregates, wormlike aggregates, stripe patterns, perforated layers and complete overlayers, were obtained by adjusting the upper block layer thickness. Furthermore, these nanopatterns had a unique stimuli-responsive property, i.e., switching between different morphologies reversibly after being treated with selective solvents. </p> <p> POEGMA-block-poly(2-(methacryloyloxy)ethyl trimethylammonium chloride) (PMETAC) brushes, having two hydrophilic segments, were synthesized by si-ATRP method. A variety of nanopatterns and their stimuli-responsive ability were observed. The adsorption behaviors of fibrinogen on these patterns were thoroughly studied by ellipsometry, water contact angel measurement, AFM and radio labelling method. </p> <p> A novel thermo-responsive copolymer, poly(2-(2-methoxyethoxy)ethyl methacrylate -co-oligo(ethylene glycol) methacrylate) (P(ME02MA-co-OEGMA)), was also grafted onto silicon wafers. Its thermo-responsive behavior and chain conformation in aqueous solution were studied by neutron reflectometry (NR). Both extended and collapsed brushes exhibited good protein adsorption resistance. </p> / Thesis / Doctor of Philosophy (PhD)

No description available.

<p>This dissertation describes an investigation into the free radical batch polymerization of methyl methacrylate to high conversion. The overall objective was to develop a kinetic model to accurately predict conversion and molecular weight distribution for the polymerization. The dissertation is divided into three self-contained parts.</p> <p>Part I describes the development and testing of the kinetic model. New gel permeation chromatograph (GPC) data interpretation methods (developed in Part I I), the free volume concept of diffusion theory, and newly obtained isothermal kinetic data, are combined with computer implemented optimization techniques, to show that classical kinetics apply to high conversions.</p> <p>Part II details the development of three new GPC interpretation techniques. The two most recent are evaluated in Part I.</p> <p>The third has been used by other workers. Other interpretation methods are also evaluated and discussed. Part I I I describes the development of a high shear concentric cylinder viscometer and its use with Newtonian standards. This is a prelude to future studies in polymer rheology and polymerization under shear conditions.</p> / Doctor of Philosophy (PhD)

Sub-micron patterning is fundamental to the fabrication of numerous devices Traditional commercial manufacturing methods either lack the resolution needed to attain the appropriate size or are prohibitively expensive due to low throughput or the necessity of expensive equipment. Imprint lithography is a rapid, inexpensive alternative to making sub-micron features that can be tailored to work with a variety of materials. Imprint lithography, while traditionally used with pure polymers has been tailored to be used with nanoparticle-polymer hybrid films. This work has achieved high-fidelity pattern transfer onto polymer-nanoparticle hybrid films with feature sizes as small as 250 nm. The polymer-nanoparticle hybrid was fabricated by creating a liquid suspension of functionalized ZnO nanoparticles and poly(methyl methacrylate) (PMMA) in a solvent. The ZnO particles were functionalized by adding nonanoic acid in order to facilitate the dispersion of the particles in a non-polar solvent. This suspension was spread onto substrate, imprinted with a patterned stamp, allowed to dry, and was demolded. The final result was features ranging from 250 nm to 1 μm in size with good fidelity as determined by the accuracy of the feature replication and the surface roughness of the overall sample. The effect of the ZnO content as well as the method of combining the suspension components on the feature fidelity was studied. In general, it was found that feature fidelity is acceptable up to a dry-film composition of 15 vol% ZnO and that feature sizes above 500 nm were more tolerant of higher solids loading. The same imprint lithography method was also used to pattern a polymer-derived SiOC glass. The SiOC was shown to be have interesting shrinkage properties where the feature-level linear shrinkage was up to 5% more than that of the bulk. The features were shown to be stable during pyrolysis up to 1000°C and stable at operating temperatures up to 1000°C. A constant number Monte Carlo simulation was used to describe the suspension behavior to confirm the empirical results from the physical experiments. The effects of Van der Waals forces, steric stabilization, depletion flocculation, as well as the physical impediment of entangled polymer chains were considered. A similar agglomeration behavior was shown in the simulations compared to the physical experiments. This thesis shows that polymer-nanoparticle hybrid films are a compatible material for imprint lithography using appropriate suspension parameters. This is very important for a variety of applications and devices. Using imprint lithography to make these devices makes them cheaper and more accessible to the commercial market and can make a large number of theoretical devices a reality. / Ph. D. / Sub-micron patterning is an integral part of making many modern technologies such as memory storage devices or integrated circuits. As this technology becomes smaller and smaller, the limiting factor for making these devices has become the ability to manufacture effectively at the appropriate scale. Traditional commercial manufacturing methods lack the resolution needed to attain small enough features. Manufacturing methods that can make small enough features are often either extremely expensive or offer incomplete control of the feature morphology. Imprint lithography is a high-throughput, inexpensive alternative to making sub-micron features that can be tailored to work with a variety of materials. Imprint lithography is simple process in which a patterned stamp is pressed into a softened film of material in order to transfer the pattern of the stamp onto that material. Traditionally, imprint lithography works best with polymers and researchers have struggled to pattern nanoparticle-based materials. This work has achieved high-fidelity pattern transfer onto polymer-nanoparticle hybrid films with feature sizes on the same order as the polymer films found reported in literature. The polymer-nanoparticle hybrid was realized by creating a liquid suspension of functionalized ZnO nanoparticles and poly(methyl methacrylate) (PMMA) in a solvent. The ZnO particles were functionalized by adding nonanoic acid, allowing the normally polar particles to disperse in the non-polar solvent needed to dissolve the PMMA. This suspension was spread onto a glass substrate, imprinted with a patterned stamp, allowed to dry, and was demolded. The final result was the successful transfer of features ranging from 250 nm to 1 μm in size with good fidelity. The effect of the ZnO content as well as the method of combining the suspension components on the feature fidelity was studied. To help prove the broad applicability of this imprint method, it was adapted for use with polymer-derived ceramics. Additionally, a computer simulation was developed to help understand the behavior of the nanoparticle-polymer suspension during the imprint process.

The two stage Lucite Alpha Process for the industrial manufacturing of methyl methacrylate (MMA) represents one of the most efficient technologies currently available for the large scale production of this important chemical commodity. The second stage of this process, which involves the condensation of methyl propanoate (MeP) with formaldehyde over a heterogeneous fixed bed catalyst, however, still shows great scope for improvement. Herein the development of a novel homogeneous catalytic system that would promote the condensation of either propanoic acid or MeP with formaldehyde is explored. Since C–C bond forming reactions which proceed via C–H activation pathways typically display high atom efficiency, our efforts were particularly focussed on employing a functionalisation strategy that is mediated by C–H activation. In the case of propanoic acid, the possibility of achieving regioselective α-methylenation by linking the substrate to phosphorus was evaluated. Thus, a series of acyloxyphosphines and acylphosphites derived from either propionic acid or phenylacetic acid was prepared and, where stability allowed, fully characterised. Some of the resultant simple mixed anhydrides posed problems relating to their stability, and the stabilisation of such ligand systems by using electronic and / or steric effects was therefore explored. In addition, the coordination chemistry and in solution behaviour of Rh(I) and Ru(II) complexes containing these ligands was examined. Similar to the free ligands, complexes derived from these mixed anhydrides rearranged in solution via a number of decomposition pathways, with the specific pathway dependent on the nature of the auxiliary ligands. For most of these complexes, however, ligand decarbonylation was the route of preference for decomposition. Despite the instability of these complexes, a selection of Rh(I) mixed anhydride complexes were assessed for their potential as C-H activation catalysts in reactions aimed at the α-methylenation of saturated carboxylic acids. Furthermore, the stabilisation of Rh(I) mixed anhydride complexes with chelating auxilary ligands, such as bisphosphines or N-substituted diphosphinoamines, was explored. In particular, a series of new Rh(I) mixed anhydride complexes containing dppe, dppb and dppbz as secondary ligands were prepared and the effects of these secondary ligands on the in solution stability of these complexes assessed. As MeP represents the final product in the first stage of the Alpha process and not propanoic acid, the utilisation of PNP iridium pincer complexes in the regioselective sp³ C–H activation of MeP and related esters was also examined. The factors that govern the regioselectivity of such reactions were of great interest to us and, in particular, the effects of water on the reactivity and regioselectivity of these reactions were explored. For MeP, preferential C–H activation of the methoxy group was found to proceed under anhydrous conditions and the catalytic functionalisation of this site with ethene using this activation approach was considered. Formaldehyde, employed in the second stage of the Alpha process, is a difficult substance to manufacture and handle, especially on a large scale. A preliminary study on the in situ production of anhydrous formaldehyde via the catalytic dehydrogenation of methanol was therefore performed. During this study, catalytic systems based on carbonate salts and / or transition metal complexes were considered. In the hope of reducing the number of steps required in the production of MMA, a new one-pot cascade reaction for the indirect α-methylenation of MeP with methanol was developed. Although the production of MMA using this system only proceeded with low efficiency, the obtained results serve as an important proof of concept for future developments in this area. Finally, the capacity of a series of simple bases to catalyse the condensation of MeP with formaldehyde was assessed as part of a fundamental study directed towards determining the factors that govern the efficiency of this reaction. In addition, the extent to which each base effects the deprotonation in the α-position of MeP was determined with the aid of deuterium labelling experiments. Similarly, using sodium propanoate as model base a rough estimate of the kinetics of deprotonation could be made based on the degree of deuterium incorporation over time. These studies suggested that the low efficiency of this condensation reaction is not caused by ineffective deprotonation but rather by the weak nucleophilicity of the generated carbanion. For this reason, attempts to increase the electrophilicity of formaldehyde through Mannich-type condensations reactions involving secondary amine and carboxylic acid additives were made.

Indiana University-Purdue University Indianapolis (IUPUI) / Provisional restorative treatment is an essential part of fixed prosthodontics. Incorporation of adequately constructed provisional restorations will enhance the success rate of definitive restorations. Repairing or replacing failed provisional restorations is a concern for both clinicians and patients. The objective of this investigation was to study the effects of alumina nanofibers reinforcement on the mechanical properties of commercially available provisional fixed partial denture PMMA material. The hypothesis was that the addition of alumina nanofibers to commercially available PMMA resin will significantly increase its flexural strength, fracture toughness, and microhardness. Alumina nanofibers at 0.0 wt %, 0.5 wt %, 1.0 wt %, and 2.5 wt % were added to commercially available provisional fixed partial material (Jet Tooth Shade). A quaternary ammonium acetate dispersant (CC-59, Goldschmidt, Janesville, WI) was added to the acrylic monomer at 0.0 wt %, 1.0 wt %, 2.0 wt % and 5.0 wt % of the nanofiber weight (12 test groups, 1 control). Samples from each group were evaluated for flexural strength, flexural modulus, fracture toughness, and microhardness. The samples were tested after storing in distilled water for 24 hours and 7 days at 37ºC. Two-way analysis of variance (ANOVA) was used to test the effects of storage time and combinations of alumina nanofiber level and quaternary ammonium acetate dispersant level on the flexural strength, fracture toughness, and microhardness of the provisional PMMA resin. Pair-wise comparisons between groups were performed using Tukey’s multiple comparisons procedure to control the overall significance level at 5 percent. Three fracture toughness samples/group were randomly selected for Energy Dispersive Spectrometry (EDS) to qualitatively evaluate the dispersion of the fibers. The data obtained from this study showed that control sample values were in the acceptance range compared with previous research. The experimental samples did not reinforce the provisional resin in the flexural strength, modulus, fracture toughness, or microhardness. There are several factors may attribute to these results, such as poor bonding at the filler/matrix interface. The more homogeneous the mixture of PMMA and fiber, the stronger the acrylic resin. In fact, the presence of poorly bonded fibers, to which little load is transferred, can be almost equivalent to voids. In addition, as seen with EDS images, alumina nanofibers had a tendency to agglomerate. The use of a magnetic stirrer was not effective in physically separating nanofibers agglomerates. Direct dispersion of alumina nanofibers in methyl methacrylate monomer and quaternary ammonium acetate dispersant was not effective in separating the nanofibers into nano-scaled single crystals. The presence of fiber agglomerates acts as a structural defect that detrimentally affects the mechanical properties. Further studies are needed to evaluate the effectiveness of fibers, dispersion techniques, and coupling agents to enhance the mechanical properties of the provisional PMMA resin.

Cette étude porte sur l’application de la réaction de Diels-Alder dans la synthèse de réseaux polymères thermoréversibles ainsi que la compatibilisation de mélanges de polymères initialement immiscibles. Les polymères étudiés ne sont autres que le polyméthacrylate de méthyle et le polyuréthane. Les réseaux thermoréversibles sont obtenus par réaction de Diels-Alder faisant intervenir le couple furanne-maléimide. Les polymères fonctionnalisés furanne ou maléimide sont obtenus soit par modification chimique d’un polymère commercial (cas du PMMA) soit par réaction de polyaddition (cas du polyuréthane). Les réseaux sont ensuite obtenus par réaction de DA avec des agents de couplage maléimide (bis- ou tris-maléimide) pour les polymères fonctionnalisés furanne ou par réaction de DA avec des agents de couplage furanne pour les prépolymères fonctionnalisés maléimide. La thermo-réversibilité a été soulignée par DSC, par des tests de solubilité à chaud ainsi que par rhéologie. Des réseaux interpénétrés thermoréversibles PMMA/PU ont été également obtenu par Diels-Alder et ce grâce à la présence d’interaction supramoléculaire entre les deux phases. / This study focuses on the application of the Diels-Alder reaction in the synthesis of thermoreversible polymer networks and compatibilization of immiscible polymer blends. The studied polymers are polymethyl methacrylate and polyurethane. Thermoreversible networks were obtained by a Diels-Alder involving furan-maleimide couple. The furan or maleimide functionalized polymers were obtained either by chemical modification of a commercial polymer (case of PMMA) or by polyaddition reaction (case of polyurethane). Networks were then obtained by DA reaction with maleimide coupling agents (bis-or tris-maleimide) for furan functionalized polymers or DA reaction with furan coupling agents for maleimide functionalized prepolymers. The thermoreversibility was highlighted by DSC, solubility tests (at high temperature) as well as rheology. Thermoreversible interpenetrating PMMA/PU networks were also obtained by Diels-Alder reaction and this is due to the presence of supramolecular interaction between the two phases

O objetivo deste trabalho foi avaliar a influência de diferentes aminas terciárias no grau de conversão, na contração de polimerização, na taxa de contração, na microdureza Knoop, na estabilidade de cor e na transmitância de luz de resinas experimentais, contendo, em peso, BisGMA e TEGDMA (3:1), 0,25% de canforquinona (CQ) e 1% de amina (DMAEMA, CEMA, DMPT, DEPT ou DABE). A influência de diferentes protocolos de fotoativação também foi investigada. O grau de conversão foi avaliado através de FTIR-ATR e a contração pelo método do disco aderido. A partir da diferenciação numérica dos dados de contração em relação ao tempo, obteve-se a taxa de contração de polimerização. A estabilidade de cor e a transmitância foram avaliadas em diferentes períodos de envelhecimento artificial. Os resultados foram avaliados pelos testes de ANOVA, Tukey e T3 de Dunnett (&#945; = 0,05). As propriedades estudadas variaram em função da amina. O grau de conversão e a contração de polimerização variaram na sequência: CQ < DEPT < DMPT &#8804; CEMA &#8776; DABE < DMAEMA. O grau de conversão e a contração também foram influenciados pelo protocolo de fotoativação, sendo observadas correlações positivas entre o grau de conversão e a contração e entre o grau de conversão e a taxa de contração. A cor variou na sequência: DMAEMA < DEPT < DMPT < CEMA < DABE. A transmitância variou na sequência: DEPT &#8776; DABE < DABE &#8776; DMPT &#8776; CEMA < DMPT &#8776; CEMA &#8776; DMAEMA, sendo mais evidente para o comprimento de onda de 400nm. Não foram observadas correlações entre o grau de conversão e as propriedades ópticas. A resina contendo DMAEMA apresentou maior grau de conversão, contração, taxa de contração e dureza, além de melhor estabilidade nas propriedades ópticas. / The aim of this work was to evaluate de influence of different tertiary amines on degree of conversion (DC), shrinkage-strain, shrinkage-strain-rate, Knoop microhardness, and colour and transmittance stabilities of experimental resins containing BisGMA / TEGDMA (3:1 wt), 0,25wt% camphorquinone, 1wt% amine (DMAEMA, CEMA, DMPT, or DABE). Different light-curing protocols were also evaluated. DC was evaluated with FTIR-ATR and shrinkage-strain with the bonded-disc method. Shrinkage-strain-rate data were obtained from numerical differentiation of shrinkage-strain data with respect to time. Colour stability and transmittance were evaluated during different periods of artificial aging, according to ISO 7491:2000. Results were evaluated with ANOVA, Tukey and Dunnetts T3 tests (&#945; = 0.05). The studied properties varied according to amines. DC and shrinkage-strain were maximum at the sequence: CQ < DEPT < DMPT &#8804; CEMA &#8776; DABE < DMAEMA. Both DC and shrinkage were also influenced by the curing protocol, with positive correlations between DC and shrinkage-strain and DC and shrinkage-strain-rate. Colour varied in the sequence: DMAEMA < DEPT < DMPT < CEMA < DABE. Transmittance varied in the sequence: DEPT &#8776; DABE < DABE &#8776; DMPT &#8776; CEMA < DMPT &#8776; CEMA &#8776; DMAEMA, being more evident at the wavelength of 400nm. No correlations between DC and optical properties were observed. The resin containing DMAEMA showed higher DC, shrinkage-strain, shrinkage-strain-rate and microhardness, in addition with better optical properties.

A exploração não racional dos recursos florestais nativos, no Brasil, tem provocado a redução da oferta de espécies de uso consagrado em diversos segmentos, notadamente na construção civil e na indústria de móveis. A alternativa mais imediata tem sido o emprego da madeira de reflorestamento, em particular, dos gêneros Eucalyptus e Pinus, freqüentes nas regiões sul e sudeste do país. Porém, muitas das espécies disponíveis comercialmente não apresentam propriedades fisico-mecânicas que as tornem capazes de promover a substituição das espécies tradicionalmente empregadas. Neste contexto, o presente trabalho tem como objetivo demonstrar a viabilidade de se obterem compósitos polímero-madeira (CPMs) que podem apresentar comportamento equivalente ou superior ao da madeira sem tratamento, proveniente das regiões de reflorestamento dos mencionados gêneros. Para tal, foi feita a impregnação da madeira das espécies Eucalyptus grandis e Pinus caribaea var. hondurensis por apresentarem maior disponibilidade e densidade compatível para viabilizar o processo. Empregaram-se os monômeros poliméricos de estireno e metacrilato de metila e, como iniciador no processo de polimerização, o peróxido de benzoíla. Foi utilizado o método de vácuo-pressão para a impregnação da solução monômero-iniciador. Os resultados mostraram, para os CPMs de Pinus, um significativo aumento nos valores de todas as propriedades estudadas. Nos CPMs de Eucalyptus, em decorrência de sua baixa permeabilidade, somente os valores das durezas paralela e normal às fibras apresentaram aumento. / Large exploration of native forestry resources in Brazil has led to a decrease in supply of the most widely used species in several sectors, notably in civil construction and furniture industries. The most immediate remedy has been the use of reforestation timber, obtained from the common Eucalyptus and Pinus species available in the south and southwest regions of the country. However, most of these species do not present adequate physical and mechanical properties to viably the mentioned uses. In this context, the main objective of the present research is to demonstrate the viability of obtaining wood-polymer composites (WPCs), which may exhibit similar or superior physical and mechanical properties than untreated aforementioned species from reforestation regions of Brazil. In order to achieve this goal, the impregnation of Eucalyptus grandis and Pinus caribaea var. hondurensis, which have compatible density and are available in large amounts to permit such processing, was carried out. In the process, polymeric monomers of styrene and methyl methacrylate were employed with benzyl peroxide, whose functions as an initiator in the polymerization process. Vacuum-pressure method was used in the impregnation of the monomer-initiator solution. Properties of the WPCs – Pinus were significantly improved in all tests, however, because of its low permeability, only hardness parallel and perpendicular to grain showed increase for the WPCs – Eucaliptus.

O objetivo deste estudo foi avaliar, in vitro, o comportamento citotóxico e a produção de citocinas induzidos pelos materiais restauradores resinosos contendo novos monômeros KaloreTM (GC FUJI) e FiltekTMSilorane (3M ESPE) em comparação com as resinas compostas convencionais Charisma® (Heraeus-Kulzer) e FiltekTM Z250 (3M ESPE), em cultura de fibroblastos L929 e macrófagos RAW 264.7 de camundongos. As células foram estimuladas com as resinas compostas, fotopolimerizadas ou não, a partir da colocação em contato indireto ou pela extração de seus componentes durante 15, 45 e 120 dias. Após a incubação por 6, 12 e 24 horas, a viabilidade celular foi avaliada pelo Ensaio MTT e a produção de citocinas foi investigada pelo ensaio imunoenzimático (ELISA). Os dados obtidos foram analisados utilizando-se análise de variância de uma via (One-way ANOVA) e pós-teste de Tukey (&alpha;=0,05). A produção de TNF-&alpha; e IL-6 não foi detectada em fibroblastos da linhagem L929, após 6, 12 e 24 horas de contato indireto com as resinas compostas KaloreTM e FiltekTM Silorane. Por outro lado, a produção de TNF-&alpha; foi detectada em macrófagos da linhagem RAW 264.7, mas não foi influenciada pelo contato indireto com as resinas compostas, com exceção da resina FiltekTM Silorane que inibiu a produção de TNF-&alpha;, após 12 horas de incubação. Os extratos obtidos das resinas compostas KaloreTM e FiltekTM Silorane incubadas por 15 dias, se mostraram mais citotóxicos do que os extratos incubados por 45 e 120 dias. A citotoxicidade da resina composta KaloreTMnão foi influenciada pela fotopolimerização enquanto a citotoxicidade da resina FiltekTM Silorane foi maior no grupo não fotopolimerizado. Os extratos das resinas compostas Charisma® e FiltekTM Z250, obtidos aos 15, 45 e 120 dias de incubação, não foram citotóxicos 24 horas após a estimulação das células. Ainda, a resina FiltekTM Silorane, fotopolimerizada ou não, estimulou a produção de IL-6 no período de 45 dias de extração. A resina KaloreTM, diferentemente da resina FiltekTM Silorane, estimulou a produção de IL-10, aos 15 dias de extração. Entretanto, no período de 45 de extração, a resina KaloreTM fotopolimerizada inibiu a produção de IL-10, após 12 horas de incubação, e aos 120 dias de extração não houve produção detectável de IL-10 em nenhum dos grupos avaliados. / The aim of this study was to evaluate in vitro the cytotoxicity and the production of cytokines induced by resin-based restorative materials containing new monomers KaloreTM (GC FUJI) and FiltekTM Silorane (3M ESPE) compared with conventional composite resins Charisma® (Heraeus-Kulzer) and FiltekTM Z250 (3M ESPE), in mice L929 fibroblast and RAW 264.7 macrophages culture. Cells were stimulated with the composite resins, light-cured or not, by indirect contact or extraction during 15, 45, and 120 days. After incubation for 6, 12, and 24 hours, cell viability was assessed by MTT assay and production of cytokines was investigated by enzyme-linked immunosorbent assay (ELISA). Data obtained were analyzed using oneway analysis of variance (ANOVA) and Tukey post-test ( &alpha; = 0.05). Production of TNF-&alpha; and IL-6 was not detected in L929 fibroblasts either 6, 12 or 24 hours following indirect contact with the KaloreTM and FiltekTM Silorane composite resins. On the other hand, the production of TNF-&alpha; was detected in RAW 264.7 macrophages, but was not influenced by indirect contact with composite resins, with the exception of the FiltekTM Silorane resin that inhibited the production of TNF-&alpha;, after 12 hours of incubation. The extracts obtained from incubation for 15 days with composite resins KaloreTM and FiltekTM Silorane were more cytotoxic than extracts incubated for 45 and 120 days. Cytotoxicity of composite KaloreTM was not influenced by light curing while cytotoxicity of FiltekTM Silorane resin was higher in the group that not received light-cure. Extracts of Charisma® and FiltekTM Z250 composite resins, obtained at 15, 45, and 120 days of incubation, were not cytotoxic 24 hours after stimulation of the cells. Also, FiltekTM Silorane, light-cured or not, stimulated the production of IL-6 following 45 days of incubation. KaloreTM resin extract for 15 days, unlike FiltekTM Silorane resin, stimulated the production of IL-10. However, during periods of 45 days of extraction, KaloreTM resin, light-cured, inhibited the production of IL-10, after 12 hours of incubation, and 120 days of extraction there was no detectable production of IL-10 in any of the groups.