Tuning the activity of alternative Ru-based initiators for ring-opening metathesis polymerization of norbornene and norbornadiene by the substituent in 4-CH2R-piperidine

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

Direct laser writing by two-photon polymerization as a tool for developing microenvironments for evaluation of bacterial growth

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

Indirect doping of microstructures fabricated by two-photon polymerization with gold nanoparticles

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Cuspal movement related to different polymerization protocols

Objective: The aim of this study to investigate the effects of different polymerization protocols on the cuspal movement in class II composite restorations. Materials and methods: Human premolar teeth were prepared with class II cavities and then restored with composite and three-step and two-step etch-and-rinse adhesive systems under different curing techniques (n = 10). It was used a lightemittingdiode curing unit and the mode of polymerization were: standard (exposure for 40 seconds at 700 mW/cm2), pulse-delay (initial exposure for 6 seconds at 350 mW/cm2 followed by a resting period of 3 minutes and a final exposure of 37 seconds at 700 mW/cm2) and soft-start curing (exposure 10 seconds at 350 mW/cm2 and 35 seconds at 700 mW/cm2). The cuspal distance (µm) was measured before and after the restorative procedure and the difference was recorded as cuspal movement. The data were submitted to two-way ANOVA and Bonferroni test (p < 0.05). Results: The type of adhesive system did not influenced the cuspal movement for all the curing methods. Standard protocol showed the highest values of cuspal movement and was statistically different from the pulse-delay and soft-start curing modes. Conclusion: Although the cuspal displacement was not completely avoided, alternative methods of photocuring should be considered to minimize the clinical consequences of composites contraction stress.

Effect of post-polymerization heat treatment on a denture base acrylic resin: histopathological analysis in rats

This work examined the histological effects, on the rat palatal mucosa, of a denture base acrylic resin, submitted or not to a post-polymerization heat-treatment. Methods: Fifteen adult female Wistar rats, with sixty days old, weighting 150 g – 250 g were divided in G1: animals being maintained under the same conditions as the experimental groups following described, but without the use acrylic palatal plates (control group); G2: use of heat-polymerized acrylic resin palatal plates made of Lucitone 550; G3: use of palatal plates identical to G2, but subjected to a post-polymerization treatment in a water bath at 55°C for 60 min. The plates covered all the palate and were fixed in the molar region with light-cured resin, thus being kept there for 14 days. After the sacrifice, the palate was removed, fixed in formaldehyde 10% and decalcified with EDTA. Sections were stained using haematoxylin and eosin. Images in duplicate were made from the central region of the cuts, to measure the thickness (μm) of the keratin layers (TKC), epithelium total (TET) and connective tissue (TCC). Statistical analyses were carried out by one-way ANOVA and Tukey post-tests (α=0.05). Results: According to the results there was significant difference in the thickness of keratin between G2 and G3, with G1 having the intermediate value and similar to the other groups. There was a significant difference in the connective tissue with G3

The effect of polymerization mode on monomer conversion, free radical entrapment, and interaction with hydroxyapatite of commercial self-adhesive cements

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Maximizing the utility of bio-based diisocyanate and chain extenders in crystalline segmented thermoplastic polyester urethanes: effect of polymerization protocol

High molecular weight semi crystalline thermoplastic poly(ester urethanes), TPEUs, were prepared from a vegetable oil-based diisocyanate, aliphatic diol chain extenders and poly(ethylene adipate) macro diol using one-shot, pre-polymer and multi-stage polyaddition methods. The optimized polymerization reaction achieved ultra-high molecular weight TPEUs (>2 million as determined by GPC) in a short time, indicating a very high HPMDI diol reactivity. TPEUs with very well controlled hard segment (HS) and soft segment (SS) blocks were prepared and characterized with DSC, TGA, tensile analysis, and WAXD in order to reveal structure property relationships. A confinement effect that imparts elastomeric properties to otherwise thermoplastic TPEUs was revealed. The confinement extent was found to vary predictably with structure indicating that one can custom engineer tougher polyurethane elastomers by "tuning" soft segment crystallinity with suitable HS block structure. Generally, the HPMDI-based TPEUs exhibited thermal stability and mechanical properties comparable to entirely petroleum-based TPEUs. (C) 2014 Elsevier Ltd. All rights reserved.

Effect of polymerization methods and thermal cycling on color stability of acrylic resin denture teeth

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

Inhibition of diethylnitrosamine-initiated alcohol-promoted hepatic inflammation and precancerous lesions by flavonoid luteolin is associated with increased sirtuin 1 activity in mice

Chronic and excessive alcohol consumption is an established risk for hepatic inflammation and carcinogenesis. Luteolin is one of the most common flavonoids present in plants and has potential beneficial effects against cancer. In this study, we examined the effect and potential mechanisms of luteolin supplementation in a carcinogen initiated alcohol-promoted pre-neoplastic liver lesion mouse model. C57BL/6 mice were injected with diethylnitrosamine (DEN) [i.p. 25 mg/kg of body weight (BW)] at 14 days of age. At 8 weeks of age mice were group pair-fed with Lieber-DeCarli liquid control diet or alcoholic diet [ethanol (EtOH) diet, 27% total energy from ethanol] and supplemented with a dose of 30 mg luteolin/kg BW per day for 21 days. DEN-injected mice fed EtOH diet displayed a significant induction of pre-neoplastic lesions, a marker associated with presence of steatosis and inflammation. Dietary luteolin significantly reduced the severity and incidence of hepatic inflammatory foci and steatosis in DEN-injected mice fed EtOH diet, as well the presence of preneoplastic lesions. There was no difference on hepatic protein levels of sirtuin 1 (SIRT1) among all groups; however, luteolin supplementation significantly reversed alcohol-reduced SIRT1 activity assessed by the ratio of acetylated and total forkhead box protein O1 (FoXO1) and SIRT1 target proliferator-activated receptor gamma, coactivator 1 alpha (PGC1α). Dietary intake of luteolin prevents alcohol promoted pre-neoplastic lesions, potentially mediated by SIRT1 signaling pathway.

Color stability of the artificial iris button in an ocular prosthesis before and after acrylic resin polymerization

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

Polymerization kinetics and polymerization stress in resin composites after accelerated aging as a function of the expiration date

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Effect of polymerization techniques and cleaning solution on flexural resistance of acrylic resin chemically activated

The purpose of this study was to evaluate the impact of different disinfection solutions on flexural resistance of chemically-activated acrylic resin. Test pieces were made of clear acrylic resin using a rectangular mold and employing two techniques: wet polymerization under pressure (n = 20) and dry polymerization under pressure (n = 20). Test pieces were subdivided into four equal groups: distilled water (control), sodium bicarbonate, 1% sodium hypochlorite and effervescent ats. The 30-day cycling technique consisted of immersing the test pieces in 100 ml of solution for 10 min three times a day and placing them in closed containers containing artificial saliva at 37°C. Subsequently, the flexural resistance of samples was tested. Data were analyzed using two-way analysis of variance (ANOVA) with forces serving as the dependent variables and the polymerization technique and cleaning agents as independent variables. Post hoc multiple comparisons were performed using Tukey’s test. There was no statistically significant difference in the flexural strength between the two polymerization techniques. The greatest flexural strength was observed for the effervescent tablets group followed by the control and 1% sodium hypochlorite groups which were statistically similar. Thus, the sodium bicarbonate solution caused the lowest flexural resistance of the test pieces.

New Studies Initiated by the U.S. Geological Survey— Effects of Nutrient Enrichment on Stream Ecosystems

In 2001, the U.S. Geological Survey’s National Water-Quality Assessment (NAWQA) Program began an intensive study of nutrient enrichment—elevated concentrations of nitrogen and phosphorus— in streams in five agricultural basins across the Nation (see map, p. 2). This study is providing nationally consistent and comparable data and analyses of nutrient conditions, including how these conditions vary as a result of natural and human-related factors, and how nutrient conditions affect algae and other biological communities. This information will benefit stakeholders, including the U.S. Environmental Protection Agency (USEPA) and its partners, who are developing nutrient criteria to protect the aquatic health of streams in different geographic regions.

Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry Characterization of Primary Amine End-Functionalized Polystyrene and Poly(methyl methacrylate) Synthesized by Living Anionic Polymerization Techniques

The reaction of living anionic polymers with 2,2,5,5-tetramethyl-1-(3-bromopropyl)-1-aza-2,5- disilacyclopentane (1) was investigated using coupled thin layer chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Structures of byproducts as well as the major product were determined. The anionic initiator having a protected primary amine functional group, 2,2,5,5-tetramethyl- 1-(3-lithiopropyl)-1-aza-2,5-disilacyclopentane (2), was synthesized using all-glass high-vacuum techniques, which allows the long-term stability of this initiator to be maintained. The use of 2 in the preparation of well-defined aliphatic primary amine R-end-functionalized polystyrene and poly(methyl methacrylate) was investigated. Primary amino R-end-functionalized poly(methyl methacrylate) can be obtained near-quantitatively by reacting 2 with 1,1-diphenylethylene in tetrahydrofuran at room temperature prior to polymerizing methyl methacrylate at -78 °C. When 2 is used to initiate styrene at room temperature in benzene, an additive such as N,N,N',N'- tetramethylethylenediamine is necessary to activate the polymerization. However, although the resulting polymers have narrow molecular weight distributions and well-controlled molecular weights, our mass spectra data suggest that the yield of primary amine α-end-functionalized polystyrene from these syntheses is very low. The majority of the products are methyl α-end-functionalized polystyrene.

Well-Defined Poly(4-vinylbenzocyclobutene): Synthesis by Living Anionic Polymerization and Characterization

Living anionic polymerization of 4-vinylbenzocylobutene was performed in benzene at room temperature using sec-butyllithium as the initiator. Results of the kinetic studies indicated the termination- and transfer-free nature of the polymerization. Homopolymers with predictable molecular weights and narrow molecular weight distributions were produced, excluding the interference of the cyclobutene rings during initiation and propagation. Thermogravimetric analysis of poly(4-vinylbenzocyclobutene) in air showed a small weight gain at ~200 °C, a rapid decomposition at ~455 °C, and a gradual decomposition at ~566 °C. This behavior was attributed to the formation of radicals from the pendent benzocyclobutene functionality through o-quinodimethane intermediates and simultaneous decomposition/cross-linking reactions at high temperature. The living nature of the polymerization was also examined via sequential copolymerization with butadiene to form diblock copolymers.