Síntese e atividade citotóxica de alguns azido-ciclopaladados estabilizados com ligantes bifosfínicos

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

Self-assembly of cyclometallated Pd(II) compounds directed by C-H center dot center dot center dot pi interactions: A structural evidence for metalloaromaticity in a cyclopalladated ring

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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.

New layered double hydroxides intercalated with substituted pyrroles. 1. In situ polymerization of 4-(1H-pyrrol-1-yl)benzoate

The two-dimensional hybrid organic-inorganic materials Zn-2-Cr and Zn-2-Al-LDHs (Layered Double Hydroxides) containing 4-(1H-pyrrol-1yl)benzoate anions as the interlayer anions were synthesized by the co-precipitation method at constant pH followed by subsequent hydrothermal treatment for 72 h. The materials were characterized by PXRD, C-13 CP-MAS NMR, ESR, TGA, and TEM. The basal spacing found by the X-ray diffraction technique is coincident with the formation of bilayers of the intercalated anions. Solid-state C-13 NMR and ESR data strongly suggest the partial in situ polymerization of the 4-(1H-pyrrol-1yl)benzoate anions during coprecipitation. (c) 2006 Elsevier Ltd. All rights reserved.

The effect of polymerization cycles on porosity of microwave-processed denture base resin

Statement of problem. Although most of the physical properties of denture base resin polymerized by microwave energy have been shown to be similar to resins polymerized by the conventional heat polymerization method, the presence of porosity is a problem.Purpose. This study evaluated the effect of different microwave polymerization cycles on the porosity of a denture base resin designed for microwave polymerization.Material and methods. Thirty-two rectangular resin specimens (65 X 40 X 5 mm) were divided into 3 experimental groups (A, B, and C; Onda-Cryl, microwave-polymerized resin) and I control group (T; Classico, heat-polymerized resin), according to the following polymerization cycles: (A) 500 W for 3 minutes, (B) 90 W for 13 minutes + 500 W for 90 seconds, (C) 320 W for 3 minutes + 0 W for 4 minutes + 720 W for 3 minutes, and (T) 74degreesC for 9 hours. Porosity was calculated by measurement of the specimen volume before and after its immersion in water. Data were analyzed using 1-way analysis of variance (alpha = .05).Results. The mean values and SDs of the percent mean porosity were: A = 1.05% +/- 0.28%, B = 0.91% +/- 0.15%, C = 0.88% +/- 0.23%, T = 0.93% +/- 0.23%. No significant differences were found in mean porosity among the groups evaluated.Conclusion. Within the limitations of this study, a denture base resin specifically designed for microwave Polymerization tested was not affected by different polymerization cycles. Porosity was similar to the conventional heat-polymerized denture base resin tested.

Polymerization shrinkage: effects of boundary conditions and filling technique of resin composite restorations

Objective: To evaluate the linear polymerization shrinkage (LPS) and the effect of polymerization shrinkage of a resin composite and resin-dentin bond strength under different boundary conditions and filling techniques.Methods: Two cavities (4 x 4 x 2 MM) were prepared in bovine incisors (n = 30). The teeth were divided into three groups, according to boundary conditions: In group TE, the total-etch technique was used. In group EE, only enamel was conditioned, and in group NE, none of the watts of the cavities were conditioned. A two-step adhesive system was applied to all cavities. The resin composite was inserted in one (B) or three increments (1), and tight-cured with 600 mW/cm(2) (80 s). The LPS (%) was measured in the top-bottom direction, by placing a probe in contact with resin composite during curing. Enamel and total mean gap widths were measured (400 x) in three slices obtained after sectioning the restorations. Then, the slices were sectioned again, either to obtain sticks from the adhesive interface from the bottom of the cavity or to obtain resin composite sticks (0.8 mm(2)) to be tested for tensile strength (Kratos machine, 0.5 mm/min). The data was subjected to a two-way repeated measures ANOVA and Tukey's test for comparison of the means (alpha = 0.05).Results: the highest percentage of LPS was found for the TE when bulk fitted, and the lowest percentage of LPS was found in the Hand NE when incrementally fitted. The resin dentin bond strength was higher and the total mean gap width was tower for TE group; no significant effect was detected for the main factor fitting techniques. No difference was detected for the tensile strength of resin composite among the experimental groups.Conclusions: the filling technique is not able to minimize effects of the polymerization shrinkage, and bonding to the cavity watts is necessary to assure reduced mean gap width and high bond strength values. (C) 2004 Elsevier Ltd. All rights reserved.

Moonlets wandering on a leash-ring

Since the Voyager flybys, embedded moonlets have been proposed to explain some of the surprising structures observed in Saturn's narrow F ring. Experiments conducted with the Cassini spacecraft support this suggestion. Images of the F ring show bright compact spots, and seven occultations of stars by the F ring, monitored by ultraviolet and infrared experiments, revealed nine events of high optical depth. These results point to a large number of such objects, but it is not clear whether they are solid moonlets or rather loose particle aggregates. Subsequent images suggested an irregular motion of these objects so that a determination of their orbits consistent with the F ring failed. Some of these features seem to cross the whole ring. Here we show that these observations are explained by chaos in the F ring driven mainly by the 'shepherd' moons Prometheus and Pandora. It is characterized by a rather short Lyapunov time of about a few hundred orbital periods. Despite this chaotic diffusion, more than 93 per cent of the F-ring bodies remain confined within the F ring because of the shepherding, but also because of a weak radial mobility contrasted by an effective longitudinal diffusion. This chaotic stirring of all bodies involved prevents the formation of 'propellers' typical of moonlets, but their frequent ring crossings explain the multiple radial 'streaks' seen in the F ring. The related 'thermal' motion causes more frequent collisions between all bodies which steadily replenish F-ring dust and allow for ongoing fragmentation and re-accretion processes (ring recycling).

Residual monomer of reline acrylic resins - Effect of water-bath and microwave post-polymerization treatments

Objectives. This study compared the residual monomer (RM) in four hard chair-side reline resins (Duraliner II-D, Kooliner-K, Tokuso Rebase Fast-TRF and Ufi Gel hard-UGH) and one heat-polymerized denture base resin (Lucitone 550-L), which was processed using two polymerization cycles (short-LS and long-LL). It was also investigated the effect of two after polymerization treatments on this RM content.Methods. Specimens (n = 18) of each material were produced following the manufacturers' instructions and then divided into three groups. Group I specimens were left untreated (GI-control). Specimens of group II (GII) were given post-polymerization treatment by microwave irradiation. In group III (GIII), specimens were submitted to immersion in water at 55 degrees C (reline resins-10 min; denture base resin L-60min). The RM was analyzed using high performance liquid chromatography (HPLC) and expressed as a percentage of RM. Data were analyzed by two-way ANOVA followed by Tukey's test (alpha = 0.05).Results. Comparing control specimens, statistical differences were found among all materials (p < 0.05), and the results can be arranged as K (1.52%) > D (0.85%) > UGH (0.45%) > LL (0.24%) > TRF (0.14%) > LS (0.08%). Immersion in hot water (GIII) promoted a significant (p < 0.05) reduction in the RM for all materials evaluated compared to control (GI), with the exception of LL specimens. Materials K, UGH and TRF exhibited significantly (p < 0.05) lower values of RM after microwave irradiation (GII) than in the control specimens.Significance. The reduction in RM promoted by water-bath and microwave post-polymerization treatments could improve the mechanical properties and biocompatibility of the relining and denture base materials. (c) 2006 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Titanium and zirconium complexes containing sterically hindered hydrotris(pyrazolyl)borate ligands: synthesis, structural characterization, and ethylene polymerization studies

The synthesis, characterization and ethylene polymerization behavior of a set of Tp'MCl3 complexes (4, M = Ti, Tp' HB(3-neopentyl-pyrazolyl)(3)(-) (Tp(NP)); 5, M = Ti, Tp'= HB(3-tert-butyl-pyrazolyl)(3)(-) (Tp(tBu)); 6, M = Ti, Tp' = HB(3-phenyl-pyrazolyl)(3)(-) (Tp(Ph)); 7, M = Zr, Tp' = HB(3-phenyl-pyrazolyl)(3)(-) (Tp(ph)); 8, M = Zr, Tp' = HB(3-tert-butyl-pyrazolyl)(3)(-) (Tp(tBu))) is described. Treatment of these tris(pyrazolyl)borate Group IV compounds with methylalumoxane (MAO) generates active catalysts for ethylene polymerization. For the polymerization reactions performed in toluene at 60 degreesC and 3 atm of ethylene pressure, the activities varied between 1.3 and 5.1 X 10(3) g of PE/mol[M](.)h. The highest activity is reached using more sterically open catalyst precursor 4. The viscosity-average molecular weights ((M-v) over bar) of the PE's produced with these catalyst precursors varying from 3.57 to 20.23 x 10(5) gmol(-1) with melting temperatures in the range of 127-134 degreesC. Further polymerization studies employing 7 varying Al/Zr molar ratio and temperature of polymerization showed that the activity as well as the polymer properties are dependent on these parameters. In that case, higher activity was attained at 60 degreesC. The viscosity-average molecular weights of the polyethylene's decreases with increasing AI/Zr molar ratio. (C) 2003 Elsevier B.V. All rights reserved.

Some comments on the F ring-Prometheus-Pandora environment

The system formed by the F ring and two close satellites, Prometheus and Pandora, has been analysed since the time that Voyager visited the planet Saturn. During the ring plane crossing in 1995 the satellites were found in different positions as predicted by the Voyager data. Besides the mutual effects of Prometheus and Pandora, they are also disturbed by a massive F ring. Showalter et al. [Icarus 100 (1992) 394] proposed that, the core of the ring has a mass which corresponds to a moonlet varying in size from 15 to 70 kin in radius which can prevent the ring from spreading due to dissipative forces, such as Poynting-Robertson drag and collisions. We have divided this work into two parts. Firstly we analysed the secular interactions between Prometheus-Pandora and a massive F ring using the secular theory. Our results show the variation in eccentricity and inclination of the satellites and the F ring taking into account a massive ring corresponding to a moonlet of different sizes. There is also a population of dust particles in the ring in the company of moonlets at different sizes [Icarus 109 (1997) 304]. We also analysed the behaviour of these particles under the effects of the Poynting-Robertson drag and radiation pressure. Our results show that the time scale proposed for a dust particle to leave the ring is much shorter than predicted before even in the presence of a coorbital moonlet. This result does not agree with the confinement model proposed by Dermott et al. [Nature 284 (1980) 309]. In 2004, Cassini mission will perform repeated observations of the whole system, including observations of the satellites and the F ring environment. These data will help us to better understand this system. (C) 2003 COSPAR. Published by Elsevier Ltd. All rights reserved.