Comparison between different conditions of the chemical polymerization of polyaniline on top of PET films

Composites produced during the in situ chemical polymerization of aniline on top of a poly(ethylene terephthalate) (PET) film, in different conditions, were studied by open-circuit potential (Voc), ultraviolet-visible, and infrared spectroscopy, electrical conductivity measurements, scanning electron microscopy, and atomic force microscopy. The polymerization monitoring by Voc showed a maximum associated with the intermediate pernigraniline oxidation state and a final formation of polyaniline (PANI) in the doped emeraldine salt (ES) form. Furthermore, high electrical conductivity values were obtained for the PANI-ES coating prepared under selected conditions. A globular formation was observed for the doped PANI-ES coating with globules of sizes of the same order and same shape of the PET, demonstrating the influence of the substrate on the coating morphology.

Kinetics of spermatogenesis in the Mongolian gerbil (Meriones unguiculatus)

The Mongolian gerbil (Meriones unguiculatus) is a small rodent native to the arid regions of Mongolia and Northeastern China. The present study provides descriptions of both the cellular associations of the seminiferous-epithelium cycle and relative frequencies of stages in the gerbil. Based on the development of the acrosomic system and the nuclear morphology changes using the PAS-H staining technique, the transformation of spermatids into spermatozoa was divided into 15 steps. The first 12 steps were used to identify 12 stages or cellular associations and the other three steps were spread among the first six stages of the cycle of the seminiferous epithelium. The relative frequencies found for stages I through XII were: 13.15; 8.06; 8.98; 6.48; 5.37; 6.71; 7.36; 7.45; 7.27; 5.83; 11.53 and 11.81, respectively. Stage I had the highest frequency while stage V proved the lowest frequency among the XII stages. The pattern of spermatogenesis is similar to those of rodents used as laboratory animals. The present description is the first for this rodent and provides the foundation for a variety of future studies of the testis in this animal. © 2002 Elsevier Science Ltd. All rights reserved.

Polymerization shrinkage evaluation of three packable composite resins using a gas pycnometer.

Modern restorative dentistry has been playing an outstanding role lately since composite resins, allied to adhesive systems, have been widely applied on anterior and posterior teeth restorations. The evolution of composite resins has mostly been verified due to the improvement of their aesthetic behavior and the increase in their compressive and abrasive strengths. In spite of these developments, the polymerization shrinkage inherent to the material has been a major deficiency that, so far, has been impossible to avoid. Using a gas pycnometry, this research investigated the polymerization shrinkage of three packable composite resins: Filtek P60 (3M), Prodigy Condensable (Kerr), and SureFil (Dentsply/Caulk), varying the distance from the light source to the surface of the resins (2 mm or 10 mm). The pycnometer Accupyc 1330 (Micromeritics, USA) precisely records helium displacement, allowing fast and reliable measurements of the volume of composite resin immediately before and after polymerization, without interference of temperature or humidity. Results were not found to be statistically different for the three tested resins, either for 2 mm or 10 mm-distance from the light source to the composite surface.

Thermogravimetric studies of the decomposition kinetics of four different Hevea rubber clones using Ozawa's approach

Thermal degradation of natural rubber extracted from four different rubber clones of the Hevea brasiliensis species was investigated by thermogravimetry using Ozawa's approach to assess the kinetic parameters of the decomposition process. The results are discussed in terms of the order of reaction, kinetic parameters such as activation energy as a function of conversion degree, and thermal stability for each of the clones.

Oxygen uptake kinetics and time to exhaustion in cycling and running: A comparison between trained and untrained subjects

The objective of the present study was to compare pulmonary gas exchange kinetics (VO 2 kinetics) and time to exhaustion (Tlim) between trained and untrained individuals during severe exercise performed on a cycle ergometer and treadmill. Eleven untrained males in running (UR) and cycling (UC), nine endurance cyclists (EC), and seven endurance runners (ER) were submitted to the following tests on separate days: (i) incremental test for determination of maximal oxygen uptake (VO 2max) and the intensity associated with the achievement of VO 2max (IVO 2max) on a mechanical braked cycle ergometer (EC and UC) and on a treadmill (ER and UR); (ii) all-out exercise bout performed at IVO 2max to determine the time to exhaustion at IVO 2max (Tlim) and the time constant of oxygen uptake kinetics (τ). The τ was significantly faster in trained group, both in cycling (EC = 28.2 ± 4.7 s; UC = 63.8 ± 25.0 s) and in running (ER = 28.5 ± 8.5 s; UR = 59.3 ± 12.0 s). Tlim of untrained was significantly lower in cycling (EC = 384.4 ± 66.6 s vs. UC; 311.1 ± 105.7 s) and higher in running (ER = 309.2 ± 176.6 s vs. UR = 439.8 ± 104.2 s). We conclude that the VO 2 kinetic response at the onset of severe exercise, carried out at the same relative intensity is sensitive to endurance training, irrespective of the exercise type. The endurance training seems to differently influence Tlim during exercise at IVO 2max in running and cycling. © 2003 Taylor & Francis Ltd.

Synthesis and characterization of poly-o-toluidine: Kinetic and structural aspects

Poly(o-methylaniline) (poly-o-toluidine, PTOL) was synthesized by chemical oxidation of o-toluidine with ammonium peroxydisulfate in an aqueous 1.0 mol L -1 HCl solution. The progress of polymerization was followed by measuring the open-circuit potential (OCP) of a Pt electrode immersed in the reaction medium with the polymerization time. The chemical synthesis of PTOL was carried out at different monomer:oxidant (M:O) molar ratios (4:1, 2:1, 1.5:1, 1:1, and 0.66:1), and the products obtained were characterized by infrared spectroscopy, gel permeation chromatography, and X-ray diffraction. The molecular weight and percentage of crystallinity of PTOL are higher for samples synthesized in an excess of the monomer, i.e. at higher M:O ratios. However, the yield of PTOL prepared at higher M:O ratios is considerably low, in particular at a 4:1 M:O ratio, which is the M:O ratio most commonly used in the literature to synthesize polyaniline and its derivatives.

Kinetics and crystal structure of human purine nucleoside phosphorylase in complex with 7-methyl-6-thio-guanosine

Purine nucleoside phosphorylase (PNP) catalyzes the reversible phosphorolysis of nucleosides and deoxynucleosides, generating ribose 1-phosphate and the purine base, which is an important step of purine catabolism pathway. The lack of such an activity in humans, owing to a genetic disorder, causes T-cell impairment, and drugs that inhibit this enzyme may have the potential of being utilized as modulators of the immunological system to treat leukemia, autoimmune diseases, and rejection in organ transplantation. Here, we describe kinetics and crystal structure of human PNP in complex with 7-methyl-6-thio-guanosine, a synthetic substrate, which is largely used in activity assays. Analysis of the structure identifies different protein conformational changes upon ligand binding, and comparison of kinetic and structural data permits an understanding of the effects of atomic substitution on key positions of the synthetic substrate and their consequences to enzyme binding and catalysis. Such knowledge may be helpful in designing new PNP inhibitors. © 2005 Elsevier Inc. All rights reserved.

Effect of post-polymerization heat treatments on the cytotoxicity of two denture base acrylic resins

Introduction: Most denture base acrylic resins have polymethylmethacrylate in their composition. Several authors have discussed the polymerization process involved in converting monomer into polymer because adequate polymerization is a crucial factor in optimizing the physical properties and biocompatibility of denture base acrylic resins. To ensure the safety of these materials, in vitro cytotoxicity assays have been developed as preliminary screening tests to evaluate material biocompatibility. 3H-thymidine incorporation test, which measures the number of cells synthesizing DNA, is one of the biological assays suggested for cytotoxicity testing. Aim: The purpose of this study was to investigate, using 3H-thymidine incorporation test, the effect of microwave and water-bath post-polymerization heat treatments on the cytotoxicity of two denture base acrylic resins. Materials and Methods: Nine disc-shaped specimens (10 x 1 mm) of each denture base resin (Lucitone 550 and QC 20) were prepared according to the manufacturers' recommendations and stored in distilled water at 37°C for 48 h. The specimens were assigned to 3 groups: 1) post-polymerization in a microwave oven for 3 min at 500 W; 2) post-polymerization in water-bath at 55°C for 60 min; and 3) without post-polymerization. For preparation of eluates, 3 discs were placed into a sterile glass vial with 9 mL of Eagle's medium and incubated at 37°C for 24 h. The cytotoxic effect of the eluates was evaluated by 3H-thymidine incorporation. Results: The results showed that the components leached from the resins were cytotoxic to L929 cells, except for the specimens heat treated in water bath (p<0.05). Compared to the group with no heat treatment, water-bath decreased the cytotoxicity of the denture base acrylic resins. Conclusion: The in vitro cytotoxicity of the tested denture base materials was not influenced by microwave post-polymerization heat treatment.

Degree of conversion and molecular weight of one denture base and three reline resins submitted post-polymerization treatments

The effect of post-polymerization treatments (MW-microwave irradiatron and WB-water-bath) on the degree of conversion (DC) of three reline resins (Ufi Gel hard-U, Kooliner-K, and Tokuso Rebase Fast-T) and one denture base resin (Lucitone 550-L), submitted to two polymerization cycles (LS-short and LL-long), was evaluated by using FT-Raman spectroscopy (n = 5). The molecular weight (Mw) of the powder of all materials and of K polymerized specimens (control; MW; and WB; n = 3) was analyzed using GPC. DC data were analyzed using Kruskal-Wallis test (α = .05). For control specimens, there were no significant differences between U (68%) and LL (77%) and among LL, K (81%), and T (84%). LS (92%) had the highest DC (P<0.05). Only material K exhibited an increased DC after WB (P<0.05). All powders had Mw from 4.0 × 105 to 6.5 × 105 and narrow Mw distributions (2.1 to 3.6). Polymerization and post-polymerization produced K specimens with Mw similar to that of K powder.

Effect of a post-polymerization treatments on the flexural strength and vickers hardness of reline and acrylic denture base resins

This study evaluated the effect of water-bath and microwave post-polymerization treatments on the flexural strength and Vickers hardness of four autopolymerizing reline resins (Duraliner II-D, Kooliner-K, Tokuso Rebase Fast-TR and Ufi Gel Hard C-UGH) and one heat-polymerized acrylic resin (Lucitone 550-L), processed using two polymerization cycles (short cycle - 90 minutes at 73°C and 100°C for 30 minutes; and long cycle - 9 hours at 71°C). For each material, thirty specimens (64 x 10 x 3.3 mm) were made and divided into 3 groups (n=10). Specimens were tested after: processing (control group); water-bath at 55°C for 10 minutes (reline materials) or 60 minutes (L); and microwave irradiation. Flexural strength tests were performed at a crosshead speed of 5 mm/min using a three-point bending device with a span of 50 mm. The flexural strengths values were calculated in MPa. One fragment of each specimen was submitted to Vickers hardness test. Data were analyzed by 2-way ANOVA followed by Tukey's HSD test (α=0.05). L microwaved specimens (short cycle) exhibited significantly higher flexural strength means than its respective control group (p<0.05). Water-bath promoted a significant increase (p<0.05) in flexural strength of K and L (long cycle). The hardness of the tested materials was not influenced by the post-polymerization treatments. Post-polymerization treatments could be used to improve the flexural strength of some materials tested.

Martensite aging kinetics in the Cu-10 wt.%Al and Cu-10 wt.%Al-10 wt.%Ag alloys

The martensite aging kinetics in the Cu-10 wt.%Al and Cu-10 wt.%Al-10 wt.%Ag alloys was studied using microhardness measurements, classical differential thermal analysis (DTA), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and in-situ high-temperature X-ray diffractometry (XRD). The results for the Cu-10%Al alloy indicated a process dominated by the martensite ordering assisted by migration of quenched-in vacancies and followed by the consumption of the α phase. For the Cu-10%Al-10%Ag alloy the dominant process is the consumption of the α phase associated with a decrease in the ordering degree of the martensitic phase. © 2007 Springer Science+Business Media, LLC.

Application of non-isothermal cure kinetics on the interaction of poly(ethylene terephthalate) - Alkyd resin paints

Samples of paint (P), reused PET (PET-R) and paint/PET-R mixtures (PPET-R) were evaluated using DSC to verify their physical-chemical properties and thermal behavior. Films from paints and PPET-R are visually similar. It was possible to establish that the maximum amount of PET-R that can be added to paint without significantly altering its filming properties is 2%. The cure process (80-203°C) was identified through DSC curves. The kinetic parameters, activation energy (E a) and Arrhenius parameters (A) for the samples containing 0.5 to 1% of PET-R, were calculated using the Flynn-Wall-Ozawa isoconversional method. It was observed that for greater amounts of PET-R added, there is a decrease in the E a values for the cure process. A Kinetic compensation effect (KCE), represented by the equation InA=-2.70+0.31E a was observed for all the samples. The most suitable kinetic model to describe this cure process is the autocatalytic Šesták-Berggreen, model applied to heterogeneous systems. © 2007 Springer Science+Business Media, LLC.

Influence of microwave polymerization method and thickness on porosity of acrylic resin

Purpose: This study evaluated the influence of polymerization cycle and thickness of maxillary complete denture bases on the porosity of acrylic resin. Materials and Methods: Two heat-activated denture base resins - one conventional (Clássico) and one designed for microwave polymerization (Onda-Cryl) - were used. Four groups were established, according to polymerization cycles: A (Onda-Cryl, short microwave cycle), B (Onda-Cryl, long microwave cycle), C (Onda-Cryl, manufacturing microwave cycle), and T (Clássico, water bath). Porosity was evaluated for different thicknesses (2.0, 3.5, and 5.0 mm; thicknesses I, II, and III, respectively) by measurement of the specimen volume before and after its immersion in water. The percent porosity data were submitted to Kruskal-Wallis for comparison among the groups. Results: The Kruskal-Wallis test detected that the combinations of the different cycles and thicknesses showed significant differences, and the mean ranks of percent porosity showed differences only in the thinnest (2.0 mm) microwave-polymerized specimens (A = 53.55, B = 40.80, and C = 90.70). Thickness did not affect the results for cycle T (I = 96.15, II = 70.20, and III = 82.70), because porosity values were similar in the three thicknesses. Conclusions: Microwave polymerization cycles and the specimen thickness of acrylic resin influenced porosity. Porosity differences were not observed in the polymerized resin bases in the water bath cycle for any thickness. © 2007 by The American College of Prosthodontists.

Analysis of the kinetics of phase and amplitude gratings recorded in azopolymer films

In this work we use a stabilized holographic technique to study both refractive index and absorption gratings recorded in thin films made of Disperse Red 1 (DR1) embedded in an organic polymer matrix (PMMA) deposited on glass substrate. Gratings are recorded by linearly polarized illumination with the interference pattern of two crossing beams. One of the beams is phase modulated and the interference signals between the transmitted and diffracted waves are detected by a tuned lock-in amplifier. The technique allows measuring separately changes of the refractive index and the absorption coefficient during the course of the photoreaction process. The time evolution of the diffraction efficiencies during recording has shown bi-exponential kinetics for both gratings. © 2008 American Institute of Physics.