STRATEGIES FOR PREPARATION OF MOLECULARLY IMPRINTED POLYMERS MODIFIED ELECTRODES AND THEIR APPLICATION IN ELECTROANALYSIS: A REVIEW

Molecularly imprinted polymers (MIP's) have been applied in several areas of analytical chemistry, including the modification of electrodes. The main purpose of such modification is improving selectivity; however, a gain in sensitivity was also observed in many cases. The most frequent approaches for these modifications are the electrodeposition of polymer films and sol gel deposits, spin and drop coating and self-assembling of films on metal nanoparticles. The preparation of bulk (body) modified composites as carbon pastes and polymer agglutinated graphite have also been investigated. In all cases several analytes including pharmaceuticals, pesticides, and inorganic species, as well as molecules with biological relevance have been successfully used as templates and analyzed with such devices in electroanalytical procedures. Herein, 65 references are presented concerning the general characteristics and some details related to the preparation of MIP's including a description of electrodes modified with MIP's by different approaches. The results using voltammetric and amperometric detection are described.

Kinetic parameters and monomeric conversion of different dental composites using standard and soft-start photoactivation modes

This paper evaluates the photopolymerization kinetics and degree of conversion of different commercial dental composites when photoactivated by a LED curing unit using two different modes (standard and soft-start mode). The investigation was performed on with RelyX ARC (dual-cured), Filtek Z-350 (Nanocomposite), Filtek Z-250 (Hybrid), and Filtek Z-350flow (Flowable) resin composites. The analysis used was attenuated total reflection with a Fourier transform infrared (ATR-FTIR). The RelyX ARC resin demonstrated the highest degree of conversion with both LED photoactivation modes. For this resin a 28% decrease in maximum rate was observed and the time to reach its highest rate was almost 2.3 times higher than when the soft-start photoactivation light curing was used. Z-350flow resin recorder a higher maximum rate using the soft-start mode rather than the standard mode. In contrast, the Z-250 showed a higher value using the standard mode. Although Z-250 and Z-350 showed a higher total degree of conversion effectiveness using the soft-start mode, RelyX and Z-350flow achieved a higher value using the standard mode.

Materials prepared from biopolyethylene and curaua fibers: Composites from biomass

Composites of high-density biopolyethylene (HDBPE) obtained from ethylene derived from sugarcane ethanol and curaua fibers were formed by first mixing in an internal mixer followed by thermopressing. Additionally, hydroxyl-terminated polybutadiene (LHPB), which is usually used as an impact modifier, was mainly used in this study as a compatibilizer agent. The fibers, HDBPE and LHPB were also compounded using an inter-meshing twin-screw extruder and, subsequently, injection molded. The presence of the curaua fibers enhanced some of the properties of the HDBPE, such as its flexural strength and storage modulus. SEM images showed that the addition of LHPB improved the adhesion of the fiber/matrix at the interface, which increased the impact strength of the composite. The higher shear experienced during processing probably led to a more homogeneous distribution of fibers, making the composite that was prepared through extruder/injection molding more resistant to impact than the composite processed by the internal mixer/thermopressing. (c) 2012 Elsevier Ltd. All rights reserved.

Synthesis and characterization of CeO2-graphene composite

The synthesis and characterization of graphite oxide (GO), graphene (GS), and the composites: GS-CeO2 and GO-CeO2 are reported. This synthesis was carried out by mixing aqueous solutions of CeCl3 center dot 7H(2)O and GO, which yields the oxidized composite GO-CeO2. GO-CeO2 was hydrothermally reduced with ethylene glycol, at 120 A degrees C, yielding the reduced composite GS-CeO2. GO, GS ,and the composites with CeO2 were characterized by CHN, TG/DTG, BET, XRD, SEM microscopy, FTIR, and Raman spectroscopy. The estimation of crystallite size of CeO2 anchored on GO and on GS by Raman, XRD, and SEM agreed very well showing diameters about 5 nm. The role of particles of CeO2 coating carbon sheets of GO and GS was discussed.

Annealing effects on nanostructured gold-polymethylmethacrylate composites: Small-angle x-ray scattering analysis

Composites formed of a polymer-embedded layer of sub-10 nm gold nanoclusters were fabricated by very low energy (49 eV) gold ion implantation into polymethylmethacrylate. We used small angle x-ray scattering to investigate the structural properties of these metal-polymer composite layers that were fabricated at three different ion doses, both in their original form (as-implanted) and after annealing for 6 h well above the polymer glass transition temperature (150 degrees C). We show that annealing provides a simple means for modification of the structure of the composite by coarsening mechanisms, and thereby changes its properties. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4720464]

Determination of chlorine in food samples via the AlCl molecule using high-resolution continuum source molecular absorption spectrometry in a graphite furnace

Determination of chlorine using the molecular absorption of aluminum mono-chloride (AlCl) at the 261.418 nm wavelength was accomplished by high-resolution continuum source molecular absorption spectrometry using a transversely heated graphite tube furnace with an integrated platform. For the analysis. 10 mu L of the sample followed by 10 mu L of a solution containing Al-Ag-Sr modifier, (1 g L-1 each), were directly injected onto the platform. A spectral interference due to the use of Al-Ag-Sr as mixed modifier was easily corrected by the least-squares algorithm present in the spectrometer software. The pyrolysis and vaporization temperatures were 500 degrees C and 2200 degrees C, respectively. To evaluate the feasibility of a simple procedure for the determination of chlorine in food samples present in our daily lives, two different digestion methods were applied, namely (A) an acid digestion method using HNO3 only at room temperature, and (B) a digestion method with Ag, HNO3 and H2O2, where chlorine is precipitated as a low-solubility salt (AgCl), which is then dissolved with ammonia solution. The experimental results obtained with method B were in good agreement with the certified values and demonstrated that the proposed method is more accurate than method A. This is because the formation of silver chloride prevented analyte losses by volatilization. The limit of detection (LOD, 3 sigma/s) for Cl in methods A and B was 18 mu g g(-1) and 9 mu g g(-1), respectively, 1.7 and 3.3 times lower compared to published work using inductively coupled plasma optical emission spectrometry, and absolute LODs were 2.4 and 1.2 ng, respectively. (C) 2012 Elsevier B.V. All rights reserved.

Composites from a forest biorefinery byproduct and agrofibers: Lignosulfonate-phenolic type matrices reinforced with sisal fibers

The replacement of phenol with sodium lignosulfonate and formaldehyde with glutaraldehyde in the preparation of resins resulted in a new resol-type phenolic resin, sodium lignosulfonate-glutaraldehyde resin, in addition to sodium lignosulfonate-formaldehyde and phenol-formaldehyde resins. These resins were then used to prepare thermosets and composites reinforced with sisal fibers. Different techniques were used to characterize raw materials and/or thermosets and composites, including inverse gas chromatography, thermogravimetric analysis, and mechanical impact and flexural tests. The substitution of phenol by sodium lignosulfonate in the formulation of the composite matrices increased the impact strength of the respective composites from approximately 400 Jm(-1) to 800 J m(-1) and 1000 J m(-1), showing a considerable enhancement from the replacement of phenol with sodium lignosulfonate. The wettability of the sisal fibers increased when the resins were prepared from sodium lignosulfonate, generating composites in which the adhesion at the fiber-matrix interface was stronger and favored the transference of load from the matrix to the fiber during impact. Results suggested that the composites experienced a different mechanism of load transfer from the matrix to the fiber when a bending load was applied, compared to that experienced during impact. The thermogravimetric analysis results demonstrated that the thermal stability of the composites was not affected by the use of sodium lignosulfonate as a phenolic-type reagent during the preparation of the matrices.

Evaluation of epoxy resin sealer after three root canal filling techniques by confocal laser scanning microscopy

The aim of this study was to evaluate the penetration of endodontic sealer into the dentin tubules, the integrity of the sealer layer perimeter, and the sealer area at the apical third after different filling techniques by confocal laser scanning microscopy (CLSM). Forty-five mandibular premolars were mechanically prepared with ProTaper files, until F5 file. Thereafter, they were filled with an epoxy-resin sealer (AH Plus) mixed with Rhodamine B dye (0.1% proportion) and allocated in three groups: Group 1, single master cone; Group 2, cold lateral compaction; and Group 3, Thermafil. For confocal laser scanning microscopy analysis, the specimens were transversely sectioned at 4 mm from the apex. The images at x10 and x40 were analyzed by Imagetool 3.0 software. Significant differences were not found among the three experimental groups according the dentin-impregnate area by the sealer (P = 0.68) and between the sealer and root canal perimeter (P = 0.18). However, root canal filling techniques were significantly different when apical sealer areas were compared (P = 0.001). Thermafil group showed smaller sealer areas (8.09%) while cold lateral compaction and gutta-percha master cone showed similar areas (17.37 and 21.18%, respectively). The dentin-impregnated area was not dependent on the root canal filling technique. Single master cone, cold lateral condensation and Thermafil techniques presented integrity of the sealer perimeter close to 100% and Thermafil resulted in a significantly thinner sealer layer. Microsc. Res. Tech. 75:12771280, 2012. (C) 2012 Wiley Periodicals, Inc.

Effect of the root canal final rinse protocols on the debris and smear layer removal and on the push-out strength of an epoxy-based sealer

The aim of the present study was to evaluate the efficacy of QMiX, SmearClear, and 17% EDTA for the debris and smear layer removal from the root canal and its effects on the push-out bond strength of an epoxy-based sealer by scanning electron microscopy (SEM). Forty extracted human canines (n = 10) were assigned to the following final rinse protocols: G1-distilled water (control), G2–17% EDTA, G3-SmearClear, and G4-QMiX. The specimens were submitted to a SEM analysis to evaluate the presence of debris and smear layer, respectively, in the apical or cervical segments. In sequence, forty extracted human maxillary canines with the root canals instrumented were divided into four groups (n = 10) similar to the SEM analysis study. After the filling with AH Plus, the roots were transversally sectioned to obtain dentinal slices. The specimens were submitted to a push-out bond strength test using an electromechanical testing machine. The statistical analysis for the SEM and push-out bond strength studies were performed using the Kruskal–Wallis and Dunn tests (α = 5%). There was no difference among the G2, G3, and G4 efficacy in removing the debris and smear layer (P > 0.05). The efficacy of these groups was superior to the control group. The push-out bond strength values of G2, G3, and G4 were superior to the control group. The ability to remove the debris and smear layer by SmearClear and QMiX was as effective as the 17% EDTA. The final rinse with these solutions promoted similar push-out bond strength values.

Characterization and use of swine deep bedding ashes in cementitious composites

The deep bedding is a swine alternative production, especially in the finishing phase, whose byproduct can be recycled, reducing the environmental impact. The objectives of this study were to characterize the ash coming from the controlled burning of the swine deep bedding (SDBA) based on rice husk, and to evaluate their performance in composites as a partial substitute for Portland cement (PC). To measure the differences between SDBA and rice husk ash (RHA) as a reference, we have characterized: particle size distribution, real specific density, x-ray diffraction, electrical conductivity, scanning electron microscopy, chemical analysis and loss on ignition. Samples were prepared for two experimental series: control, and another one with the partial replacement of 30% of SDBA in relation to the mass of the Portland cement. According to the results obtained for physical and mechanical characterization, the composites with SDBA can be used as a constructive element in the rural construction.

Determination of tetracycline in environmental water samples at a graphite-polyurethane composite electrode

A bare graphite-polyurethane composite was evaluated in the tetracycline (TC) determination in natural water samples. Using differential pulse voltammetry (DPV), a linear response was observed in the range of 4.00-40.0 µmol L-1 with limit of detection of 2.80 µmol L-1, without the need of surface renewing between successive runs. During the tetracycline determination in water samples, recoveries between 92.6 and 100% were found. The results for TC determination in water samples after a pre-concentration stage agreed with spiked value at a 95% confidence level according to student t-test.

Clinical evaluation of the failure rate of metallic brackets bonded with orthodontic composites

The purpose of the present study was to evaluate in vivo the failure rate of metallic brackets bonded with two orthodontic composites. Nineteen patients with ages ranging from 10.5 to 38.7 years needing corrective orthodontic treatment were selected for study. The enamel surfaces from second premolars to second premolars were treated with Transbond Plus-Self Etching Primer (3M Unitek). Next, 380 orthodontic brackets were bonded on maxillary and mandibular teeth, as follows: 190 with Transbond XT composite (3M Unitek) (control) and 190 with Transbond Plus Color Change (3M Unitek) (experimental) in contralateral quadrants. The bonded brackets were light cured for 40 s, and initial alignment archwires were inserted. Bond failure rates were recorded over a six-month period. At the end of the evaluation, six bond failures occurred, three for each composite. Kaplan-Meyer method and log-rank test (Mantel-Cox) was used for statistical analysis, and no statistically significant difference was found between the materials (p=0.999). Both Transbond XT and Transbond Plus Color Change composites had low debonding rates over the study period.

Color stability of modern composites subjected to different periods of accelerated artificial aging

The aim of this study was to evaluate the color stability of composites subjected to different periods of accelerated artificial aging (AAA). A polytetrafluorethylene matrix (10 x 2 mm) was used to fabricate 24 test specimens of three different composites (n=8): Tetric Ceram (Ivoclar/Vivadent); Filtek P90 and Z250 (3M ESPE), shade A3. After light activation for 20 s (FlashLite 1401), polishing and initial color readout (Spectrophotometer PCB 687; BYK Gardner), the test specimens were subjected to AAA (C-UV; Comexim), in 8-h cycles: 4 h exposure to UV-B rays at 50°C and 4 h condensation at 50°C. At the end of each cycle, color readouts were taken and the test ended when the mean value of ΔE attained a level ≥3.30. Tetric Ceram presented alteration in ΔE equal to 3.33 in the first aging cycle. For Filtek P90 and Z250, two (ΔE=3.60) and four (ΔE=3.42) AAA cycles were necessary. After each cycle, there was a reduction of luminosity in all the samples (ΔL). It was concluded that a short period of AAA was sufficient to promote clinically unacceptable color alteration in composites, and that this alteration was material-dependent.

Analysis of surface hardness of artificially aged resin composites

This study evaluated the effect of artificially accelerated aging (AAA) on the surface hardness of eight composite resins: Filtek Z250, Filtek Supreme, 4 Seasons, Herculite, P60, Tetric Ceram, Charisma, and Filtek Z100. Sixteen specimens were made from the test piece of each material, using an 8.0 × 2.0 mm teflon matrix. After 24 hours, eight specimens from each material were submitted to three surface hardness readings using a Shimadzu Microhardness Tester for 5 seconds at a load of 50 gf. The other eight specimens remained in the artificially accelerated aging machine for 382 hours and were submitted to the same surface hardness analysis. The means of each test specimen were submitted to the Kolmogorov-Smirnov test (p > 0.05), ANOVA and Tukey test (p < 0.05). With regard to hardness (F = 86.74, p < 0.0001) the analysis showed significant differences among the resin composite brands. But aging did not influence the hardness of any of the resin composites (F = 0.39, p = 0.53). In this study, there was interaction between the resin composite brand and the aging factors (F = 4.51, p < 0.0002). It was concluded that notwithstanding the type of resin, AAA did not influence surface hardness. However, with regard to hardness there was a significant difference among the resin brands.

Optical storage in azobenzene-containing epoxy polymers processed as Langmuir Blodgett films

In this study, azocopolymers containing different main-chain segments have been synthesized with diglycidyl ether of bisphenol A (DGEBA, DER 332, n=0.03) and the azochromophore Disperse Orange 3 (DO3) cured with twomonoamines, viz. benzylamine (BA) and m-toluidine (MT). The photoinduced birefringence was investigated in films produced with these azopolymers using the spin coating (SC) and Langmuir Blodgett (LB) techniques. In the LB films, birefringence increased with the content of azochromophore and the film thickness, as expected. The nanostructured nature of the LB films led to an enhanced birefringence and faster dynamics in the writing process, compared to the SC films. In summary, the combination of azocopolymers and the LBmethod may allow materials with tuned properties for various optical applications, including in biological systems were photoisomerization may be used to trigger actions such as drug delivery.