Multi-walled carbon nanotubes modified screen-printed electrodes for cisplatin detection

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Aplicação de carbono vítreo monolítico para produção de eletrodos a partir da resina furfurílica com diferentes variações de pH

Nowadays, we live in a time of rapid research for technological advances, in a way that this pursuit of new technologies is deeply connected to the diversity of new materials that have been developed by mankind. It deals with issues such as materials with enhanced properties which offer better quality, less cost and high performance, while they are accessible both in their production and moment of operation. In this context, it was required to develop electrodes that were easy to prepare as well as which present high electric conductivity and good mechanic proprieties by using carbonaceous material as basis. For this reason, the best parameters of the furfuryl resin cures were established with different pH variations through viscosimetric measurements and differential scanning calorimetry. By scanning electron microscopy (SEM) was possible to identify an increased porosity in the samples with pH 7 and pH 8, as compared to samples with lower pH content. After carbonization of the material, the characterization of monolithic glassy carbon was held by means of FT-IR techniques, Raman spectroscopy, X-ray diffraction and cyclic voltammetry. The spectra showed that the change in pH does not have significant influence on the crystallographic ordering of the material and its structural characteristics. As for the electrochemical character, the CVM electrodes showed excellent response, with good reversibility and wide potential window. Some voltammetric curve deviations were only observed for the sample with pH 4, which may be related to processing parameters adopted

Aplicação de carbono vítreo monolítico para produção de eletrodos a partir da resina furfurílica com diferentes variações de pH

Nowadays, we live in a time of rapid research for technological advances, in a way that this pursuit of new technologies is deeply connected to the diversity of new materials that have been developed by mankind. It deals with issues such as materials with enhanced properties which offer better quality, less cost and high performance, while they are accessible both in their production and moment of operation. In this context, it was required to develop electrodes that were easy to prepare as well as which present high electric conductivity and good mechanic proprieties by using carbonaceous material as basis. For this reason, the best parameters of the furfuryl resin cures were established with different pH variations through viscosimetric measurements and differential scanning calorimetry. By scanning electron microscopy (SEM) was possible to identify an increased porosity in the samples with pH 7 and pH 8, as compared to samples with lower pH content. After carbonization of the material, the characterization of monolithic glassy carbon was held by means of FT-IR techniques, Raman spectroscopy, X-ray diffraction and cyclic voltammetry. The spectra showed that the change in pH does not have significant influence on the crystallographic ordering of the material and its structural characteristics. As for the electrochemical character, the CVM electrodes showed excellent response, with good reversibility and wide potential window. Some voltammetric curve deviations were only observed for the sample with pH 4, which may be related to processing parameters adopted

Mechanistic changes observed in heavy water for nitrate reduction reaction on palladium-modified Pt(hkl) electrodes

Reduction of nitrate on palladium-modified platinum single-crystal electrodes has been investigated both voltammetrically and spectroscopically in acidic media (pH = 1). Results obtained in H2O and D2O solvents are compared for the three crystallographic orientations. FTIR and differential electrochemical mass spectrometry (DEMS) results clearly indicate that the isotopic substitution of the solvent has a large effect in the mechanism of the reaction, changing the nature of the detected products. For Pt(111)/Pd and Pt(100)/Pd, N2O is detected as the main product of nitrate reduction when D2O is used as solvent, while no N2O is detected when the reaction is performed in H2O. For Pt(110)/Pd, N2O is detected in both solvents, although the use of D2O clearly favours the preferential formation of this product. The magnitude of voltammetric currents is also affected by the nature of the solvent. This has been analysed considering, in addition to the different product distribution, the existence of different transport numbers and optical constants of the solvent.

Borohydride electrooxidation on Au and Pt electrodes

Direct borohydride fuel cells (DBFCs) are attractive energy generators for powering portable electronic devices, mainly due to their high energy density and number of electrons per borohydride ion. However, the lack of a highly efficient electrocatalyst for the borohydride oxidation reaction limits the performance of these devices. The most commonly studied electrocatalysts for this reaction are composed of gold and platinum. Nevertheless, for these metals, the borohydride electrooxidation reaction mechanism (BOR) is not completely understood, and the total oxidation reaction, involving eight electrons per BH4- species, competes with parallel reactions, with a lower number of exchanged electrons and/or with heterogeneous chemical hydrolysis. Considering the above-mentioned issues, this work presents recent advances in the knowledge of the BOR pathways on polycrystalline (bulk) Au and Pt electrocatalysts. It presents the studies of the BOR reaction on Au and Pt electrodes using in situ Fourier Transform Infrared Spectroscopy (FUR), and on-line Differential Electrochemical Mass Spectrometry (DEMS). The spectroscopic and spectrometric data provided physical evidence of intermediate species and the formation of H-2 in the course of the BOR as a function of the electrode potential. These results enabled to advance in the knowledge about the BOR pathways on Au and Pt electrocatalysts. (C) 2012 Elsevier Ltd. All rights reserved.

Influence of the Sol-Gel pH Process and Compact Film on the Efficiency of TiO2-Based Dye-Sensitized Solar Cells

The influence of pH during hydrolysis of titanium(IV) isopropoxide on the morphological and electronic properties of TiO2 nanoparticles prepared by the sol-gel method is investigated and correlated to the photoelectrochemical parameters of dye-sensitized solar cells (DSCs) based on TiO2 films. Nanoparticles prepared under acid pH exhibit smaller particle size and higher surface area, which result in higher dye loadings and better short-circuit current densities than DSCs based on alkaline TiO2-processed films. On the other hand, the product of charge collection and separation quantum yields in films with TiO2 obtained by alkaline hydrolysis is c. a. 27% higher than for the acid TiO2 films. The combination of acid and alkaline TiO2 nanoparticles as mesoporous layer in DSCs results in a synergic effect with overall efficiencies up to 6.3%, which is better than the results found for devices employing one of the nanoparticles separately. These distinct nanoparticles can be also combined by using the layer-by-layer technique (LbL) to prepare compact TiO2 films applied before the mesoporous layer. DSCs employing photoanodes with 30 TiO2 bilayers have shown efficiencies up to 12% higher than the nontreated photoanode ones. These results can be conveniently used to develop optimized synthetic procedures of TiO2 nanoparticles for several dye-sensitized solar cell applications.

Electrochemical reactions of catechol, methylcatechol and dopamine at tetrahedral amorphous carbon (ta-C) thin film electrodes

The electrochemical reactions of dopamine, catechol and methylcatechol were investigated at tetrahedral amorphous carbon (ta-C) thin film electrodes. In order to better understand the reaction mechanisms of these molecules, cyclic voltammetry with varying scan rates was carried out at different pH values in H2SO4 and PBS solutions. The results were compared to the same redox reactions taking place at glassy carbon (GC) electrodes. All three catechols exhibited quasi-reversible behavior with sluggish electron transfer kinetics at the ta-C electrode. At neutral and alkaline pH, rapid coupled homogeneous reactions followed the oxidation of the catechols to the corresponding o-quinones and led to significant deterioration of the electrode response. At acidic pH, the extent of deterioration was considerably lower. All the redox reactions showed significantly faster electron transfer kinetics at the GC electrode and it was less susceptible toward surface passivation. An EC mechanism was observed for the oxidation of dopamine at both ta-C and GC electrodes and the formation of polydopamine was suspected to cause the passivation of the electrodes.

Coupled diusion and mechanics in battery electrodes

Thesis (Ph.D.)--University of Washington, 2016-08

Inkjet-printed poly(N-isopropylacrylamide)/graphene electrodes for selective electroanalytical sensing

The main research topic of the present master thesis consisted in the modification and electrochemical testing of inkjet printed graphene electrodes with a thin polymeric hydrogel layer made of cross-linked poly(N-isopropylacrylamide) (PNIPAAM) acting as a functional layer to fabricate selective sensors. The first experimental activities dealt with the synthesis of the polymeric hydrogel and the modification of the active surface of graphene sensors through photopolymerization. Simultaneous inkjet printing and photopolymerization of the hydrogel precursor inks onto graphene demonstrated to be the most effective and reproducible technique for the modification of the electrode with PNIPAAM. The electrochemical performance of the modified electrodes was tested through cyclic voltammetry. Voltammograms with standard redox couples with either positive, neutral or negative charges, suggested an electrostatic filtering effect by the hydrogel blocking negatively charged redox species in near neutral pH electrolyte solutions from reaching the electrode surface. PNIPAAM is a known thermo-responsive polymer, but the variation of temperature did not influence the filtering properties of the hydrogels for the redox couples studied. However, a variation of the filter capacity of the material was observed at pH 2 in which the PNIPAAM hydrogel, most likely in protonated form, became impermeable to positively charged redox species and permeable to negatively charged species. Finally, the filtering capacity of the electrodes modified with PNIPAAM was evaluated for the electrochemical determination of analytes in presence of negatively charge potential interferents, such as antioxidants like ascorbic acid. The outcome of the final experiments suggested the possibility to use the inkjet-printed PNIPAAM thin layer for electroanalytical applications as an electrostatic filter against interferents of opposite charges, typically present in complex matrices, such as food and beverages.

Remediation Of 17-α-ethinylestradiol Aqueous Solution By Photocatalysis And Electrochemically-assisted Photocatalysis Using Tio2 And Tio2/wo3 Electrodes Irradiated By A Solar Simulator.

TiO2 and TiO2/WO3 electrodes, irradiated by a solar simulator in configurations for heterogeneous photocatalysis (HP) and electrochemically-assisted HP (EHP), were used to remediate aqueous solutions containing 10 mg L(-1) (34 μmol L(-1)) of 17-α-ethinylestradiol (EE2), active component of most oral contraceptives. The photocatalysts consisted of 4.5 μm thick porous films of TiO2 and TiO2/WO3 (molar ratio W/Ti of 12%) deposited on transparent electrodes from aqueous suspensions of TiO2 particles and WO3 precursors, followed by thermal treatment at 450 (°)C. First, an energy diagram was organized with photoelectrochemical and UV-Vis absorption spectroscopy data and revealed that EE2 could be directly oxidized by the photogenerated holes at the semiconductor surfaces, considering the relative HOMO level for EE2 and the semiconductor valence band edges. Also, for the irradiated hybrid photocatalyst, electrons in TiO2 should be transferred to WO3 conduction band, while holes move toward TiO2 valence band, improving charge separation. The remediated EE2 solutions were analyzed by fluorescence, HPLC and total organic carbon measurements. As expected from the energy diagram, both photocatalysts promoted the EE2 oxidation in HP configuration; after 4 h, the EE2 concentration decayed to 6.2 mg L(-1) (35% of EE2 removal) with irradiated TiO2 while TiO2/WO3 electrode resulted in 45% EE2 removal. A higher performance was achieved in EHP systems, when a Pt wire was introduced as a counter-electrode and the photoelectrodes were biased at +0.7 V; then, the EE2 removal corresponded to 48 and 54% for the TiO2 and TiO2/WO3, respectively. The hybrid TiO2/WO3, when compared to TiO2 electrode, exhibited enhanced sunlight harvesting and improved separation of photogenerated charge carriers, resulting in higher performance for removing this contaminant of emerging concern from aqueous solution.

Dentin Bond Strength Of A Fluoride-releasing Adhesive System Submitted To Ph-cycling.

To evaluate the microtensile bond strength (µTBS) of a fluoride-containing adhesive system submitted to a pH-cycling and storage time regimen for primary outcomes. As secondary outcomes the fluoride released amount was evaluated. Twelve dentin surfaces from sound third molar were divided into 2 groups according to adhesive systems: Clearfil SE Protect (PB) and Clearfil SE Bond (SE). Sticks obtained (1.0 mm2) from teeth were randomly divided into 3 subgroups according to storage regimen model: immediate (24h); 5-month deionized water (W); and pH-cycling model (C). All sticks were tested for µTBS in a universal testing machine. Fluoride concentration was obtained from 1-4 days and 30-day in W and 1-4 days in demineralization (DE)/remineralization (RE) solutions from C, using a fluoride-specific electrode. µTBS and fluoride released data were, respectively, submitted to ANOVA in a split plot design and Tukey, and Friedman' tests (a=0.05). There was no significant interaction between adhesive system and storage regimen for µTBS. W showed the lowest µTBS values. There was no significant difference between 24 h and C models for µTBS. There was no significant difference between adhesive systems. Failure mode was predominantly cohesive within composite for the 24 h and W, for the C group it was mixed for SE and cohesive within composite for PB adhesive system. Fluoride concentrations in the DE/RE solutions were less than 0.03125 ppm and not detected in W. In conclusion, the fluoride-containing adhesive system performed similarly to the regular one. Hydrolytic degradation is the main problem with both adhesive systems, regardless of fluoride contents.

Modeling The Effects Of Temperature And Ph On The Resistance Of Alicyclobacillus Acidoterrestris In Conventional Heat-treated Fruit Beverages Through A Meta-analysis Approach.

In this work, all publicly-accessible published findings on Alicyclobacillus acidoterrestris heat resistance in fruit beverages as affected by temperature and pH were compiled. Then, study characteristics (protocols, fruit and variety, °Brix, pH, temperature, heating medium, culture medium, inactivation method, strains, etc.) were extracted from the primary studies, and some of them incorporated to a meta-analysis mixed-effects linear model based on the basic Bigelow equation describing the heat resistance parameters of this bacterium. The model estimated mean D* values (time needed for one log reduction at a temperature of 95 °C and a pH of 3.5) of Alicyclobacillus in beverages of different fruits, two different concentration types, with and without bacteriocins, and with and without clarification. The zT (temperature change needed to cause one log reduction in D-values) estimated by the meta-analysis model were compared to those ('observed' zT values) reported in the primary studies, and in all cases they were within the confidence intervals of the model. The model was capable of predicting the heat resistance parameters of Alicyclobacillus in fruit beverages beyond the types available in the meta-analytical data. It is expected that the compilation of the thermal resistance of Alicyclobacillus in fruit beverages, carried out in this study, will be of utility to food quality managers in the determination or validation of the lethality of their current heat treatment processes.

Uso de membranas de Nafion para a construção de sensores ópticos para medidas de pH

The behaviour of Nafion® polymeric membranes containing acid-base dyes, bromothymol blue (BB) and methyl violet (MV), were studied aiming at constructing an optical sensor for pH measurement. BB revealed to be inadequate for developing sensing phases due to the electrostatic repulsion between negative groups of their molecules and the negative charge of the sulfonate group of the Nafion®, which causes leaching of the dye from the membrane. On the other hand, MV showed to be suitable due to the presence of positive groups in its structure. The membrane prepared from a methanolic solution whose Nafion®/dye molar ratio was 20 presented the best analytical properties, changing its color from green to violet in the pH range from 0.6 to 3.0. The membrane can be prepared with good reproducibility, presenting durability of ca. 6 months and response time of 22 s, making possible its use for pH determination in flow analysis systems.

Estudo da capacidade de complexação e sua relação com algumas variáveis ambientais em cinco represas do Rio Tietê/Brasil

The copper and cadmium complexation properties in natural sediment suspensions of reservoirs of the Tietê River were studied using the solid membrane copper and cadmium ion-selective electrodes. The complexation and the average conditional stability constants were determined under equilibrium conditions at pH=6.00 ± 0.05 in a medium of 1.0 mol L-1 sodium nitrate, using the Scatchard method. The copper and cadmium electrodes presented Nernstian behavior from 1x10-6 to 1x10-3 mol L-1 of total metal concentration. Scatchard graphs suggest two classes of binding sites for both metals. A multivariate study was done to correlate the reservoirs and the variables: complexation properties, size, total organic carbon, volatile acid sulfide, E II and pH.

Antioxidative responses of cell suspension cultures of two Coffea arabica varieties to low aluminum levels at pH 5.8

The effects of aluminum (Al) on the activities of antioxidant enzymes and ferritin expression were studied in cell suspension cultures of two varieties of Coffea arabica, Mundo Novo and Icatu, in medium with pH at 5.8. The cells were incubated with 300 µM Al3+, and the Al speciation as Al3+ was 1.45% of the mole fraction. The activities of superoxide dismutase (SOD), catalase (CAT), and glutathione S-transferase (GST) were increased in Mundo Novo, whereas glutathione reductase (GR) and guaiacol peroxidase (GPOX) activities remained unchanged. SOD, GR, and GST activities were increased in Icatu, while CAT activity was not changed, and GPOX activity decreased. The expression of two ferritin genes (CaFer1 and CaFer2) were analyzed by Real-Time PCR. Al caused a downregulation of CaFER1 expression and no changes of CaFER2 expression in both varieties. The Western blot showed no alteration in ferritin protein levels in Mundo Novo and a decrease in Icatu. The differential enzymes responses indicate that the response to Al is variety-dependent.