Biomimetic sensor based on 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H- porphyrin iron (III) chloride and MWCNT for selective detection of 2,4-D

Exploitation of the electronic properties of carbon nanotubes for the development of voltammetric and amperometric sensors to monitor analytes of environmental relevance has increased in recent years. This work reports the development of a biomimetic sensor based on a carbon paste modified with 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphyrin iron (III) chloride (a biomimetic catalyst of the P450 enzyme) and multi-wall carbon nanotubes (MWCNT), for the sensitive and selective detection of the herbicide 2,4- dichlorophenoxyacetic acid (2,4-D). The sensor was evaluated using cyclic voltammetry and amperometry, for electrochemical characterization and quantification purposes, respectively. Amperometric analyses were carried out at -100 mV vs. Ag/AgCl(KClsat), using a 0.1 mol L-1 phosphate buffer solution at pH 6.0 as the support electrolyte. Under these optimized analytical conditions, the sensor showed a linear response between 9.9 × 10-6 and 1.4 × 10-4 mol L-1, a sensitivity of 1.8 × 104 (±429) μA L mol -1, and limits of detection and quantification of 2.1 × 10 -6 and 6.8 × 10-6 mol L-1, respectively. The incorporation of functionalized MWCNT in the carbon paste resulted in a 10-fold increase in the response, compared to that of the biomimetic sensor without MWCNT. In addition, the low applied potential (-100 mV) used to obtain high sensitivity also contributed to the excellent selectivity of the proposed sensor. The viability of the application of this sensor for analysis of soil samples was confirmed by satisfactory recovery values, with a mean of 96% and RSD of 2.1% (n = 3). © 2013 Elsevier B.V.

Development of an electrochemical sensor based on nanostructured hausmannite-type manganese oxide for detection of sodium ions

The preparation and electrochemical characterization of hausmannite-type manganese oxide to use as a sensing material for sodium ion is described. This paper reports a new via synthetic to obtain of the hausmannite-type manganese oxide and its application in the construction of modified electrode as a voltammetric sensor. The electrochemical activity of hausmannite-type manganese oxide is controlled by intercalation/deintercalation of the sodium ions within the oxide lattice. The detection is based on the measurement of anodic current generated by oxidation of MnIII-MnIV at electrode surface. The best electrochemical response was obtained for a sensor composition of 20% (w/w) hausmannite oxide in the paste, a TRIS buffer solution of pH 6.0-7.0 and a scan rate of 50 mV s-1. A sensitive linear voltammetric response for sodium ions was obtained in the concentration range of 2.01 × 10 -5-2.09 × 10-4 mol L-1 with a slope of 355 μA L mmol-1 and a detection limit of 7.50 × 10 -6 mol L-1 using cyclic voltammetry. The use of hausmannite has significantly improved the selectivity of the sensor compared to the birnessite-type manganese oxide modified electrode. Under the working conditions, the proposed method was successfully applied to determination of sodium ions in urine samples. © 2013 Elsevier B.V.

A new hybrid polyhedral cubic silsesquioxane chemically modified with 4-amino-5-(4-pyridyl)-4H-1,2,4-triazole-3-thiol (APTT) and copper hexacyanoferrate(III) for voltammetric determination of nitrite

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

Electrochemical behavior of ruthenium-hexacyanoferrate modified glassy carbon electrode and catalytic activity towards ethanol electrooxidation

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Electrochemical Properties of Oxo-Manganese Complex Biomimicking Enzyme Active Sites and Its Electrocatalytic Application for Dopamine Determination

This work describes the characterization of the [Mn2 IV,IVO2(terpy)2(H2O)2]4+ complex in aqueous solution by UV-vis spectrophotometry, cyclic voltammetry, and linear sweep voltammetry with a rotating disk electrode. The pH effect, potential scan rate, effect of perfluorosulfonate polymer, and anion of supporting electrode on the electrochemical behavior of the modified electrode for better performance were investigated. The potential peak of the modified electrode was linearly dependent upon the ratio [ionic charge]/[ionic radius]. The modified electrode exerted an electrocatalytic effect on dopamine oxidation in aqueous solution with a decrease in the overpotential compared with the unmodified glassy carbon electrode. This way, the modified electrode showed an enzymatic biomimicking behavior. Tafel plot analyses were used to elucidate the kinetics and mechanism of dopamine oxidation. © 2013 Springer Science+Business Media New York.

A cubic silsesquioxane modified with purpald®: Preparation, characterization and a voltammetric application for determination of sulfite

A novel composite formed by interaction of a octa(3-chloropropyl)octasilsesquioxane modified with Purpald®, and its subsequent reaction with silver and hexacyanoferrate (III) (AgHSP), was synthesized and initially characterized by Fourier transform infrared spectra (FTIR) and cyclic voltammetry. The cyclic voltammogram of the modified graphite paste electrode with AgHSP, showed one redox couple with formal potential Eθ'=0.64V (vs Ag/AgCl, KNO3, 1.0 mol L-1; v = 20 mV s-1), attributed to the Fe2+(CN)6/ Fe3+(CN)6 process. The redox couple presents an electrocatalytic response for determination of sulfite. The modified electrode showed a linear response from 7.0×10-5 to 1.0×10-3 mol L-1 with the corresponding equation Y(μA) = 18.05 + 29.983×103 [sulfite], and a correlation coefficient of r=0.999. The method showed a detection limit of 0.115×10-4 mol L-1 with a relative standard deviation of ± 4% (n = 3) and amperometric sensitivity of 29.983×10-3A mol L-1. The modified electrode showed a excellent stability and good reproducibility during experiments. © 2013 by ESG.

Sensitive voltammetric sensor for fast detection of mycolic acids present in mycobacteria

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

The relation between structural features and electrochemical activity of MnO2 nanoparticles synthesized from a polyol-made Mn 3O4 precursor

A simple hybrid synthesis processing method was developed to synthesize γ-MnO2 nanocrystalline particles. The polyol method was modified by the addition of nitric acid in order to allow the synthesizing of single-phase Mn3O4 in a large scale. In the sequence, the acid digestion technique was used to transform Mn3O4 into γ-MnO2. Structural and morphological characterization was carried out by X-ray diffractometry, Infrared and Raman spectroscopy, thermogravimetric analysis, nitrogen adsorption isotherm, scanning electron microscopy, and transmission electron microscopy. The electrochemical properties were investigated by cyclic voltammetry and galvanostatic charge-discharge measurements. The synthesized material exhibits a specific capacitance of 125.1 F g-1 at a mass loading of 0.98 mg cm-2. The relation between structural features and electrochemical activity is discussed by comparing the synthesized material with commercial electrolytic manganese dioxide. © 2013 Springer-Verlag Berlin Heidelberg.

Determination of Total Nitrosamines in Vegetables Cultivated Organic and Conventional Using Diamond Electrode

Vegetables were analyzed for total N-nitrosamines (NAs) and the influence of disinfection processes was assessed. Differences in NAs found in cabbage, spinach, and broccoli were determined by square wave voltammetry using a boron-doped diamond electrode. Analysis of samples showed that all samples contained detectable levels of NAs but the results indicated that organic contained less than conventionally grown products. The sum of the total NAs was higher in the cabbage samples, ranging between 2.8-3.1 ppb and lower in broccoli samples at 0.2-1.1 ppb. The method described is simple, rapid, selective, and sensitive. The results suggested that the disinfection process affects the level of NAs, in this manner affecting the level of human exposure to NAs. © 2012 Springer Science+Business Media New York.

On the electrochemical behavior of Cu-16%Zn-6.5%Al alloy containing the β'-phase (martensite) in borate buffer

In this work, the electrochemical behavior of Cu-16(wt.%)Zn-6.5(wt.%)Al alloy containing the β'-phase (martensite) was studied in borate buffer solution (pH 8.4) by means of open-circuit potential (EOC), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The alloy EOC was -0.29 V vs. Hg/HgO/OH-, similar to that of pure copper in this medium, indicating that the processes which occur on the alloy surface are mainly governed by copper. EIS response was related to the dielectric and transmission properties of the complex oxide layer. The CVs showed peaks concerning the redox reactions for copper and zinc. These peaks were assigned to the formation and reduction of copper and zinc species. Furthermore, they showed that the copper oxidation was suppressed by the presence of zinc and aluminum in the alloy composition. The copper and zinc oxidation to form complex oxide layers and the reduction of the different metallic oxides generated in the anodic potential scan suggest that a solid state reaction could determine the metallic oxide formation. © 2013 Elsevier Ltd. All rights reserved.

A novel LTCC electrochemical cell construction and characterization: A detection compartment for portable devices

In this work we described for the first time the construction of a 25 μL electrochemical cell from low temperature co-fired ceramic (LTCC) material and carbon screen-printed electrode applicable in portable devices. Firstly, a carbon screen-printed electrode was prepared and characterized by cyclic voltammetry and scanning electron microscopy. Afterwards carbon polymeric film and metal pastes were dropped into the LTCC cell cavities in order to determine the device electrodes, and this arrangement was also electrochemically characterized. The great advantage of this promising device is the simple construction method and its widespread applicability in reusable portable devices. © 2013 The Royal Society of Chemistry.

Ethanol electro-oxidation in an alkaline medium using Pd/C, Au/C and PdAu/C electrocatalysts prepared by electron beam irradiation

Carbon-supported Pd, Au and bimetallic PdAu (Pd:Au 90:10, 50:50 and 30:70 atomic ratios) electrocatalysts were prepared using electron beam irradiation. The obtained materials were characterized by energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD) and transmission electron microscopy (TEM), and their catalytic activities toward ethanol electro-oxidation were evaluated in an alkaline medium using electrochemical techniques, in situ attenuated total reflectance Fourier transformed infrared spectroscopy (ATR-FTIR) analysis and a single alkaline direct ethanol fuel cell (ADEFC). EDX analyses showed that the actual Pd: Au atomic ratios were very similar to the nominal ones. X-ray diffractograms of PdAu/C electrocatalysts evidenced the presence of Pd-rich (fcc) and Au-rich (fcc) phases. TEM analysis showed a homogeneous dispersion of nanoparticles on the carbon support, with an average size in the range of 3-5 nm and broad size distributions. Cyclic voltammetry (CV) and chronoamperometry (CA) experiments revealed the superior ambient activity toward ethanol electro-oxidation of PdAu/C electrocatalysts with Pd: Au ratios of 90:10 and 50:50. In situ ATR-FTIR spectroscopy measurements have shown that the mechanism for ethanol electro-oxidation is dependent on catalyst composition, leading to different reaction products, such as acetaldehyde and acetate, depending on the number of electrons transferred. Experiments on a single ADEFC were conducted between 50 and 900 C, and the best performance of 44 mW cm-2 in 2.0molL-1 ethanol was obtained at 850C for the Pd:Au 90:10 catalysts. This superior performance is most likely associated with enhancement of ethanol adsorption on Pd, oxidation of the intermediates, the presence of gold oxide-hydroxyl species, low mean particle diameters and better distribution of particles on the support. © 2013 Elsevier Ltd. All rights reserved.

Cost-effective composite electrode for the fast voltammetric screening and determination of riboflavin (B2) and pyridoxine (B6) in pharmaceuticals

Different solid composites made by mechanical dispersions of graphite particles into heated paraffin (from 65 to 80% graphite, in mass) were prepared and assessed in order to optimize their use in electrochemical and electroanalytical procedures for bioanalysis. Besides these, composites were also evaluated by thermoanalytical techniques aiming to study their conservation and long-term stability (over eight months without special care), among others. Best results were found at 80% m/m graphite in paraffin. Such electrode combines low-cost, stability, sensitivity, ease of maintenance and clearance, besides the possibilities of manufacture in many different forms and shapes (with or without modifications) and applicability in a wide range of pH. Electrochemical studies by different voltammetric techniques involving vitamins from complex B (riboflavin and pyridoxine) leaded to a better understanding about their electrooxidative processes onto carbon-composite electrodes, specially regarding reversibility and pH-dependence. Data were also acquired and optimized with analytical purposes, being square-wave voltammetry in pH 4.2 chosen by its many advantages. Good linearity between peak responses as function of concentration were reached from 5 to 43 μmol L-1 for riboflavin (peak at -0.257 V) and up to 8.5 × 10-4 mol L -1 for pyridoxine (peak at +1.04 V), best studied conditions; limits of detection (at an S/N of 3) for both analites showed to be circa 1.0 mol L-1. Different commercial samples were analyzed for riboflavin (EMS® complex B syrup) and pyridoxine (Citoneurin 5000 Merck® ampoules) providing 96.6% and 98.7% recoveries, respectively.

Electrochemical sensor for ranitidine determination based on carbon paste electrode modified with oxovanadium (IV) salen complex

The preparation and electrochemical characterization of a carbon paste electrode modified with the N,N-ethylene-bis(salicyllideneiminato)oxovanadium (IV) complex ([VO(salen)]) as well as its application for ranitidine determination are described. The electrochemical behavior of the modified electrode for the electroreduction of ranitidine was investigated using cyclic voltammetry, and analytical curves were obtained for ranitidine using linear sweep voltammetry (LSV) under optimized conditions. The best voltammetric response was obtained for an electrode composition of 20% (m/m) [VO(salen)] in the paste, 0.10 mol L- 1 of KCl solution (pH 5.5 adjusted with HCl) as supporting electrolyte and scan rate of 25 mV s- 1. A sensitive linear voltammetric response for ranitidine was obtained in the concentration range from 9.9 × 10- 5 to 1.0 × 10- 3 mol L- 1, with a detection limit of 6.6 × 10- 5 mol L- 1 using linear sweep voltammetry. These results demonstrated the viability of this modified electrode as a sensor for determination, quality control and routine analysis of ranitidine in pharmaceutical formulations. © 2013 Published by Elsevier B.V.

Fast assembly of non-thiolated DNA on gold surface at lower pH

In a typical protocol for attaching DNA to a gold electrode, thiolated DNA is incubated with the electrode at neutral pH overnight. Here we report fast adsorption of non-thiolated DNA oligomers on gold electrodes at acidic pH (i.e., pH ~3.0). The peak-to-peak potential difference and the redox peak currents in typical cyclic voltammetry of [Fe(CN)6]3- are investigated to monitor the attachment. Compared with incubation at neutral pH, the lower pH can significantly promote the adsorption processes, enabling efficient adsorption even in 30min. The adsorption rate is DNA concentration-dependent, while the ionic strength shows no influence. Moreover, the adsorption is base-discriminative, with a preferred order of A>C≫G, T, which is attributed to the protonation of A and C at low pH and their higher binding affinity to gold surface. The immobilized DNA is functional and can hybridize with its complementary DNA but not a random DNA. This work is promising to provide a useful time-saving strategy for DNA assembly on gold electrodes, allowing fast fabrication of DNA-based biosensors and devices. © 2013 Elsevier Inc.