Polyaniline Nanofibers-Embedded Gold Nanoparticles Obtained by Template-Free Procedure with Immobilization Prospects.

In this work, template-free nanostructured conducting polymers (nCPs)-embedded gold nanoparticles (AuNPs) from aniline, thiophene and 3,4-ethylenedioxythiophene have been prepared via a one-pot sonochemical method. The synthesis of the nanocomposite (nCPs-AuNPs) was achieved in a short period of time (5-10 min), by applying high-energy ultrasound to an aqueous mixture of a CP precursor monomer and KAuCl4, in the presence of LiClO4 as dopant. The synthesis process is simpler, greener and faster in comparison to other procedures reported in the literature. Remarkably, bulk quantities of doped polyaniline PANI-AuNPs nanofibers were obtained. Subsequently, they were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS) and Fourier transform infrared spectroscopy (FTIR), as well as by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). PANI-AuNPs nanofibers were also employed as immobilization matrix for a benchmark enzyme, glucose oxidase (GOX). Finally, glucose was determined in real samples of white and red wines by using the so-obtained GOX-PANI-AuNPs/Sonogel-Carbon biosensor, providing outstanding recoveries (99.54%). This work may offer important insights into the synthesis of nanostructured conducting polymers and also stimulates the exploration of the applications of these nanocomposites, especially in research fields such as (bio)sensors, catalysis and composite materials.

Assessment of the Polyphenol Indices and Antioxidant Capacity for Beers and Wines Using a Tyrosinase-Based Biosensor Prepared by Sinusoidal Current Method.

The application of a novel Poly(3,4-ethylenedioxythiophene)-Tyrosinase/Sonogel-Carbon electrode (PEDOT-Tyr/SNGC) biosensor to beers and wines analysis is proposed. This biosensor implies a new Sinusoidal Current (SC) electrodeposition method to immobilize the enzyme generating a nanostructure surface. The biosensors were characterized electrochemically, employing cyclic voltammetry and electrochemical impedance spectroscopy. Sensitivity, limit of detection, and correlation coefficients of the linear fitting were 2.40 × 10-4 µA·µM-1, 4.33 µM, and R² = 0.9987, respectively. Caffeic acid is used as the reference polyphenol. A sampling of nine beers (four lager, three stout, and two non-alcoholic beers), and four wines (three red and one white wine) purchased in a local store was performed. The Polyphenol indeces for beers and wines have been assessed using the proposed biosensor, and the obtained values are in agreement with the literature data. Antioxidant properties of the samples using the 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid (ABTS) radical spectrophotometric method were also evaluated. The correlation between the polyphenol index and the antioxidant capacity was obtained for beers and wines.

Simple and cost-effective pH and T sensors from top to bottom: New chemical probes based on sonogel-carbon transducers for plasma analyses.

The present work introduces two novel approaches to fabricate simple and cost-effective pH and temperature probes. Sinusoidal voltage methodologies were employed to electrodeposit polyaniline (PANI) at different growth times (10-20 min) on the surface of an affordable Sonogel-Carbon electrode to conform a robust pH sensor. The presence of PANI and its phases were corroborated by electrochemical means. The sensibility, reversibility and selectivity of the produced sensor were very adequate to apply it in physiological samples. In this regard, the proposed sensor was evaluated in artificial blood serum as well as untreated plasma samples obtaining outstanding results in comparison with a gold reference technique (error <2 %). In addition, a new composite sonogel material, intrinsically modified with multiwalled carbon nanotubes, was attached on top of an electrode couple to one-step fabricate a new temperature probe, relating resistance of the probe with the surroundings temperature. In this case, an optical microscopy characterization was performed to study the sturdiness of the layer. Remarkably, suitable results in terms of sensitivity and selectivity were obtained. The probes were assessed in artificial and untreated plasma samples as well, with the corresponding validation step (error <1 %) by using a commercial temperature probe.

Recent advances in graphite powder-based electrodes.

Graphite powder-based electrodes have the electrochemical performance of quasi-noble metal electrodes with intrinsic advantages related to the possibility of modification to enhance selectivity and their easily renewable surface, with no need for hazardous acids or bases for their cleaning. In contrast with commercial electrodes, for example screen-printed or sputtered-chip electrodes, graphite powder-based electrodes can also be fabricated in any laboratory with the form and characteristics desired. They are also readily modified with advanced materials, with relatively high reproducibility. All these characteristics make them a very interesting option for obtaining a large variety of electrodes to resolve different kinds of analytical problems. This review summarizes the state-of-the-art, advantages, and disadvantages of graphite powder-based electrodes in electrochemical analysis in the 21st century. It includes recent trends in carbon paste electrodes, devoting special attention to the use of emergent materials as new binders and to the development of other composite electrodes. The most recent advances in the use of graphite powder-modified sol-gel electrodes are also described. The development of sonogel-carbon electrodes and their use in electrochemical sensors and biosensors is included. These materials extend the possibilities of applications, especially for industrial technology-transfer purposes, and their development could affect not only electroanalytical green chemistry but other interesting areas also, for example catalysis and energy conversion and storage.

An electrochemical alternative for evaluating the antioxidant capacity in walnut kernel extracts.

A fast, precise and inexpensive alternative for evaluating the antioxidant activity (AA) in walnut kernel extracts is proposed. Traditional ABTS assay and an electrochemical index approach have been applied to evaluate the AA in walnuts. A fast and efficient defatting of the walnuts by ultrasound assisted extraction (UAE) was carried out. Later, for the extraction of polyphenolic compounds, a procedure based on UAE in ethanolic medium was used. The AA of the sample ethanolic extracts was expressed as both % of inhibition by the ABTS spectrophotometric method and the electrochemical index approach (EI) obtained by the ratio between current and potential peak values using differential pulse voltammetry (DPV) at a Sonogel-Carbon electrode. The behaviour of the EI approach have been explored using six polyphenols standards and walnut kernel extracts at pH 2. All the polyphenols appeared at an oxidation potential between 0.476 and 0.778 V. Eleven samples available to consumers were analysed. A high significant correlation (R2 = 0.927) between the spectrophotometric measurements and the EI approach of the walnut extracts was obtained.

A handling-free methodology for rapid determination of Cu species in seawater based on direct solid micro-samplers analysis by high-resolution continuum source graphite furnace atomic absorption spectrometry.

A very simple, sensible and advanced new methodology for the determination of copper species in seawater has been developed. The method consisted of two steps: first a separation/preconcentration of copper species by using liquid phase microextraction-based solvent bars followed by the direct analysis of these solid polymeric micro-samplers in an atomic absorption spectrometer provided with a device for direct analysis. For liquid microextraction, di-2-pyridylketone benzoylhydrazone (dPKBH) dissolved in octan-1-ol was selected as the extracting agent due to its ability to transport inorganic Cu species from seawater samples. The optimum chemical and physical conditions for copper micro-extraction were sample pH 8, a dPKBH concentration of 0.010 mol L-1, a stirring speed of 800 rpm and an extraction time of 10 min. A graphite furnace temperature program was optimised to assure the complete elimination of the solvent bar matrix, and the atomisation step took place at 2200 °C. The method exhibited a limit of detection of 0.026 µg L-1 of copper and a linear range up to 1.50 µg L-1, showing great repeatability and reproducibility (4.07% and 4.43%, respectively). Suitability of the method was confirmed by analysing a certified reference material (CASS-4) under optimum conditions, being the first time ever that a direct solid analysis-based method has been used for the determination of total dissolved copper concentration in seawater. Furthermore, the method was applied to the determination of the operationally defined transportable Cu fraction in seawater samples at natural conditions and the results were compared with theoretical data provided by Visual MINTEQ® 3.1 software. A mathematical model that permits to estimate total dissolved copper concentration was obtained, and the non-transportable copper fraction was calculated by difference.

A simple phosphorus determination in walnuts and assessment of the assimilable fraction.

In this work, a method for the determination of phosphorus in walnuts has been developed due to the fact that there is no specific method for this purpose. A closed-vessel microwave-assisted digestion of the samples was optimized and a modified molybdenum blue spectrophotometric method was carried out with excellent precision and selectivity. To differentiate assimilable and non-assimilable phosphorus, an easy extraction procedure using 1 M NH4Cl was used. FTIR spectra ensured that the phytate extraction was successful. A sampling of thirteen different walnuts available to consumers from different crops and geographical origin was performed. Comparative statistical tools to differentiate walnuts were also carried out. Significant differences based on total content of phosphorus were obtained. Finally, a correlation study between total phosphorus concentration and the non-assimilable fraction showed a non-linear relationship (R2 = 0.435). Therefore, in relation to consumer health the total phosphorus determination must be complemented with information about assimilable phosphorus.

A comparison of three amperometric phenoloxidase-Sonogel-Carbon based biosensors for determination of polyphenols in beers.

Three phenoloxidases based biosensors were successfully developed using as electrochemical transducer a new type of electrode recently developed by our group: the "Sonogel-Carbon electrode". The employed enzymes were Trametes versicolor laccase (Lac), Mushroom tyrosinase (Tyr), and Horseradish peroxidase (HRP). Immobilization step was accomplished by doping the electrode surface with a mixture of the individual enzyme and Nafion ion exchanger as additive-protective. The biosensor responses, optimized in beer real samples, were evaluated for five individual polyphenols. It was found that the developed biosensors were sensitive to nanomolar concentrations of the tested polyphenols. As example, the limit of detection, sensitivity, and response linear range for caffeic acid for Nafion-Lac/Sonogel-Carbon biosensor were 0.06µmolL(-1), 99.6nAµmol(-1)L, and 0.04-2µmolL(-1), respectively. The stability and reproducibility of the biosensors were evaluated by applying them directly to beer real samples. It has been demonstrated that the Nafion-Lac/Sonogel-Carbon system is the more stable with a relative standard deviation of 3.3% (n=10), maintaining 84% of its stable response for at least three weeks. Estimation of polyphenol index in eight lager beers and a comparison of the results with those obtained by a classical method was carried out.

Selective methods for polyphenols and sulphur dioxide determination in wines.

A critical review to the methods recommended by international bodies and widely used in the winery industry and research studies was performed. A Laccase biosensor was applied to the selective determination of polyphenols in wines. The biosensor response was characterised and it responds mainly to o-diphenols which are the principal polyphenols responsible for the stability and sensory qualities of wines. The spectrophotometric method to determine free and total sulphur dioxide recommended for beers was applied directly to wines. A sampling of 14 red and white wines was performed and they were analysed for biosensor polyphenol index (IBP) and sulphur dioxide concentration (SO2). The antioxidant capacity by the ABTS(+) spectrophotometric method was also determined. A correlation study was performed to elucidate the influence of the polyphenols and SO2 on the wines stability. High correlations were found between IBP and antioxidant capacity and low correlation between SO2 and antioxidant capacity. To evaluate the benefits of wine drinking a new parameter (IBP/SO2) is proposed.