Electrochemical Sensing Platform Based on Metal Nanoparticles for Epinephrine and Serotonin.

A sensing platform based on nanocomposite materials composed of gold metal nanoparticles (AuNPs) and conducting polymer (CP) matrix has been developed for serotonin and epinephrine detection. The CP-AuNPs nanocomposite materials have been synthesized onto glassy carbon electrodes (GCE) by using novel electrochemical procedures based on sinusoidal currents (SC). The SC procedures ensured good control of the metal nanoparticles distribution, increased electrochemical surface area, and enhanced analytical performance. The proposed sensing platform displayed good analytical performance toward serotonin and epinephrine detection. A wide linear analytical response toward epinephrine in the range from 10 to 640 µM and a low detection limit of 1.4 µM epinephrine has been obtained. The sensing platform has also displayed a linear response toward serotonin in the range from 10 to 320 µM, with a detection limit of 5.7 µM serotonin. The sensing platform has been successfully applied in the analysis of epinephrine and serotonin in real samples of tap water and urine with good accuracy.

Copper(II) Oxide Nanoparticles Embedded within a PEDOT Matrix for Hydrogen Peroxide Electrochemical Sensing.

The aim of this study is the preparation of nanostructured copper(II) oxide-based materials (CuONPs) through a facile additive-free polyol procedure that consists of the hydrolysis of copper(II) acetate in 1,4-butane diol and its application in hydrogen peroxide sensing. The nonenzymatic electrochemical sensor for hydrogen peroxide determination was constructed by drop casting the CuONP sensing material on top of a glassy carbon electrode (GCE) modified by a layer of poly(3,4-ethylenedioxythiophene) conducting polymer (PEDOT). The PEDOT layer was prepared on GCE using the sinusoidal voltage method. The XRD pattern of the CuONPs reveals the formation of the monoclinic tenorite phase, CuO, with average crystallite sizes of 8.7 nm, while the estimated band gap from UV-vis spectroscopy is of 1.2 eV. The SEM, STEM, and BET analyses show the formation of quasi-prismatic microaggregates of nanoparticles, with dimensions ranging from 1 µm up to ca. 200 µm, with a mesoporous structure. The developed electrochemical sensor exhibited a linear response toward H2O2 in the concentration range from 0.04 to 10 mM, with a low detection limit of 8.5 µM of H2O2. Furthermore, the obtained sensor possessed an excellent anti-interference capability in H2O2 determination in the presence of interfering compounds such as KNO3 and KNO2.

A Sensitive Electrochemical Sensor Based on Sonogel-Carbon Material Enriched with Gold Nanoparticles for Melatonin Determination.

In this work, the development of an electrochemical sensor for melatonin determination is presented. The sensor was based on Sonogel-Carbon electrode material (SNGCE) and Au nanoparticles (AuNPs). The low-cost and environmentally friendly SNGCE material was prepared by the ultrasound-assisted sonogel method. AuNPs were prepared by a chemical route and narrow size distribution was obtained. The electrochemical characterization of the SNGCE/AuNP sensor was carried out by cyclic voltammetry in the presence of a redox probe. The analytical performance of the SNGCE/AuNP sensor in terms of linear response range, repeatability, selectivity, and limit of detection was investigated. The optimized SNGCE/AuNP sensor displayed a low detection limit of 8.4 nM melatonin in synthetic samples assessed by means of the amperometry technique. The potential use of the proposed sensor in real sample analysis and the anti-matrix capability were assessed by a recovery study of melatonin detection in human peripheral blood serum with good accuracy.

Sinusoidal voltage electrodeposition of PEDOT-Prussian blue nanoparticles composite and its application to amperometric sensing of H2O2 in human blood.

A selective electrochemical sensor based on poly(3,4-ethylenedioxythiophene) (PEDOT) - Prussian blue nanoparticles (PBNPs) for hydrogen peroxide (H2O2) determination was prepared by innovative sinusoidal voltage (SV) method. The successful incorporation of citrate-stabilized PBNPs into PEDOT matrix was confirmed by energy dispersive X-ray analysis (EDX), Raman spectroscopy, UV-Vis spectroelectrochemistry and cyclic voltammetry measurements. The SV preparation method provides a PEDOT-PBNPs coating with rough surface morphology and good electrocatalytic activity toward H2O2 reduction. The amperometric response of PEDOT-PBNPs-based sensor at -50 mV vs. Ag/AgCl is linear within the range of concentrations from 5 µM to 1 mM H2O2 with a detection limit of 1.4 µM H2O2. The proposed Pt/PEDOT-PBNPs sensor displays good repeatability, reproducibility, operational stability as well as good selectivity toward H2O2 determination in the presence of interfering species like dopamine (DA), uric acid (UA), KNO2 glucose (Glu), KNO3 and ascorbic acid (AA), and was successfully applied to H2O2 determination in human blood samples without biofouling.

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.

Physicochemical and Antioxidant Properties of Riboflavin in Dextran70/HSA Systems.

Physicochemical properties of Riboflavin (Vitamin B2) (RF), in Dextran 70 (Dx70) (a biological relevant glucidic type macromolecule) and Human Serum Albumin (HSA) (a carrier/transport protein) based system, have been studied by absorption, fluorescence, circular dichroism and electrochemistry. No significant changes on the fluorescence of RF in Dx70/HSA systems with and without the influence of temperature (30-60 °C range) were observed. No changes on the intrinsic Tryptophan fluorescence in Dx70/RF/HSA system, have been evidenced. HSA secondary structure when RF binds in Dx70/RF/HSA systems, with a renaturation effect of Dx70, was found. In Dx70/RF/HSA system the major process which RF undergoes is the proton transfer, Ered = -0.43 V. Using the chemiluminescence method, an improvement of the antioxidant activity of RF into the Dx70/RF/HSA system, was also found. RF concentration in Dx70/RF/HSA systems is important in RF oxidative damages when it reacts with target molecules and thus promotes their oxidation. The results have relevance in the oxidative stress process and in pharmaceutical formulations containing RF.

Development of amperometric biosensors based on nanostructured tyrosinase-conducting polymer composite electrodes.

Bio-composite coatings consisting of poly(3,4-ethylenedioxythiophene) (PEDOT) and tyrosinase (Ty) were successfully electrodeposited on conventional size gold (Au) disk electrodes and microelectrode arrays using sinusoidal voltages. Electrochemical polymerization of the corresponding monomer was carried out in the presence of various Ty amounts in aqueous buffered solutions. The bio-composite coatings prepared using sinusoidal voltages and potentiostatic electrodeposition methods were compared in terms of morphology, electrochemical properties, and biocatalytic activity towards various analytes. The amperometric biosensors were tested in dopamine (DA) and catechol (CT) electroanalysis in aqueous buffered solutions. The analytical performance of the developed biosensors was investigated in terms of linear response range, detection limit, sensitivity, and repeatability. A semi-quantitative multi-analyte procedure for simultaneous determination of DA and CT was developed. The amperometric biosensor prepared using sinusoidal voltages showed much better analytical performance. The Au disk biosensor obtained by 50 mV alternating voltage amplitude displayed a linear response for DA concentrations ranging from 10 to 300 µM, with a detection limit of 4.18 µM.

Raman and in situ FTIR-ATR characterization of polyazulene films and its derivate.

Polymers from azulene (A) and 2-[(E)-2-azulen-1-ylvinyl]thiophene (B) electrochemically synthesized are materials with a broad absorbance in the UV-vis spectral region. An experimental approach to correlate the Raman and in situ FTIR spectra from azulene based polymers according to the effective conjugation coordinate theory (ECC) is presented. Film characterization was made by Raman and Fourier transform infrared attenuated total reflectance, FTIR-ATR spectroscopy. Throughout the whole work A was used as a model compound. The polymers were synthesized at different polymerization potentials in order to create different structures. Polyazulene showed a divergent Raman response upon change in excitation wavelength, lambda(exc)= 514 nm and lambda(exc)= 780 nm, in comparison to common conducting polymers. The FTIR-ATR measurements were made during charging-discharging of the polymers. The IR spectra of the conducting state show new doping induced infrared active vibrations (IRAV) in the region between 1600 and 700 cm(-1) and a broad electronic absorption in the high energy range (4000-8000 cm(-1)). Two different structures of the polymer from B are formed, and both follow the trends for conducting polymers upon charging.