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This work presents the simultaneous quantification of four non-steroidal anti-inflammatory drugs (NSAIDs), paracetamol, diclofenac, naproxen, and aspirin, in mixture solutions, by a laboratory-made working electrode based on carbon paste modified with multi-wall carbon nanotubes (MWCNT-CPE) and Differential Pulse Voltammetry (DPV). Preliminary electrochemical analysis was performed using cyclic voltammetry, and the sensor morphology was studied by scanning electronic microscopy and electrochemical impedance spectroscopy. The sample set ranging from 0.5 to 80 µmol L-1 was prepared using a complete factorial design (34) and considering some interferent species such as ascorbic acid, glucose, and sodium dodecyl sulfate to build the response model and an external randomly subset of samples within the experimental domain. A data compression strategy based on discrete wavelet transform was applied to handle voltammograms' complexity and high dimensionality. Afterward, Partial Least Square Regression (PLS) and Artificial Neural Networks (ANN) predicted the drug concentrations in the mixtures. PLS-adjusted models (n = 12) successfully predicted the concentration of paracetamol and diclofenac, achieving correlation values of R ≥ 0.9 (testing set). Meanwhile, the ANN model (four layers) obtained good prediction results, exhibiting R ≥ 0.968 for the four analyzed drugs (testing stage). Thus, an MWCNT-CPE electrode can be successfully used as a potential sensor for voltammetric determination and NSAID analysis.

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This work describes an electrochemical sensor for the selective recognition and quantification of amoxicillin and a ß-lactam antibiotic in real samples. This sensor consists of a carbon paste electrode (CPE) modified with mag-MIP (magnetic molecularly imprinted polymer), which was prepared by precipitation method via free radical using acrylamide (AAm) as functional monomer, N,N'-methylenebisacrylamide (MBAA) as a crosslinker, and potassium persulfate (KPS) as initiator, to functionalized magnetic nanoparticles. The magnetic non-imprinted polymers (mag-NIP) were prepared using the same experimental procedure without analyte and used for the preparation of a CPE for comparative studies. The morphological, structural, and electrochemical characteristics of the nanostructured material were evaluated using Field emission gun scanning electron microscopy (FEG-SEM), Transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), Vibrating sample magnetometry (VSM), X-ray diffraction (XRD), and voltammetric technique. Electrochemical experiments performed by square wave voltammetry show that the mag-MIP/CPE sensor had a better signal response compared to the non-imprinted polymer-modified electrode (mag-NIP/CPE). The sensor showed a linear range from 2.5 to 57 µmol L-1 of amoxicillin (r 2 = 0.9964), with a limit of detection and a limit of quantification of 0.75 and 2.48 µmol L-1, respectively. No significant interference in the electrochemical signal of amoxicillin was observed during the testing experiments in real samples (skimmed milk and river water). The proposed mag-MIP/CPE sensor could be used as a good alternative method to confront other techniques to determine amoxicillin in different samples.

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A poly(acrylic acid-co-itaconic acid) (PAA-co-IA)/NaOH hydrogel containing bamboo-type multiwall carbon nanotubes (B-MWCNTs) doped with nitrogen (PAA-co-IA/NaOH/B-MWCNTs) was synthesized and characterized by SEM, absorption of water, point of zero charges, infrared spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. The possible use of the PAA-co-IA/NaOH/B-MWCNT hydrogel as an electrode modifier and pre-concentrator agent for Cd(II) sensing purposes was then evaluated using carbon paste electrodes via differential pulse voltammetry. The presence of the B-MWCNTs in the hydrogel matrix decreased its degree of swelling, stabilized the structure of the swollen gel, and favored the detection of 3 ppb Cd(II), which is comparable to the World Health Organization's allowable maximum value in drinking water. A calibration curve was obtained in the concentration range of 2.67 × 10-8 to 6.23 × 10-7 M (i.e., 3 and 70 ppb) to determine a limit of detection (LOD) of 19.24 µgL-1 and a sensitivity of 0.15 µC ppb-1. Also, the Zn(II), Hg(II), Pb(II) and Cu(II) ions interfered moderately on the determination of Cd(II).

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Tannic acid is often used as additive in beers and is an important parameter to be evaluated in quality control of beverages. Thus, this paper describes the improvement of a carbon paste electrode through its modification with poly(ethylene glycol) for determination of tannic acid in beers. Microscopic and electrochemical techniques were used to characterize the modified surface. The electrochemical behavior of tannic acid and the optimization of experimental parameters (pH, supporting electrolyte and accumulation step) on the modified surface were performed by cyclic voltammetry. The calibration plot for tannic acid by differential pulse voltammetry was linear in the range of 0.08-2.10 µmol L-1 with limits of detection and quantification of 72.6 and 220 nmol L-1, respectively. Lastly, the carbon paste electrode improved with poly(ethylene glycol) was effectively implemented in the quantification of tannic acid in beer samples. The results were similar to those furnished by the Folin-Ciocalteu method.

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From UV-Vis spectrophotometric measurements the acidity constants of Rutin in aqueous media, at 25 °C and 0.1 M ionic strength, were determined as: pK1 = 4.392 ±â€¯0.167, pK2 = 7.130 ±â€¯0.050, pK3 = 8.661 ±â€¯0.042 and pK4 = 12.354 ±â€¯0.020 and the molar absorptivity coefficients of all the Rutin pH-dependent species were reported as a function of wavelength. Furthermore, the electrochemical behavior of Rutin at neutral pH was investigated using a bare carbon paste electrode, CPE. It was found that both: Rutin electrochemical oxidation and reduction are reversible, adsorption-controlled processes, involving 2 electron transfers. Moreover, the bare CPE was used for the electrochemical quantification of Rutin in neutral aqueous media, displaying the following features: (1.078 ±â€¯0.440) µM, (3.594 ±â€¯0.400) µM and (0.308 ±â€¯0.014) µA µM-1 for the detection and quantification limits and sensitivity, respectively, within the 1-11 µM linear range. Meanwhile the spectrophotometric method displayed the following analytical features: (3.385 ±â€¯1.318) µM, (11.283 ±â€¯3.114) µM and (0.0120 ±â€¯0.0001) AU µM-1 for the detection and quantification limits and sensitivity, respectively within the 11-110 µM linear range. In like manner, the bare CPE is also shown as a robust electrochemical sensor that allows Rutin quantification even in the presence of ascorbic acid, commonly found in Rutin samples.

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A simple, inexpensive, highly sensitive, selective, and novel electrochemical method was developed for determination of the Bisphenol A in samples of tap water, blood serum, and urine using a bentonite-modified carbon paste electrode. The graphite, bentonite and the working electrodes (without and chemically modified) were characterized by scanning electron microscopy, infrared absorption spectroscopy, and X-ray diffraction. The electrodes were electrochemically characterized using cyclic voltammetry, square wave voltammetry, and electrochemical impedance spectroscopy. The studied electrochemical variables were: electrode area, standard heterogeneous rate constant, charge transfer coefficient and double-layer capacitance. The bentonite as a sensor modifier had a strong influence on these variables. For the development of the methodology to quantify Bisphenol A, the instrumental parameters (frequency, amplitude, and step potential) and experimental parameters (pH, bentonite quantity) were optimized. The analytical curve to Bisphenol showed a linear response of the oxidation peak current intensity vs. the concentration in the range of 6.8 × 10-10 to 1.5 × 10-8 mol mL-1, with a limit of detection (LOD) of 2.11 × 10-11 mol mL-1 and limit of quantification (LOQ) of 7.04 × 10-11 mol mL-1. Recovery experiments were performed by adding known amounts of Bisphenol A in tap water, blood serum, and urine samples. Recovery rates using the standard addition method were in the range of 97.8-101.8%. The results demonstrated the method feasibility for quantifying Bisphenol A in these samples.

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Molecularly imprinted polymers provide an excellent platform for the modification of selective electrodes for sensing applications. Herein, we present a novel modified carbon paste electrode (CPE) with a selective molecularly imprinted polymer (MIP) for recognition of sesquiterpene ß-caryophyllene, constituted of important plants oil-resins and extracts. The non-covalent MIP was synthesized using AA, EGDMA, and AIBN as a functional monomer, cross-linker and initiator agent, respectively. Structural and chemical characterization of the synthesized MIP was conducted through scanning electron microscopy (SEM), Fourier-transform infrared (FT-IR) spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). It was possible to verify the functional features of the synthesized MIP related to the extraction process of the template molecule. The CPE modified with MIP for sesquiterpene ß-caryophyllene recognition was characterized by electrochemical techniques as cyclic voltammetry (CV) and square wave voltammetry (SWV). The highest selective recognition electrode enables to detect concentrations in the range between 1.5 × 10-7 and 7.5 × 10-7 M, showing great potential for applications in monitoring content of sesquiterpene ß-caryophyllene in technological processes and for predicting the quality of extracts, oils, and resins of plants.

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This work presents a simple and low-cost analytical approach to detect adulterations in ground roasted coffee by using voltammetry and chemometrics. The voltammogram of a coffee extract (prepared as simulating a home-made coffee cup) obtained with a single working electrode is submitted to pattern recognition analysis preceded by variable selection to detect the addition of coffee husks and sticks (adulterated/unadulterated), or evaluate the shelf-life condition (expired/unexpired). Two pattern recognition methods were tested: linear discriminant analysis (LDA) with variable selection by successive projections algorithm (SPA), or genetic algorithm (GA); and partial least squares discriminant analysis (PLS-DA). Both LDA models presented satisfactory results. The voltammograms were also evaluated for the quantitative determination of the percentage of impurities in ground roasted coffees. PLS and multivariate linear regression (MLR) preceded by variable selection with SPA or GA were evaluated. An excellent predictive power (RMSEP = 0.05%) was obtained with MLR aided by GA.

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A sensitive, fast, and inexpensive square wave voltammetric method using a cobalt phthalocyanine modified carbon paste electrode was developed for simultaneous determination of citric, lactic, malic and tartaric acids in fruit juices. To overcome the strong overlap of voltammetric signals caused by calibrated and uncalibrated constituents, multivariate curve resolution with alternating least squares (MCR-ALS) was used. Data were previous treated for correction of baseline and potential shift. The MCR-ALS calibration models were constructed and evaluated using a validation set obtained from a Taguchi design. The values predicted by the optimized MCR-ALS models were unbiased and no statistically significant difference was observed between proposed and reference methods, applying the paired t-test at a confidence level of 95%. As far as the authors know, a voltammetric method that simultaneously determines four organic acids in complex samples such as fruit juices without any previous pretreatment has not yet been reported in the literature.

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This paper describes a simple, inexpensive, highly sensitive, selective, and efficient electrochemical method to determine glyphosate (GLY) in samples of milk, orange juice, and agricultural formulation. The oxidation reaction on the electrode surface was electrochemically characterised by cyclic voltammetry (CV) and square wave voltammetry (SWV). The investigation of GLY at carbon paste electrode revealed a non-reversible oxidation peak at +0.95 V versus Ag/AgCl, which was used for electrochemical detection of GLY. The operating parameters (pH, frequency, step potential, and amplitude) were optimised in relation to the peak current intensity, and a calibration curve was set up in a concentration range of 4.40 × 10-8-2.80 × 10-6 mol L-1, with a detection limit of 2 × 10-9 mol L-1. After calibration curve was plotted, the developed procedure was applied to determine GLY in previously contaminated samples: milk and orange juice, and in a commercial formulation, obtaining recovery values between 98.31% and 103.75%. These results show that the proposed method can be used for GLY quantification in different samples with high sensitivity, specificity, stability, and reproducibility.

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The electrocatalytic oxidation of tartaric acid on a carbon paste electrode modified with cobalt (II)-phthalocyanine was demonstrated and applied to the development of a highly sensitive, simple, fast and inexpensive voltammetric sensor to determine tartaric acid. The electrochemical behavior of the modified electrode was investigated by cyclic and square wave voltammetry, and the effect of experimental variables, such as dispersion and loading of cobalt (II)-phthalocyanine, together with optimum conditions for sensing the analyte by square wave voltammetry were assessed. In addition, the absence of a significant memory effect combined with the ease of electrode preparation led to the development of a sensitive and direct method to determine tartaric acid in wines. Interferences from other low molecular weight organic acids commonly present in wines were circumvented by using a multiway calibration technique, successfully obtaining the second order advantage by modeling voltammetric data with unfolded partial least square with residual bilinearization (U-PLS/RBL). A linear response range between 10 and 100 µmol L-1 (r = 0.9991), a relative prediction error of 4.55% and a recovery range from 96.41 to 102.43% were obtained. The proposed method is non-laborious, since it does not use sample pretreatment such as filtration, extraction, pre-concentration or cleanup procedures.

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This work reports for the first time the use of chemically activated biochar as electrode modifier for nickel determination. The biochar activation was performed by refluxing with HNO3, which promoted a higher nickel preconcentration compared to unmodified and modified biochar precursor electrodes. Morphological and structural characterization revealed the increase of surface acid groups, surface area and porosity of biochar after activation. Nickel determination was investigated adopting an alternative voltammetric methodology based on monitoring the Ni(II)/Ni(III) redox couple. In the proposed method, it was not necessary to use a complexing agent and the biochar itself was responsible for the analyte preconcentration. A linear response for Ni(II) concentration range from 1.0 to 30 µmol L-1 and a limit of detection of 0.25 µmol L-1 were obtained. The method was successfully applied for Ni(II) determination in spiked samples of bioethanol fuel and discharge water, with recoveries values between 103 and 109%.

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New insights into the design of highly sensitive, carbon-based electrochemical sensors are presented in this work by exploring the interesting properties of graphene oxide (GO) and ionic liquids (ILs). An electrochemical sensor based on the carbon paste electrode (CPE) modified with GO and IL was developed for the sensitive detection of ofloxacin using square-wave adsorptive anodic stripping voltammetry (SWAdASV). GO sheets were obtained from the acid treatment of graphene and characterized by scanning and transmission electronic microscopy (SEM and TEM) and selected area electron diffraction (SAED), and the electrochemical behavior of the modified GO-IL/CPE was explored by electrochemical impedance spectroscopy studies. The CPE modification with GO and IL allowed an 8.2 fold increase in the analytical sensitivity for ofloxacin sensing compared to the unmodified CPE. Under the optimized experimental conditions using the SWAdASV technique, the GO-IL/CPE sensor provided an analytical curve for ofloxacin in the concentration range of 7.0×10-9 to 7.0×10-7molL-1, with a sensitivity of 7.7×106µALmol-1 and limit of detection of 2.8×10-10molL-1 (0.28nmolL-1). The proposed sensor was successfully applied for the ofloxacin determination in human urine and ophthalmic samples, with recoveries near 100%. The results were similar those obtained by a spectrophotometric comparative method.

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Biochar is a carbonaceous material similar produced by pyrolysis of biomass under oxygen-limited conditions. Pyrolysis temperature is an important parameter that can alters biochar characteristics (e.g. surface area, pore size distribution and surface functional groups) and affects it efficacy for adsorption of several probes. In this work, biochar samples have been prepared from castor oil cake using different temperatures of pyrolysis (200-600°C). For the first time, a voltammetric procedure based on carbon paste modified electrode (CPME) was used to investigate the effect of temperature of pyrolysis on the adsorptive characteristics of biochar for Pb(II), Cd(II) and Cu(II) ions. Besides the electrochemical techniques, several characterizations have been performed to evaluate the physicochemical properties of biochar in function of the increase of the pyrolysis temperature. Results suggest that biochar pyrolized at 400°C (BC400) showed a better potential for ions adsorption. The CPME modified with BC400 showed better relative current signal with adsorption affinity: Pb(II)>Cd(II)>Cu(II). Kinetic studies revealed that the pseudo-second order model describes more accurately the adsorption process suggesting that the surface reactions control the adsorption rate. Values found for amount adsorbed were 15.94±0.09; 4.29±0.13 and 2.38±0.39µgg(-1) for Pb(II), Cd(II) and Cu(II) ions, respectively.

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A carbon paste electrode was used for the electrochemical quantification of carbendazim in water and orange juice samples. Carbendazim oxidation on the electrode surface was found to be controlled by adsorption. The novel electrochemical procedure for carbendazim quantification employed differential pulse voltammetry using a carbon paste electrode under optimal conditions. Carbendazim oxidation currents were linear at concentrations of 2.84 to 45.44 µg L(-1), with a limit of detection of 0.96 µg L(-1). The proposed method was applied to carbendazim quantification in ultrapurified water, river water, and orange juice. Recovery rates in water and orange juice samples were in the 97%-101% range, indicating that the method can be employed to determine carbendazim in these matrices, with advantages including shorter analysis time and lower cost than routine methods such as chromatography or spectroscopy. The electrode showed good reproducibility, remarkable stability, and especially good surface renewability by simple mechanical polishing. The recovery rates observed were highly concordant with those obtained for high-performance liquid chromatography, having a relative standard deviation of less than 1.3%.

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This work describes the construction and application of carbon paste electrodes modified with biochar and antimony microparticles (SbBCPE) for voltammetric determination of paraquat using a simple and sensitive procedure based on voltammetric stripping analysis. Some parameters such as amount of biochar and antimony used in the composition of the carbon paste and instrumental parameters were examined in detail. Under optimized conditions, an analytical curve was obtained for paraquat determination employing SbBCPE, which showed a linear response ranging from 0.2 to 2.9 µmol L(-1), with limit of detection and quantification of 34 nmol L(-1) and 113 nmol L(-1), respectively, after paraquat pre-concentration of 120 s. The repeatability study presented a RSD=2.0% for 10 consecutive measurements using the same electrode surface and the reproducibility study showed a RSD=2.7% for measurements with 10 different electrode surfaces. The proposed sensor was successfully applied for paraquat determination in tap water and citric fruit juice spiked samples and good recoveries were obtained without any sample pre-treatment, showing its promising analytical performance.

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El comportamiento y el desempeño electroquímico del electrodo de pasta de carbono químicamente modificado por un líquido iónico (EPCQM), en la detección del galato de propilo, se investigaron matemáticamente desde el punto de vista de la estabilidad del estado estacionario. El modelo matemático correspondiente se analizó por medio de la teoría de estabilidad lineal y análisis de bifurcaciones. Los resultados de modelaje son comparados con los experimentales (para este sistema y semejantes), bien como con los teóricos para otros casos.

The behavior and the electrochemical function of the carbon paste electrode, chemically modified by ionic liquid, have been investigated mathematically from the point of view of steady-state stability. The corresponding mathematical model is analyzed by linear stability theory and bifurcation analysis. The modeling results are being compared with experimental results (for this system and for the similar ones), and with theoretical results for other cases.

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Background A simple, rapid, low-cost and environmentally friendly method was developed to determine dopamine (DA) in the presence of ascorbic (AA) and uric acid (UA) based on a novel technique to prepare a graphene-chitosan (GR-CS) nanocomposite and modify it on the surface of carbon paste electrode (CPE). For our design, CS acts as a media to disperse and stabilize GR, and then GR plays a key role to selective and sensitive determination of DA. Results Under physiological conditions, the linear range for dopamine was determined from 1 × 10- 4 to 2 × 10- 7 mol/L with a good correlation coefficient of 0.9961 in the presence of 1000-fold interference of AA and UA. The detection limit was estimated to be 9.82 × 10- 8 mol/L (S/N = 3). In order to study the stability and reproducibility, GR/CS/CPE underwent successive measurements in 10 times and then tested once a d for 30 d. The result exhibited 98.25% and 91.62% activities compared with the original peak current after 10-time measurements and 30-d storage. Conclusion The GR/CS/CPE has wide linear concentration range, low detection limit, and good reproducibility and stability, which suggests that our investigations provide a promising alternative for clinic DA determination.

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We have developed an eletroanalytical method that employs Cu(2+) solutions to determine arsenic in sugarcane brandy using an electrode consisting of carbon paste modified with carbon nanotubes (CNTPE) and polymeric resins. We used linear sweep (LSV) and differential-pulse (DPV) voltammetry with cathodic stripping for CNTPE containing mineral oil or silicone as binder. The analytical curves were linear from 30 to 110µgL(-1) and from 10 to 110µgL(-1) for LSV and DPV, respectively. The limits of detection (L.O.D.) and quantification (L.O.Q.) of CNTPE were 10.3 and 34.5µgL(-1) for mineral oil and 3.4 and 11.2µgL(-1) for silicone. We applied this method to determine arsenic in five commercial sugarcane brandy samples. The results agreed well with those obtained by hydride generation combined with atomic absorption spectrometry (HG AAS).

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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.

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