Heparin-stabilized gold nanoparticles embedded in graphene for the electrochemical determination of esculetin.

A conductive nanocomposite consisting of heparin-stabilized gold nanoparticles embedded in graphene was prepared and characterized to develop an electrochemical sensor for the determination of esculetin in tea and jam samples. The gold nanoparticles were characterized by spectroscopic and microscopic techniques. The different proportions of graphene in the nanocomposite were evaluated and characterized by electrochemical practices. The heterostructure material on the glassy carbon electrode with esculetin showed π-π stacking interactions with an adsorption-controlled process. The voltammetric profile of esculetin using the proposed nanomaterial presented oxidation and reduction peaks at +0.61 and +0.58 V vs. Ag/AgCl, respectively, facilitating the electron transfer with esculetin through the transfer of two moles of protons and two moles of electrons per mole of esculetin. Using optimized conditions and square wave voltammetry, the calibration curve was obtained with two linear ranges, from 0.1 to 20.5 µmol L-1, with a detection limit of 43.0 nmol L-1. The electrochemical sensor showed satisfactory results for repeatability and stability, although interferences were observed in the presence of high concentrations of ascorbic acid or quercetin. The sensor was successfully applied in the determination of esculetin in samples of mulberry jam, white mulberry leaf tea, and white mulberry powder tea, presenting adequate recovery ranges. This directive provides valuable insights for the development of novel electrochemical sensors using heparin-based conductive nanomaterials with improved sensitivity and sensibility.

Green Synthesis of Gold Nanoparticles Using Peach Extract Incorporated in Graphene for the Electrochemical Determination of Antioxidant Butylated Hydroxyanisole in Food Matrices.

Butylated hydroxyanisole (BHA) is a synthetic phenolic antioxidant widely used in various food matrices to prevent oxidative rancidity. However, its presence has been associated with liver damage and carcinogenesis in animals. Thus, an electrochemical sensor was built using a composite of gold nanoparticles synthesized in peach extract (Prunus persica (L.) Batsch) and graphene. Peach extract served as a reducing and stabilizing agent for gold nanoparticles, as a dispersing agent for graphene, and as a film former to immobilize the composite on the surface of a glassy carbon electrode. The gold nanoparticles were characterized using spectroscopic and microscopic techniques, and the electrodes were electrochemically characterized using electrochemical impedance spectroscopy and cyclic voltammetry. The sensor provided higher current responses and lower charge transfer resistances compared to the unmodified glassy carbon electrode. Under the established optimized working conditions (0.1 mol L-1 Britton-Robinson buffer, pH 4.0, and differential pulse voltammetry), the calibration curve exhibited a linear range from 0.2 to 9.8 µmol L-1, with a detection limit of 70 nmol L-1. The proposed sensor represented a sensitive and practical analytical tool for the accurate determination of BHA in mayonnaise samples.

Nanocomposite based on green synthesis of gold nanoparticles decorated with functionalized multi-walled carbon nanotubes for the electrochemical determination of hydroxychloroquine.

In this study, a selective and sensitive electrochemical approach for determining hydroxychloroquine (HCQ) was proposed. A novel nanocomposite based on gold nanoparticles synthesized by green synthesis in an extract of white pitaya (Hylocereus undatus) (AuNP-Ext) decorated with functionalized multi-walled carbon nanotubes (f-MWCNTs) was presented. AuNP-Ext was characterized by ultraviolet-visible spectroscopy and the f-MWCNTs/AuNP-Ext nanocomposite by transmission electron microscopy. The nanocomposite was used to modify a glassy carbon electrode (GCE). Using the f-MWCNT-AuNP-Ext/GCE sensor, an irreversible oxidation peak at +0.74 V vs. Ag/AgCl was verified by HCQ. The calibration plot was studied in two linear ranges, from 0.03 to 3.5 µmol/L and from 3.5 to 17.0 µmol/L, with a limit of detection of 0.0093 µmol/L and a limit of quantification of 0.031 µmol/L, regarding the first linear range. The proposed sensor was successfully applied to the determination of HCQ in pharmaceutical and clinical samples without any special purification, separation or pre-treatment steps. The accuracy was verified by UV-Vis spectrometry, and this revealed that the proposed method was accurate and precise, as evidenced by F- and t-tests.

Graphene and gold nanoparticle-based bionanocomposite for the voltammetric determination of bisphenol A in (micro)plastics.

The monitoring of endocrine disruptors in the environment is one of the main strategies in the investigation of potential risks associated with exposure to these chemicals. Bisphenol A is one of the most prevalent endocrine-disrupting compounds and is prone to leaching out from polycarbonate plastic in both freshwater and marine environments. Additionally, microplastics also can leach out bisphenol A during their fragmentation in the water environment. In the quest for a highly sensitive sensor to determine bisphenol A in different matrices, an innovative bionanocomposite material has been achieved. This material is composed of gold nanoparticles and graphene, and was synthesized using a green approach that utilized guava (Psidium guajava) extract for reduction, stabilization, and dispersion purposes. Transmission electron microscopy images revealed well-spread gold nanoparticles with an average diameter of 31 nm on laminated graphene sheets in the composite material. An electrochemical sensor was developed by depositing the bionanocomposite onto a glassy carbon surface, which displayed remarkable responsiveness towards bisphenol A. Experimental conditions such as the amount of graphene, extract: water ratio of bionanocomposite and pH of the supporting electrolyte were optimized to improve the electrochemical performance. The modified electrode displayed a marked improvement in current responses for the oxidation of bisphenol A as compared to the uncovered glassy carbon electrode. A calibration plot was established for bisphenol A in 0.1 mol L-1 Britton-Robinson buffer (pH 4.0), and the detection limit was determined to equal to 15.0 nmol L-1. Recovery data from 92 to 109% were obtained in (micro)plastics samples using the electrochemical sensor and were compared with UV-vis spectrometry, demonstrating its successful application with accurate responses.

Ratiometric Electrochemical Sensor for Butralin Determination Using a Quinazoline-Engineered Prussian Blue Analogue.

A ratiometric electrochemical sensor based on a carbon paste electrode modified with quinazoline-engineered ZnFe Prussian blue analogue (PBA-qnz) was developed for the determination of herbicide butralin. The PBA-qnz was synthesized by mixing an excess aqueous solution of zinc chloride with an aqueous solution of precursor sodium pentacyanido(quinazoline)ferrate. The PBA-qnz was characterized by spectroscopic and electrochemical techniques. The stable signal of PBA-qnz at +0.15 V vs. Ag/AgCl, referring to the reduction of iron ions, was used as an internal reference for the ratiometric sensor, which minimized deviations among multiple assays and improved the precision of the method. Furthermore, the PBA-qnz-based sensor provided higher current responses for butralin compared to the bare carbon paste electrode. The calibration plot for butralin was obtained by square wave voltammetry in the range of 0.5 to 30.0 µmol L-1, with a limit of detection of 0.17 µmol L-1. The ratiometric sensor showed excellent precision and accuracy and was applied to determine butralin in lettuce and potato samples.

Nitrogen and sulfur co-doped graphene quantum dot-modified electrode for monitoring of multivitamins in energy drinks.

A glassy carbon electrode was modified with nitrogen and sulfur co-doped graphene quantum dots immobilized in chitosan for the monitoring of multivitamins. The graphene quantum dots were synthesized using a simple citric acid/l-cysteine pyrolysis procedure. The co-doping with nitrogen and sulfur in the graphene matrix was confirmed by spectroscopic techniques. Electron microscopy results showed that the synthesized quantum dots had a diameter of 3.4 ± 1.4 nm. Electrochemical techniques showed excellent current responses to vitamin oxidation provided by the modified electrode compared to the bare electrode. The parameters of square wave voltammetry were optimized in order to obtain the best current responses and to study the electrochemical oxidation of vitamins. The calibration plots for vitamins B2, B6 and B12 were constructed in 0.1 mol L-1 sodium acetate buffer (pH 5.0) with limits of detection of 0.30, 30.1 and 0.32 nmol L-1, respectively. Lastly, the modified electrode was effectively implemented in the quantification of vitamins in classic and fruit-based energy drink samples.

Electrode modified with graphene quantum dots supported in chitosan for electrochemical methods and non-linear deconvolution of spectra for spectrometric methods: approaches for simultaneous determination of triclosan and methylparaben.

Two analytical methods were developed using electrochemical and spectrometric techniques for the simultaneous determination of endocrine disruptors triclosan and methylparaben in the monitoring of personal care products. For the electroanalytical analyses, a sensitive electrode based on graphene quantum dots supported in chitosan was employed. Under optimized conditions and a working potential of typically + 0.60 V for triclosan and + 0.81 V (vs. Ag/AgCl) for methylparaben, the calibration plots obtained by differential pulse voltammetry were linear in the range 0.10 to 10.0 µmol L-1. The detection limits were 0.03 and 0.04 µmol L-1 for triclosan and methylparaben, respectively. For the spectrometric method, UV/VIS spectrometry was used with a mathematical processing of non-linear deconvolution. This processing was used to solve the problem of overlapping absorption bands of triclosan (282 nm) and methylparaben (257 nm), which enabled simultaneous determination. The calibration plots by UV/VIS spectrometry were linear in the range 1.0 to 14.0 µmol L-1 with detection limits of 0.42 and 0.37 µmol L-1, respectively, for triclosan and methylparaben. Similar results obtained from the calibration plots of individual analytes suggest that the methods can be applied for individual or simultaneous determination of these species. Both methods were employed in the analysis of five samples of personal care products: toothpaste, antiseptic soap, antiseptic deodorant, shampoo, and a bath kit (soap and shampoo). The statistical tests indicated that there were no significant differences regarding the accuracy and precision of the data provided by the two methods described herein. Graphical abstract Schematic representation for simultaneous determination of triclosan and methylparaben: electrochemical method employing an electrode modified with graphene quantum dots supported in chitosan and spectrometric method applying a non-linear deconvolution of spectrum.

Ionic liquid-supported magnetite nanoparticles as electrode modifier materials for estrogens sensing.

This paper reports the application of a carbon paste electrode modified with magnetite nanoparticles and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate in the electroanalytical determination of 17ß-estradiol and estriol. These estrogens are potential endocrine disruptors and thus it is relevant the development of devices for their monitoring. Transmission electron microscopy, scanning electron microscopy and zeta potential techniques were applied to characterization of the modifier materials. In cyclic voltammetry experiments, irreversible oxidation peaks were observed for 17ß-estradiol and estriol at +0.320 V and +0.400 V, respectively. The anodic currents obtained were approximately three times greater than those provided by the unmodified electrode due to the presence of magnetic nanoparticles and the ionic liquid, which improved the sensitivity of modified electrode. For the analysis, the parameters of the square-wave voltammetry (scan increment, amplitude and frequency) were optimized by Box-Behnken factorial design for each estrogen. For 17ß-estradiol in B-R buffer pH 12.0, the calibration plot was linear from 0.10 to 1.0 µmol L-1, with a detection limit of 50.0 nmol L-1. For estriol in B-R buffer pH 11.0, the linear range was 1.0 to 10.0 µmol L-1, with a detection limit of 300.0 nmol L-1. The modified electrode was applied in the determination of 17ß-estradiol and estriol in pharmaceutical formulations and the results were comparable to those obtained using UV/VIS spectrometry. Statistical tests were applied to evaluate the results and it was concluded that there was no significant difference regarding the precision and accuracy of the data provided by the two methods.

Silver nanoparticle-modified electrode for the determination of nitro compound-containing pesticides.

This paper reports the electroanalytical determination of pendimethalin and ethyl parathion by square-wave adsorptive stripping voltammetry using a material comprised of chitosan-stabilized silver nanoparticles to modify a glassy carbon electrode. Under optimized experimental conditions, the peak current was found to vary linearly with the concentration of pendimethalin in the range of 70 to 2000 nmol L(-1) and with concentration of ethyl parathion in the range of 40 to 8000 nmol L(-1). Detection limits of 36 and 40 nmol L(-1) were obtained for pendimethalin and ethyl parathion, respectively. The silver - nanoparticle-modified electrode was successfully employed for the analysis of pesticides in tap and mineral water (pendimethalin) and in lettuce and honey (ethyl parathion) samples. Pendimethalin recovery was between 94 and 100 %, and ethyl parathion recovery was between 97 and 101 %, indicating no significant matrix interference effects on the analytical results. The accuracy of the electroanalytical methodology using the proposed modified electrode was also compared to that of the UV-vis spectrophotometric method.