Highly sensitive voltammetric determination of Allura Red (E129) food colourant on a planar carbon fiber sensor modified with shungite.

This article presents an original planar carbon fiber electrode (PCFE), in which shungite (SHU) is used as a modifier for the first time. Shungite is a unique natural nanostructured composite consisting of carbon in the form of aggregated graphene stacks, oxides of silicon, titanium, aluminum, iron, magnesium, potassium, etc. Macro- and micro-elements, biologically active components that are present in shungite provide it with attractive antioxidant properties, make it a biocompatible and environmentally friendly material that meets the principles of green chemistry. A unique supramolecular structure of shungite carbon presents a multilayer globular-cluster formation with mesopores in the internal volume. It determines specific physical, chemical, catalytic, and adsorption properties of shungite. Carbon fiber with an irregular 3D structure was used as an effective electrode platform for strong immobilization of shungite. The PCFE was fabricated using a simple and scalable hot lamination technology that produces very low cost flexible planar electrodes. The sensor (SHU/PCFE) was characterized by scanning electron microscopy; electrochemical impedance analysis; cyclic, differential-pulse and stripping voltammetry. The SHU/PCFE showed a 2.5-fold increase in the electroactive surface area, a 1.8-fold decrease in the electron transfer resistance compared with the bare PCFE. Under optimal experimental conditions and preconcentration at +0.2 V (vs. Ag/AgCl) 180 s, the developed sensor allowed the quantification of Allura Red in the ranges of 0.001-0.1 and 0.1-2 µmol L-1 with an extremely low detection limit of 0.36 nmol L-1. Moreover, this convenient and cost-effective sensor also has good repeatability, stability and anti-interference ability. The interfering effect of sweeteners and preservatives in the determination of Allura Red does not exceed 3.6%. The practical application of the SHU/PCFE was demonstrated using drink samples, lollipops and pharmaceuticals.

Carbon Paper Modified with Functionalized Poly(diallyldimethylammonium chloride) Graphene and Gold Phytonanoparticles as a Promising Sensing Material: Characterization and Electroanalysis of Ponceau 4R in Food Samples.

This paper presents a novel eco-friendly sensing material based on carbon paper (CP) volumetrically modified with a composite nanomodifier that includes functionalized poly(diallyldimethylammonium chloride) graphene (PDDA-G) and phytosynthesized gold nanoparticles (phyto-AuNPs). The functionalization of graphene was justified by Fourier-transform infrared spectroscopy. The phyto-AuNPs (d = 6 nm) were prepared by "green" synthesis with the use of strawberry leaf extract. The sensing material was characterized using scanning electron microscopy, electrochemical impedance spectroscopy, and voltammetry. The research results indicated a more than double increase in the electroactive surface area; a decrease in the resistance of electron transfer on nanocomposite-modified CP, compared to bare CP. The phyto-AuNPs/PDDA-G/CP was used for the electrosensing of the synthetic dye Ponceau 4R. The oxidation signal of colorant enhanced 4-fold on phyto-AuNPs/PDDA-G/CP in comparison to CP. The effect of the quantity of nanomodifier, solution pH, potential scan rate, accumulation parameters, and differential pulse parameters on the peak current of Ponceau 4R was studied. Under optimal conditions, excellent sensory characteristics were established: LOD 0.6 nM and LR 0.001-2 µM for Ponceau 4R. High selectivity and sensitivity enable the use of the sensor for analyzing the content of Ponceau 4R in food products (soft drinks, candies, and popsicles) without additional sample preparation.

An Electrochemical Sensor Based on Carbon Paper Modified with Graphite Powder for Sensitive Determination of Sunset Yellow and Tartrazine in Drinks.

The paper describes the development of an electrochemical sensor to be used for the determination of synthetic food colorants such as Sunset Yellow FCF (SY) and Tartrazine (TZ). The sensor is a carbon paper (CP) electrode, manufactured by using hot lamination technology and volume modified with fine-grained graphite powder (GrP). The sensor (GrP/CP) was characterized by scanning electron microscopy, energy dispersive spectrometry, electrochemical impedance analysis, cyclic, linear sweep and differential pulse voltammetry. The mechanism of SY and TZ electrochemical oxidation on GrP/CP was studied. The developed sensor has good electron transfer characteristics and low electron resistance, high sensitivity and selectivity. Applying the differential pulse mode, linear dynamic ranges of 0.005-1.0 µM and 0.02-7.5 µM with limits of detection of 0.78 nM and 8.2 nM for SY and TZ, respectively, were obtained. The sensor was used to detect SY and TZ in non-alcoholic and alcoholic drinks. The results obtained from drink analysis prove good reproducibility (RSD ≤ 0.072) and accuracy (recovery 96-104%).

Developing Activated Carbon Veil Electrode for Sensing Salivary Uric Acid.

The paper describes the development of a carbon veil-based electrode (CVE) for determining uric acid (UA) in saliva. The electrode was manufactured by lamination technology, electrochemically activated and used as a highly sensitive voltammetric sensor (CVEact). Potentiostatic polarization of the electrode at 2.0 V in H2SO4 solution resulted in a higher number of oxygen and nitrogen-containing groups on the electrode surface; lower charge transfer resistance; a 1.5 times increase in the effective surface area and a decrease in the UA oxidation potential by over 0.4 V, compared with the non-activated CVE, which was confirmed by energy dispersive X-ray spectroscopy, electrochemical impedance spectroscopy, chronoamperometry and linear sweep voltammetry. The developed sensor is characterized by a low detection limit of 0.05 µM and a wide linear range (0.09-700 µM). The results suggest that the sensor has perspective applications for quick determination of UA in artificial and human saliva. RSD does not exceed 3.9%, and recovery is 96-105%. UA makes a significant contribution to the antioxidant activity (AOA) of saliva (≈60%). In addition to its high analytical characteristics, the important advantages of the proposed CVEact are the simple, scalable, and cost-effective manufacturing technology and the absence of additional complex and time-consuming modification operations.

Electrochemical Properties of Phytosynthesized Gold Nanoparticles for Electrosensing.

Gold nanoparticles are widely used in electrosensing. The current trend is to phytosynthesize gold nanoparticles (phyto-AuNPs) on the basis of the "green" chemistry approach. Phyto-AuNPs are biologically and catalytically active, stable and biocompatible, which opens up broad perspectives in a variety of applications, including tactile, wearable (bio)sensors. However, the electrochemistry of phytosynthesized nanoparticles is not sufficiently studied. This work offers a comprehensive study of the electrochemical activity of phyto-AuNPs depending on the synthesis conditions. It was found that with an increase in the aliquot of the plant extract, its antioxidant activity (AOA) and pH, the electrochemical activity of phyto-AuNPs grows, which is reflected in the peak potential decrease and an increase in the peak current of phyto-AuNPs electrooxidation. It has been shown that AOA is an important parameter for obtaining phyto-AuNPs with desired properties. Electrodes modified with phyto-AuNPs have demonstrated better analytical characteristics than electrodes with citrate AuNPs in detecting uric and ascorbic acids under model conditions. The data about the phyto-AuNPs' electrochemistry may be useful for creating highly effective epidermal sensors with good biocompatibility.

Electrochemical Sensor Based on a Carbon Veil Modified by Phytosynthesized Gold Nanoparticles for Determination of Ascorbic Acid.

An original voltammetric sensor (Au-gr/CVE) based on a carbon veil (CV) and phytosynthesized gold nanoparticles (Au-gr) was developed for ascorbic acid (AA) determination. Extract from strawberry leaves was used as source of antioxidants (reducers) for Au-gr phytosynthesis. The sensor was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy and electrochemical methods. Optimal parameters of AA determination were chosen. The sensor exhibits a linear response to AA in a wide concentration range (1 µM-5.75 mM) and a limit of detection of 0.05 µM. The developed sensor demonstrated a high intra-day repeatability of 1 µM AA response (RSD = 1.4%) and its stability during six weeks, selectivity of AA determination toward glucose, sucrose, fructose, citric, tartaric and malic acids. The proposed sensor based on Au-gr provides a higher sensitivity and a lower limit of AA detection in comparison with the sensor based on gold nanoparticles synthesized by the Turkevich method. The sensor was successfully applied for the determination of AA content in fruit juices without samples preparation. The recovery of 99%-111% and RSD no more than 6.8% confirm the good reproducibility of the juice analysis results. A good agreement with the potentiometric titration data was obtained. A correlation (r = 0.9867) between the results of AA determination obtained on the developed sensor and integral antioxidant activity of fruit juices was observed.

The Effect of the Antioxidant Activity of Plant Extracts on the Properties of Gold Nanoparticles.

Synthesis of gold nanoparticles (phyto-AuNPs) with the use of leaf extracts (phytosynthesis) is based on the concept of Green Chemistry. The present study is conducted to discuss how antioxidant activity (AOA) of extracts from plant leaves impacts on the kinetics of phytosynthesis, the size of the formed nanoparticles, and the stability of their nanosuspensions. Results show that the formation rate of phyto-AuNPs suspensions accelerate due to the increase in the AOA of the extracts. Accompanying the use of transmission electron microscopy (TEM), UV-Vis-spectrophotometry and dynamic light scattering (DLS), it also has been found that higher AOA of the extracts leads to a decrease in the size of phyto-AuNPs, an increase in the fraction of small (d ≤ 5 nm), and a decrease in the fraction of large (d ≥ 31-50 nm) phyto-AuNPs, as well as an increase in the zeta potential in absolute value. Phyto-AuNPs suspensions synthesized with the use of extracts are more resistant to destabilizing electrolytes and ultrasound, as compared to suspensions synthesized using sodium citrate. Thus, the AOA of the extract is an important parameter for controlling phytosynthesis and predicting the properties of phyto-AuNPs. The proposed approach can be applied to the targeted selection of plant extract that will be used for synthesizing nanoparticles with desired properties.