Electrochemically reduced graphene oxide films from Zn-C battery waste for the electrochemical determination of paracetamol and hydroquinone.

Contributing to the development of sustainable electroanalytical chemistry, electrochemically reduced graphene oxide (ERGO) films obtained from residual graphite of discharged Zn-C batteries are proposed in this work. Graphite from the cathode of discarded Zn-C batteries was recovered and used in the synthesis of graphene oxide (GO) by the modified Hummer's method. The quality of the synthesized GO was verified using different characterization methods (FT-IR, XRD, SEM, and TEM). GO films were deposited on a glassy carbon electrode (GCE) by the drop coating method and then electrochemically reduced by cathodic potential scanning using cyclic voltammetry. The electrochemical features of the ERGO films were investigated using the ferricyanide redox probe, as well as paracetamol (PAR) and hydroquinone (HQ) molecules as model analytes. From the cyclic voltammetry assays, enhanced heterogeneous electron transfer rate constants (k0) were observed for all redox systems studied. In analytical terms, the ERGO-based electrode showed higher analytical sensitivity than the bare and GO-modified GCE. Using differential pulse voltammetry, wide linear response ranges and limits of detection of 0.14 µmol L-1 and 0.65 µmol L-1 were achieved for PAR and HQ, respectively. Furthermore, the proposed sensor was successfully applied to the determination of PAR and HQ in synthetic urine and tap water samples (recoveries close to 100%). The outstanding electrochemical and analytical properties of the proposed ERGO films are added to the very low cost of the raw material, being presented as a green-based alternative for the development of electrochemical (bio)sensors with unsophisticated resources.

Carbon Nanomaterials-Based Screen-Printed Electrodes for Sensing Applications.

Electrochemical sensors consisting of screen-printed electrodes (SPEs) are recurrent devices in the recent literature for applications in different fields of interest and contribute to the expanding electroanalytical chemistry field. This is due to inherent characteristics that can be better (or only) achieved with the use of SPEs, including miniaturization, cost reduction, lower sample consumption, compatibility with portable equipment, and disposability. SPEs are also quite versatile; they can be manufactured using different formulations of conductive inks and substrates, and are of varied designs. Naturally, the analytical performance of SPEs is directly affected by the quality of the material used for printing and modifying the electrodes. In this sense, the most varied carbon nanomaterials have been explored for the preparation and modification of SPEs, providing devices with an enhanced electrochemical response and greater sensitivity, in addition to functionalized surfaces that can immobilize biological agents for the manufacture of biosensors. Considering the relevance and timeliness of the topic, this review aimed to provide an overview of the current scenario of the use of carbonaceous nanomaterials in the context of making electrochemical SPE sensors, from which different approaches will be presented, exploring materials traditionally investigated in electrochemistry, such as graphene, carbon nanotubes, carbon black, and those more recently investigated for this (carbon quantum dots, graphitic carbon nitride, and biochar). Perspectives on the use and expansion of these devices are also considered.

An electrochemical sensing platform based on carbon black and chitosan-stabilized platinum nanoparticles.

The versatility of chitosan (Ch) biopolymer as a metallic nanoparticle stabilizing agent and excellent former of thin films on glassy carbon was explored in this work for the sustainable manufacture of novel electrochemical sensors based on carbon black (CB) and chitosan-stabilized platinum nanoparticles (Ch-PtNPs). Platinum nanoparticles highly stabilized by chitosan were easily synthesized at room temperature and characterized by HR-TEM, UV-vis, and voltammetry. Ch-PtNPs presented an average diameter of 2.7 nm, and typical voltammetric peaks of Pt in sulfuric acid medium were detected for films containing Ch-PtNPs. As a proof of concept, the CB-Ch-PtNP electrode was applied in the determination of hydrogen peroxide (H2O2) and the endocrine disruptor bisphenol A (BPA). Pronounced electrocatalytic activity towards H2O2 reduction was observed in the presence of Ch-PtNPs in the films, guaranteeing the non-enzymatic determination of H2O2 by chronoamperometry, with a limit of detection of 10 µmol L-1. In the determination of BPA by differential pulse adsorptive anodic stripping voltammetry (DPAdASV), under optimal experimental conditions, a wide linear response range and a limit of detection at the nanomolar level (7.9 nmol L-1) were achieved. In addition, excellent repeatabilities of sensor response and sensor fabrication, and accuracy in the analysis of natural water samples were obtained.

A voltammetric sensor based on a carbon black and chitosan-stabilized gold nanoparticle nanocomposite for ketoconazole determination.

A modified glassy carbon electrode with carbon black (CB) and gold nanoparticles (AuNPs) within a crosslinked chitosan (CTS) film is proposed in this work. The electroanalytical performance of the modified CB-CTS-AuNPs/GCE has been evaluated towards the voltammetric sensing of ketoconazole (KTO), a widespread antifungal drug. The nanocomposite was characterized by scanning electron microscopy, X-ray diffraction spectroscopy, and electrochemistry experiments. The evaluation of the electrochemical behaviour of KTO on the proposed modified electrode shows an irreversible oxidation process at a potential of +0.65 V (vs. Ag/AgCl (3.0 mol L-1 KCl)). This redox process was explored to carry out KTO sensing using square-wave voltammetry. The analytical curve was linear in the KTO concentration range from 0.10 to 2.9 µmol L-1, with a limit of detection (LOD) of 4.4 nmol L-1 and a sensitivity of 3.6 µA L µmol-1. This modified electrode was successfully applied to the determination of KTO in pharmaceutical formulations and biological fluid samples.

Electrochemical sensor based on ionic liquid and carbon black for voltammetric determination of Allura red colorant at nanomolar levels in soft drink powders.

The ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate and carbon black (CB) nanoparticles were incorporated within a crosslinked chitosan film over the surface of a glassy carbon electrode, and the obtained architecture explored to the sensitive voltammetric sensing of Allura red colorant in soft drinking powders. The different electrodic surfaces were morphologically and electrochemically characterized. From the modification of glassy carbon electrode with IL and CB, a significantly enhanced voltammetric response was achieved toward the Allura red irreversible oxidation reaction. The type and amount of IL employed in the electrode modification step as well as all the others experimental parameters affecting the sensor response by square-wave adsorptive anodic stripping voltammetry (SWAdASV) were systematically optimized. Under the optimum experimental conditions, the proposed SWAdASV procedure provided a linear analytical curve in the concentration range of 3.98 × 10-8 to 9.09 × 10-7 mol L-1 and a low limit of detection of 9.1 × 10-10 mol L-1 (0.91 nmol L-1). The proposed sensor presented good precision and no matrice effects as shown from repeatability tests, concomitant studies and addition/recovery assays. The developed SWAdASV procedure was applied successfully in the determination of Allura red content in commercial soft drink powder samples, and the results were in close agreement with those obtained using a comparative spectrophotometric method at a confidence level of 95%.

Non-enzymatic electrochemical determination of creatinine using a novel screen-printed microcell.

A low-cost and disposable microcell was constructed with a screen-printed electrode for the non-enzymatic electrochemical determination of creatinine. The working electrode was modified with carbon black and maintained in contact with paper-adsorbed iron (III) ions. A small sample volume of 3 µL was required for the device operation. Then, iron (III) ions were complexed in the presence of creatinine in a chemical step, followed by an electrochemical reduction of non-complexed metallic ions in excess. Cyclic voltammetry and differential-pulse voltammetry experiments were employed for the electrochemical characterizations and analytical performance evaluation of the microcell. The working electrode modification with carbon black provided a significant increase of analytical signal. The sensor presented a linear response for creatinine concentrations ranging from 0.10 to 6.5 mmol L-1, with a limit of detection of 0.043 mmol L-1. Experiments for creatinine determination in real samples were successful performed through of standard recovery in urine.

Electrochemical paper-based microfluidic device for high throughput multiplexed analysis.

A disposable microfluidic electrochemical paper-based device for multiplexed analysis based on sixteen independent microfluidic channels with electrochemical detection is proposed. A major advantage of this work was the non-necessary use of a wax printer for devices manufacturing which has a high cost of operation. In addition, a commercial multiplexing module was used that has the multiplexing capability of 8-16 channels and, for the first time using this module, the strategy of multiplexing both the working and reference electrodes were used. These sixteen channels with the respective sensors can be operated employing one or multiple electrochemical techniques with good repeatability and reproducibility for high throughput analysis. As a proof of concept, the electrochemical performance of device was tested with ferrocenecarboxylic acid solution employing cyclic voltammetry, square-wave voltammetry, differential-pulse voltammetry and chronoamperometry. This innovative sensing platform presented capacity of production in large scale and application for clinical tests with safety and short time of assays. A biosensor was constructed using glucose oxidase on the platform for the glucose determination in urine as a non-invasive strategy. The analytical curve was linear in the glucose concentration range from 1.0 × 10-4 mol L-1 to 4 × 10-2 mol L-1, with a limit of detection of 3 × 10-5 mol L-1.

Effect of carbon black functionalization on the analytical performance of a tyrosinase biosensor based on glassy carbon electrode modified with dihexadecylphosphate film.

Carbon Black (CB) has acquired a prominent position as a carbon nanomaterial for the development of electrochemical sensors and biosensors due to its low price and extraordinary electrochemical and physical properties. These properties are highly dependent on the surface chemistry and thus, the effect of functionalization has been widely studied for different applications. Meanwhile, the influence of CB functionalization over its properties for electroanalytical applications is still being poorly explored. In this study, we describe the use of chemically functionalized CB Vulcan XC 72R for the development of sensitive electrochemical biosensors. The chemical pre-treatment increased the material wettability by raising the concentration of surface oxygenated functional groups verified from elemental analysis and FTIR measurements. In addition, it was observed an enhancement of almost 100-fold on the electron transfer rate constant (k0) related to unfunctionalized CB, confirming a remarkable improvement of the electrocatalytic properties. Finally, we constructed a Tyrosinase (Tyr) biosensor based on functionalized CB and dihexadecylphosphate (DHP) for the determination of catechol in water samples. The resulting device displayed an excellent stability with a limit of detection of 8.7 × 10-8 mol L-1 and a sensitivity of 539 mA mol-1 L. Our results demonstrate that functionalized CB provides an excellent platform for biosensors development.

Simultaneous determination of isoproterenol, acetaminophen, folic acid, propranolol and caffeine using a sensor platform based on carbon black, graphene oxide, copper nanoparticles and PEDOT:PSS.

We explored the use of carbon black (CB), graphene oxide (GO), copper nanoparticles (CuNPs) and poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) as electrode materials for the simultaneous determination of isoproterenol, acetaminophen, folic acid, propranolol and caffeine. The designed nanostructured surface was widely characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), contact angle measurements and electrochemistry. From electrochemical characterization assays carried out towards the potassium ferricyanide redox probe, fast electron transfer kinetics and a considerably higher electroactive surface area were observed for the modified electrodic surface based on CB, GO, CuNPs and PEDOT:PSS film. Using square-wave voltammetry (SWV), well defined and resolved anodic peaks were detected for isoproterenol, acetaminophen, folic acid, propranolol and caffeine, with peak-to-peak potential separation not less than 170 mV. Then, the SWV technique was explored for the simultaneous determination of quinary mixtures of these analytes, resulting in analytical curves with linear ranges and limits of detection at micromolar concentration levels. The practical viability of the proposed voltammetric sensor was illustrated in the analysis of human body fluid samples. The proposed sensor showed good repeatability and a successful application using urine and serum matrices, with recoveries close to 100%.

The application of graphene for in vitro and in vivo electrochemical biosensing.

Advances in analysis are required for rapid and reliable clinical diagnosis. Graphene is a 2D material that has been extensively used in the development of devices for the medical proposes due to properties such as an elevated surface area and excellent electrical conductivity. On the other hand, architectures have been designed with the incorporation of different biological recognition elements such as antibodies/antigens and DNA probes for the proposition of immunosensors and genosensors. This field presents a great progress in the last few years, which have opened up a wide range of applications. Here, we highlight a rather comprehensive overview of the interesting properties of graphene for in vitro, in vivo, and point-of-care electrochemical biosensing. In the course of the paper, we first introduce graphene, electroanalytical methods (potentiometry, voltammetry, amperometry and electrochemical impedance spectroscopy) followed by an overview of the prospects and possible applications of this material in electrochemical biosensors. In this context, we discuss some relevant trends including the monitoring of multiple biomarkers for cancer diagnostic, implantable devices for in vivo sensing and, development of point-of-care devices to real-time diagnostics.

Electrochemical sensor based on graphene oxide and ionic liquid for ofloxacin determination at nanomolar levels.

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.

A novel architecture based upon multi-walled carbon nanotubes and ionic liquid to improve the electroanalytical detection of ciprofibrate.

Voltammetric studies have been carried out using a glassy carbon electrode (GCE) modified with multi-walled carbon nanotubes (MWCNTs) and the ionic liquid 1-butyl-3-methylimidazolium chloride (IL). Studies on the electrochemical properties of GCEs modified with MWCNTs and IL within different polymeric films (dihexadecylphosphate (DHP), Nafion, and chitosan (CTS)) were performed using a [Fe(CN)6](4-/3-) electrochemical probe. The modified GCE with different polymeric films was also tested for ciprofibrate (CPF) sensing in the presence and absence of IL in the film. The presence of IL and the MWCNTs improved the electrochemical response for CPF in all cases due to a synergic effect, and the IL-MWCNTs-DHP/GCE showed a great voltammetric profile for CPF detection. The IL-MWCNTs-DHP/GCE and differential pulse voltammetry (DPV) were used for the determination of CPF. An analytical curve was obtained for CPF in the concentration range of 2.50 × 10(-7) to 7.41 × 10(-6) mol L(-1) with a detection limit of 9.20 × 10(-8) mol L(-1). The proposed DPV method was successfully applied for CPF determination in pharmaceutical samples, and the results obtained agree with the results obtained using a spectrophotometric method at a confidence level of 95%.

Differential pulse adsorptive stripping voltammetric determination of nanomolar levels of atorvastatin calcium in pharmaceutical and biological samples using a vertically aligned carbon nanotube/graphene oxide electrode.

A novel vertically aligned carbon nanotube/graphene oxide (VACNT-GO) electrode is proposed, and its ability to determine atorvastatin calcium (ATOR) in pharmaceutical and biological samples by differential pulse adsorptive stripping voltammetry (DPAdSV) is evaluated. VACNT films were prepared on a Ti substrate by a microwave plasma chemical vapour deposition method and then treated with oxygen plasma to produce the VACNT-GO electrode. The oxygen plasma treatment exfoliates the carbon nanotube tips exposing graphene foils and inserting oxygen functional groups, these effects improved the VACNT wettability (super-hydrophobic) which is crucial for its electrochemical application. The electrochemical behaviour of ATOR on the VACNT-GO electrode was studied by cyclic voltammetry, which showed that it underwent an irreversible oxidation process at a potential of +1.08 V in pHcond 2.0 (0.2 mol L(-1) buffer phosphate solution). By applying DPAdSV under optimized experimental conditions the analytical curve was found to be linear in the ATOR concentration range of 90 to 3.81 × 10(3) nmol L(-1) with a limit of detection of 9.4 nmol L(-1). The proposed DPAdSV method was successfully applied in the determination of ATOR in pharmaceutical and biological samples, and the results were in close agreement with those obtained by a comparative spectrophotometric method at a confidence level of 95%.