Highly Sensitive Graphene-Based Electrochemical Sensor for Nitrite Assay in Waters.

The importance of nitrite ions has long been recognized due to their extensive use in environmental chemistry and public health. The growing use of nitrogen fertilizers and additives containing nitrite in processed food items has increased exposure and, as a result, generated concerns about potential harmful health consequences. This work presents the development of an electrochemical sensor based on graphene/glassy carbon electrode (EGr/GC) with applicability in trace level detection of nitrite in water samples. According to the structural characterization of the exfoliated material, it appears as a mixture of graphene oxide (GO; 21.53%), few-layers graphene (FLG; 73.25%) and multi-layers graphene (MLG; 5.22%) and exhibits remarkable enhanced sensing response towards nitrite compared to the bare electrode (three orders of magnitude higher). The EGr/GC sensor demonstrated a linear range between 3 × 10-7 and 10-3 M for square wave voltammetry (SWV) and between 3 × 10-7 and 4 × 10-4 M for amperometry (AMP), with a low limit of detection LOD (9.9 × 10-8 M). Excellent operational stability, repeatability and interference-capability were displayed by the modified electrode. Furthermore, the practical applicability of the sensor was tested in commercially available waters with excellent results.

Carbon nanomaterial functionalization with pesticide-detoxifying carboxylesterase.

Four carbon materials, spent coffee-ground biochar, carbon black, short CNTs, and nitrogen-doped few-layer graphene (N-graphene) were tested for their functionalization with a commercial carboxylesterase. Their robustness to variations in time and key physicochemical parameters (temperature and pH) was analysed. In general, carbon nanomaterials showed better performance than biochar, both in terms of binding capacity and resilience in harsh conditions, at statistically significant levels. Among the tested materials, functionalized N-graphene also showed the highest level of inhibition of carboxylesterase by pesticide exposure. Therefore, N-graphene was selected for biotechnological application of pesticide scavenging toxicity in T. thermophila, a ciliate bioindicator of water quality. While immobilization of the enzyme was not effective in the case of carbaryl, a methyl carbamate, in the case of the organophosphorus dichlorvos, a 1- or 30-min contact time with a water solution containing 5 times the LC100 - 0.5 mM - allowed 50% and 100% rescue of ciliate survival, respectively. These results suggest that functionalization with carboxylesterase may be of additional benefit compared to bare carbon in water clean-up procedures, especially for highly hydrophilic pesticides such as dichlorvos.

Highly Sensitive Electrochemical Detection of Azithromycin with Graphene-Modified Electrode.

An electrochemical cell containing two graphite rods was filled with the appropriate electrolyte (0.2 M ammonia + 0.2 M ammonium sulphate) and connected to the exfoliation system to synthesize graphene (EGr). A bias of 7 V was applied between the anode and cathode for 3 h. After synthesis, the morphology and structure of the sample was characterized by SEM, XRD, and FTIR techniques. The material was deposited onto the surface of a glassy carbon (GC) electrode (EGr/GC) and employed for the electrochemical detection of azithromycin (AZT). The DPV signals recorded in pH 5 acetate containing 6 × 10-5 M AZT revealed significant differences between the GC and EGr/GC electrodes. For EGr/GC, the oxidation peak was higher and appeared at lower potential (+1.12 V) compared with that of bare GC (+1.35 V). The linear range for AZT obtained with the EGr/GC electrode was very wide, 10-8-10-5 M, the sensitivity was 0.68 A/M, and the detection limit was 3.03 × 10-9 M. It is important to mention that the sensitivity of EGr/GC was three times higher than that of bare GC (0.23 A/M), proving the advantages of using graphene-modified electrodes in the electrochemical detection of AZT.

Electrochemical L-Tyrosine Sensor Based on a Glassy Carbon Electrode Modified with Exfoliated Graphene.

In this study, a graphene sample (EGr) was synthesized by electrochemical exfoliation of graphite rods in electrolyte solution containing 0.1 M ammonia and 0.1 M ammonium thiocyanate. The morphology of the powder deposited onto a solid substrate was investigated by the scanning electron microscopy (SEM) technique. The SEM micrographs evidenced large and smooth areas corresponding to the basal plane of graphene as well as white lines (edges) where graphene layers fold-up. The high porosity of the material brings a major advantage, such as the increase of the active area of the modified electrode (EGr/GC) in comparison with that of bare glassy carbon (GC). The graphene modified electrode was successfully tested for L-tyrosine detection and the results were compared with those of bare GC. For EGr/GC, the oxidation peak of L-tyrosine had high intensity (1.69 × 10-5 A) and appeared at lower potential (+0.64 V) comparing with that of bare GC (+0.84 V). In addition, the graphene-modified electrode had a considerably larger sensitivity (0.0124 A/M) and lower detection limit (1.81 × 10-6 M), proving the advantages of employing graphene in electrochemical sensing.

Investigation of L-Tryptophan Electrochemical Oxidation with a Graphene-Modified Electrode.

A graphene sample (EGr) was prepared by electrochemical exfoliation of graphite rods in solution containing 0.05 M (NH4)2SO4 + 0.1 M H3BO3 + 0.05 M NaCl. The exfoliation was performed by applying a constant voltage (12 V) between the graphite rods, while the temperature was kept constant (18 °C) with a temperature-controlled cryostat. The structural investigation of the graphene sample, performed by X-ray powder diffraction (XRD), revealed that the sample consists of a mixture of few-layer (69%), multi-layer graphene (14%) and graphene oxide (17%). In addition, XPS analysis proved that the sample was triple-doped with heteroatoms such as nitrogen (1.7 at%), sulfur (2.5 at%), and boron (3 at%). The sample was deposited onto the surface of a clean, glassy carbon electrode (GC) and investigated for the non-enzymatic electrochemical detection of L-tryptophan (TRP). The electrocatalytic properties of the EGr/GC electrode led to a considerable decrease in the oxidation potential from +0.9 V (bare GC) to +0.72 V. In addition, the EGr/GC electrode has higher sensitivity (two times) and a lower detection limit (ten times) in comparison with the bare GC electrode.

Stone Paper as a New Substrate to Fabricate Flexible Screen-Printed Electrodes for the Electrochemical Detection of Dopamine.

Flexible screen-printed electrodes (HP) were fabricated on stone paper substrate and amperometrically modified with gold nanoparticles (HP-AuNPs). The modified electrode displayed improved electronic transport properties, reflected in a low charge-transfer resistance (1220 Ω) and high apparent heterogeneous electron transfer rate constant (1.94 × 10-3 cm/s). The voltammetric detection of dopamine (DA) was tested with HP and HP-AuNPs electrodes in standard laboratory solutions (pH 6 phosphate-buffered saline (PBS)) containing various concentrations of analyte (10-7-10-3 M). As expected, the modified electrode exhibits superior performances in terms of linear range (10-7-10-3 M) and limit of detection (3 × 10-8 M), in comparison with bare HP. The determination of DA was tested with HP-AuNPs in spiked artificial urine and in pharmaceutical drug solution (ZENTIVA) that contained dopamine hydrochloride (5 mg/mL). The results obtained indicated a very good DA determination in artificial urine without significant matrix effects. In the case of the pharmaceutical drug solution, the DA determination was affected by the interfering species present in the vial, such as sodium metabisulfite, maleic acid, sodium chloride, and propylene glycol.

Nitrogen-Doped Graphene: The Influence of Doping Level on the Charge-Transfer Resistance and Apparent Heterogeneous Electron Transfer Rate.

Three nitrogen-doped graphene samples were synthesized by the hydrothermal method using urea as doping/reducing agent for graphene oxide (GO), previously dispersed in water. The mixture was poured into an autoclave and placed in the oven at 160 °C for 3, 8 and 12 h. The samples were correspondingly denoted NGr-1, NGr-2 and NGr-3. The effect of the reaction time on the morphology, structure and electrochemical properties of the resulting materials was thoroughly investigated using scanning electron microscopy (SEM) Raman spectroscopy, X-ray powder diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), elemental analysis, Cyclic Voltammetry (CV) and electrochemical impedance spectroscopy (EIS). For NGr-1 and NGr-2, the nitrogen concentration obtained from elemental analysis was around 6.36 wt%. In the case of NGr-3, a slightly higher concentration of 6.85 wt% was obtained. The electrochemical studies performed with NGr modified electrodes proved that the charge-transfer resistance (Rct) and the apparent heterogeneous electron transfer rate constant (Kapp) depend not only on the nitrogen doping level but also on the type of nitrogen atoms found at the surface (pyrrolic-N, pyridinic-N or graphitic-N). In our case, the NGr-1 sample which has the lowest doping level and the highest concentration of pyrrolic-N among all nitrogen-doped samples exhibits the best electrochemical parameters: a very small Rct (38.3 Ω), a large Kapp (13.9 × 10-2 cm/s) and the best electrochemical response towards 8-hydroxy-2'-deoxyguanosine detection (8-OHdG).

Detection of 8-Hydroxy-2'-Deoxyguanosine Biomarker with a Screen-Printed Electrode Modified with Graphene.

In this work we present the preparation of graphene material by exfoliation of graphite rods via pulses of current in electrolyte, containing a mixture of boric acid (0.05 M) and sodium chloride (0.05 M). The material was morphologically and structurally characterized by SEM/TEM/HR-TEM, XRD and FTIR techniques. TEM investigation of graphene flakes deposited onto carbon-coated grids allowed the visualization of thin and transparent regions, attributed to few-layer graphene (FLG), as well as thick and dark regions attributed to multi-layer graphene (MLG). The mixed composition of the material was additionally confirmed by XRD, which further indicated that the amount of FLG within the sample was around 83%, while MLG was around 17%. The performance of a screen-printed electrode (SPE) modified with graphene (SPE-Gr) was tested for 8-hydroxy-2'-deoxyguanosine detection. The graphene-modified electrode had a higher sensitivity in comparison with that of SPE, both in standard laboratory solutions (phosphate buffered saline-PBS) and in human saliva.