The detection of phenolic compounds, i.e. resorcinol (RC) catechol (CC) and hydroquinone (HQ) are important due to their extremely hazardous impact and poor environmental degradation. In this work, a novel and sensitive composite of electrochemically reduced graphene oxide-poly(Procion Red MX-5B)/gold nanoparticles modified glassy carbon electrode (GCE/ERGO-poly(PR)/AuNPs) was assembled for voltammetric detection of benzenediol isomers (RC, CC, and HQ). The nanocomposite displayed high peak currents towards the oxidation of RC, HQ, and CC compared to non-modified GCE. The peak-to-peak separations were 0.44 and 0.10 V for RC-CC and CC-HQ, respectively. The limit of detections were 53, 53, and 79 nM for HQ, CC, and RC with sensitivities of 4.61, 4.38, and 0.56 μA/μM (S/N = 3), respectively. The nanocomposite displayed adequate reproducibility, besides good stability and acceptable recoveries for wastewater and cosmetic samples analyses.
Supercapacitor electrode based on conducting polymer of poly (3,4-ethylenedioxythipohene) (PEDOT) doped with nanocrystalline cellulose (NCC) films were prepared via electrochemical polymerization technique. Different applied potential, concentration and deposition time were varied to study the effect of electropolymerization potential, NCC concentration and deposition time on the formation of PEDOT/NCC film. The formation of electrochemically polymerized PEDOT/NCC composite was successfully proven with field emission scanning electron microscope (FESEM) and Fourier transform infrared spectroscopy (FTIR) techniques where the composites exhibited an interconnected network-like surface morphology. PEDOT/NCC deposited at 1.2 V in 1 mg/ml of NCC for 15 min showed the highest specific capacitance of 117.02 F/g at 100 mV/s with energy density and power density of 11.44 Wh/kg and 99.85 W/kg, respectively at the current density of 0.2 A/g. The incorporation of NCC into PEDOT revealed a lower resistance of charge transfers and improves the cycling stability by retaining 86% of capacitance after 1000 cycles.
A novel layer-by-layer (LBL) based electrode material for supercapacitor consists of polypyrrole/graphene oxide and polypyrrole/manganese oxide (PPy/GO|PPy/MnO2) has prepared by electrochemical deposition. The formation of LBL assembled nanocomposite is confirmed by Fourier transform infrared spectroscopy, Raman spectroscopy and X-ray diffraction. The field emission scanning electron microscopy images clearly showed that PPy/MnO2 was uniformly coated on PPy/GO. The PPy/GO|PPy/MnO2 symmetrical supercapacitor has revealed outstanding supercapacitive performance with a high specific capacitance of 786.6 F/g, an exceptionally high specific energy of 52.3 Wh/kg at a specific power of 1392.9 W/kg and preserve a good cycling stability over 1000 cycles. It is certain that PPy/GO|PPy/MnO2 has an extraordinary perspective as an electrode for future supercapacitor developments. This finding contributes to a significant impact on the evolution of electrochemical supercapacitor.
Clenbuterol (CLB) is an antibiotic and illegal growth promoter drug that has a long half-life and easily remains as residue and contaminates the animal-based food product that leads to various health problems. In this work, electrochemical immunosensor based on poly(3,4-ethylenedioxythiophene)/graphene oxide (PEDOT/GO) modified screen-printed carbon electrode (SPCE) for CLB detection was developed for antibiotic monitoring in a food product. The modification of SPCE with PEDOT/GO as a sensor platform was performed through electropolymerization, while the electrochemical assay was accomplished while using direct competitive format in which the free CLB and clenbuterol-horseradish peroxidase (CLB-HRP) in the solution will compete to form binding with the polyclonal anti-clenbuterol antibody (Ab) immobilized onto the modified electrode surface. A linear standard CLB calibration curve with R² = 0.9619 and low limit of detection (0.196 ng mL-1) was reported. Analysis of milk samples indicated that this immunosensor was able to detect CLB in real samples and the results that were obtained were comparable with enzyme-linked immunosorbent assays (ELISA).
An attractive electrochemical sensor of poly(3,4-ethylenedioxythiophene)/reduced graphene oxide electrode (PrGO) was developed for an electrochemical technique for uric acid (UA) detection in the presence of ascorbic acid (AA). PrGO composite film showed an improved electrocatalytic activity towards UA oxidation in pH 6.0 (0.1 M PBS). The PrGO composite exhibited a high current signal and low charge transfer resistance (Rct) compared to a reduced graphene oxide (rGO) electrode or a bare glassy carbon electrode (GCE). The limit of detection and sensitivity of PrGO for the detection of UA are 0.19 μM (S/N = 3) and 0.01 μA/μM, respectively, in the range of 1-300 μM of UA.
Asymmetric supercapacitors (ASC) have shown a great potential candidate for high-performance supercapacitor due to their wide operating potential which can remarkably enhance the capacitive behaviour. In present work, a novel positive electrode derived from functionalised carbon nanofibers/poly(3,4-ethylenedioxythiophene)/manganese oxide (f-CNFs/PEDOT/MnO2) was prepared using a multi-step route and activated carbon (AC) was fabricated as a negative electrode for ASC. A uniform distribution of PEDOT and MnO2 on f-CNFs as well as porous granular of AC are well-observed in FESEM. The assembled f-CNFs/PEDOT/MnO2//AC with an operating potential of 1.6 V can achieve a maximum specific capacitance of 537 F/g at a scan rate of 5 mV/s and good cycling stability (81.06% after cycling 8000 times). Furthermore, the as-prepared ASC exhibited reasonably high specific energy of 49.4 Wh/kg and low charge transfer resistance (Rct) of 2.27 Ω, thus, confirming f-CNFs/PEDOT/MnO2//AC as a promising electrode material for the future energy storage system.
A nanocomposite consisting of electrochemically reduced graphene oxide, poly(Eriochrome black T) and gold nanoparticles (ERGO-pEBT/AuNPs) was prepared for the simultaneous detection of resorcinol (RC), catechol (CC), and hydroquinone (HQ). The electrochemical oxidation of HQ, CC, and RC was analysed by using cyclic voltammetry and differential pulse voltammetry. Three well-separated potentials were found at 166, 277, and 660 mV (vs. Ag/AgCl) for HQ, CC, and RC, respectively The linear ranges were 0.52-31.4, 1.44-31.2, and 3.8-72.2 μM for HQ, CC, and RC, respectively. The limits of detections (LODs) for both individual and simultaneous detections are negligibly different are (15, 8, and 39 nM, respectively). Graphical abstract Voltammetric determination of hydroquinone, catechol, and resorcinol at ERGO-pEBT/AuNPs resulted in high peak currents and outstanding oxidation potential separation of the analytes.
Carbon nanotubes (CNTs) reinforced with gold nanoparticles (AuNPs) and chitosan nanoparticles (CTSNPs) were anchored on a screen-printed electrode to fabricate a multi-walled structure for the detection of quinoline. The surface morphology of the nanocomposites and the modified electrode was examined by an ultra-high resolution field emission scanning electron microscope (FESEM), and Fourier-transform infrared (FT-IR) spectroscopy was used to confirm the presence of specific functional groups on the multi-walled carbon nanotubes MWCNTs. Cyclic voltammetry (CV) and linear sweep voltammetry (LSV) were used to monitor the layer-by-layer assembly of ultra-thin films of nanocomposites on the surface of the electrode and other electrochemical characterizations. Under optimized conditions, the novel sensor displayed outstanding electrochemical reactivity towards the electro-oxidation of quinoline. The linear range was fixed between 0.0004 and 1.0 μM, with a limit of detection (LOD) of 3.75 nM. The fabricated electrode exhibited high stability with excellent sensitivity and selectivity, specifically attributable to the salient characteristics of AuNPs, CTSNPs, and MWCNTs and the synergistic inter-relationship between them. The newly developed electrode was tested in the field. The Ipa increased with an increase in the amount of quinoline solution added, and the peak potential deviated minimally, depicting the real capability of the newly fabricated electrode.
In the present work, polyvinyl-alcohol/titanium dioxide (PVA/TiO2) nanofibers are utilized as a light scattering layer (LSL) on top of the TiO2 nanoparticles photoanode. The TiO2 nanoparticles decorated PVA/TiO2 nanofibers display a power conversion efficiency (PCE) of 4.06%, which is 33% higher than TiO2 nanoparticles without LSL, demonstrating the incorporation of PVA/TiO2 nanofibers as LSL reduces the radiation loss and increases the excitation of the electron that leads to high PCE. The incorporation of PVA/TiO2 nanofibers as LSL also increases the electron life time and charge collection efficiency in comparison to the TiO2 nanoparticles without LSL.
Electrically conductive nanofiber is well known as an excellent nanostructured material for its outstanding performances. In this work, poly(3,4-ethylenedioxythiophene) (PEDOT)-coated polyvinyl alcohol-graphene oxide (PVA-GO)-conducting nanofibers were fabricated via a combined method using electrospinning and electropolymerization techniques. During electrospinning, the concentration of PVA-GO solution and the applied voltage were deliberately altered in order to determine the optimized electrospinning conditions. The optimized parameters obtained were 0.1 mg/mL of GO concentration with electrospinning voltage of 15 kV, which displayed smooth nanofibrous morphology and smaller diameter distribution. The electrospun PVA-GO nanofiber mats were further modified by coating with the conjugated polymer, PEDOT, using electropolymerization technique which is a facile approach for coating the nanofibers. SEM images of the obtained nanofibers indicated that cauliflower-like structures of PEDOT were successfully grown on the surface of the electrospun nanofibers during the potentiostatic mode of the electropolymerization process. The conductive nature of PEDOT coating strongly depends on the different electropolymerization parameters, resulting in good conductivity of PEDOT-coated nanofibers. The optimum electropolymerization of PEDOT was at a potential of 1.2 V in 5 min. The electrochemical measurements demonstrated that the fabricated PVA-GO/PEDOT composite nanofiber could enhance the current response and reduce the charge transfer resistance of the nanofiber.
The fabrication of an electrochemical sensor based on an iron oxide/graphene modified glassy carbon electrode (Fe3O4/rGO/GCE) and its simultaneous detection of dopamine (DA) and ascorbic acid (AA) is described here. The Fe3O4/rGO nanocomposite was synthesized via a simple, one step in-situ wet chemical method and characterized by different techniques. The presence of Fe3O4 nanoparticles on the surface of rGO sheets was confirmed by FESEM and TEM images. The electrochemical behavior of Fe3O4/rGO/GCE towards electrocatalytic oxidation of DA was investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) analysis. The electrochemical studies revealed that the Fe3O4/rGO/GCE dramatically increased the current response against the DA, due to the synergistic effect emerged between Fe3O4 and rGO. This implies that Fe3O4/rGO/GCE could exhibit excellent electrocatalytic activity and remarkable electron transfer kinetics towards the oxidation of DA. Moreover, the modified sensor electrode portrayed sensitivity and selectivity for simultaneous determination of AA and DA. The observed DPVs response linearly depends on AA and DA concentration in the range of 1-9 mM and 0.5-100 µM, with correlation coefficients of 0.995 and 0.996, respectively. The detection limit of (S/N = 3) was found to be 0.42 and 0.12 µM for AA and DA, respectively.
The diagnosis of hepatitis B virus (HBV) and monitoring of the vaccination efficiency against HBV require real-time analysis. The presence of antibody against hepatitis B virus surface antigen (anti-HBsAg) as a result of HBV infection and/or immunization may indicate individual immune status towards HBV. This study investigated the ability of a bio-nanogate-based displacement immunosensing strategy in detecting anti-HBsAg antibody, via nonspecific-binding between polyamidoamine dendrimers encapsulated gold nanoparticles (PAMAM-Au) and the 'antigenic determinant' region (aD) of HBsAg. For this purpose, maltose binding protein harbouring the aD region (MBP-aD) was synthesized as a bioreceptor and immobilized on the screen-printed carbon electrode (SPCE). Following that, PAMAM-Au was deposited on MBP-aD, forming the 'gate' and was used as a monitoring agent. Under optimal conditions, the high specificity of anti-HBsAg antibody towards MBP-aD displaced PAMAM-Au causing the decrement of anodic peak in differential pulse voltammetry (DPV) analysis. The signal changes were proportionally related to the concentration of anti-HBsAg antibody, in a range of 1 - 1000 mIU/mL with a limit of detection (LOD) of 2.5 mIU/mL. The results also showed high specificity and selectivity of the immunosensor platform in detecting anti-HBsAg antibody both in spiked buffer and human serum samples.
This article describes chemically modified polyaniline and graphene (PANI/GP) composite nanofibers prepared by self-assembly process using oxidative polymerization of aniline monomer and graphene in the presence of a solution containing poly(methyl vinyl ether-alt-maleic acid) (PMVEA). Characterization of the composite nanofibers was carried out by Fourier transform infrared (FTIR) and Raman spectroscopy, transmission electron microscopy (TEM) and scanning electron microscopy (SEM). SEM images revealed the size of the PANI nanofibers ranged from 90 to 360 nm in diameter and was greatly influenced by the proportion of PMVEA and graphene. The composite nanofibers with an immobilized DNA probe were used for the detection of Mycobacterium tuberculosis by using an electrochemical technique. A photochemical indicator, methylene blue (MB) was used to monitor the hybridization of target DNA by using differential pulse voltammetry (DPV) method. The detection range of DNA biosensor was obtained from of 10-6-10-9 M with the detection limit of 7.853 × 10-7 M under optimum conditions. The results show that the composite nanofibers have a great potential in a range of applications for DNA sensors.
Spermine (SPM) is considered a biomarker for prostate cancer and detecting it becomes highly challenging due to its electro- and optical-inactive nature. SPM has a tendency to interact with groups such as phosphates and sulfides to form macrocyclic arrangements known as nuclear aggregates of polyamines. Using this tendency, an electrochemical sensor has been developed using a polysulfide (PS) modified Au electrode (PS@Au electrode). PS has been synthesized from elemental sulfur by hydrothermal method and characterized using UV-Vis, fluorescence, FTIR, SEM, and XPS analyses. The PS@Au electrode was employed for electrochemical sensing of SPM. In the presence of SPM, a decrease in gold oxide reduction current was noted which is proportional to the concentration of SPM. The decrease in gold oxide reduction (0.5 V) current was attributed to the complexing nature of SPM-PS at the electrode interface. The reason for the decrease in current has been substantiated using XRF, XPS, and spectroelectrochemical studies. Under the optimized conditions, the PS@Au electrode exhibited a linear range of 1.55-250 µM with LOD of 0.511 ± 0.02 µM (3σ). The electrochemical strategy for SPM sensing exhibited better selectivity even in the presence of possible interferents. The selectivity stems from the selective interaction of SPM with PS on the Au electrode surface; the tested amino acids, and other molecules do not complex with PS and hence they could not interfere. The PS@Au electrode has been subjected to the determination of SPM in artificial urine samples and exhibited outstanding performance in the synthetic sample.
In this research work, electrochemical biosensor was fabricated based on immobilization of tyrosinase onto graphene-decorated gold nanoparticle/chitosan (Gr-Au-Chit/Tyr) nanocomposite-modified screen-printed carbon electrode (SPCE) for the detection of phenolic compounds. The nanocomposite film was constructed via solution casting method. The electrocatalytic activity of the proposed biosensor for phenol detection was studied using differential pulse voltammetry (DPV) and cyclic voltammetry (CV). Experimental parameters such as pH buffer, enzyme concentration, ratio of Gr-Au-Chit, accumulation time and potential were optimized. The biosensor shows linearity towards phenol in the concentration range from 0.05 to 15 μM with sensitivity of 0.624 μA/μM and the limit of detection (LOD) of 0.016 μM (S/N = 3). The proposed sensor also depicts good reproducibility, selectivity and stability for at least one month. The biosensor was compared with high-performance liquid chromatography (HPLC) method for the detection of phenol spiked in real water samples and the result is in good agreement and comparable.
A novel poly(3,4-ethylenedioxythiophene)-reduced graphene oxide/copper-based metal-organic framework (PrGO/HKUST-1) has been successfully fabricated by incorporating electrochemically synthesized poly(3,4-ethylenedioxythiophene)-reduced graphene oxide (PrGO) and hydrothermally synthesized copper-based metal-organic framework (HKUST-1). The field emission scanning microscopy (FESEM) and elemental mapping analysis revealed an even distribution of poly(3,4-ethylenedioxythiophene) (PEDOT), reduced graphene oxide (rGO) and HKUST-1. The crystalline structure and vibration modes of PrGO/HKUST-1 were validated utilizing X-ray diffraction (XRD) as well as Raman spectroscopy, respectively. A remarkable specific capacitance (360.5 F/g) was obtained for PrGO/HKUST-1 compared to HKUST-1 (103.1 F/g), PrGO (98.5 F/g) and PEDOT (50.8 F/g) using KCl/PVA as a gel electrolyte. Moreover, PrGO/HKUST-1 composite with the longest charge/discharge time displayed excellent specific energy (21.0 Wh/kg), specific power (479.7 W/kg) and an outstanding cycle life (95.5%) over 4000 cycles. Thus, the PrGO/HKUST-1 can be recognized as a promising energy storage material.
In this study, a composite material, manganese oxide/reduced titania nanotubes (Mn2O3/R-TNTs), was synthesized through incorporation of Mn2O3 onto R-TNTs via the reverse pulse electrodeposition technique. The influence of pulse reverse duty cycles on the morphological, structural and electrochemical performance of the surface was studied by varying the applied duty cycle from 10% to 90% for 5 min total on-time at an alternate potential of -0.90 V (E on) and 0.00 V (E off). FESEM analysis revealed the uniform deposition of Mn2O3 on the circumference of the nanotubes. The amount of Mn2O3 loaded onto the R-TNTs increased as a higher duty cycle was applied. Cyclic voltammetry and galvanostatic charge-discharge tests were employed to elucidate the electrochemical properties of all the synthesized samples in 1 M KCl. The specific capacitance per unit area was greatly enhanced upon the incorporation of Mn2O3 onto R-TNTs, but showed a decrease as a high duty cycle was applied. This proved that low amounts of Mn2O3 loading enhanced the facilitation of the active ions for charge storage purposes. The optimized sample, Mn2O3/R-TNTs synthesized at 10% duty cycle, exhibited high specific capacitance of 18.32 mF cm-2 at a current density of 0.1 mA cm-2 obtained from constant current charge-discharge measurements. This revealed that the specific capacitance possessed by Mn2O3/R-TNTs synthesized at 10% duty cycle was 6 times higher than bare R-TNTs.