Direct Electrochemical Sensing of Phenazine‐1‐carboxylic Acid Secreted by Pseudomonas chlororaphis subsp. aureofaciens BCRC 11057T Using Disposable Screen‐printed Carbon Electrode

A novel electrochemical approach for direct recognition of antibiotic phenazine‐1‐carboxylic acid (PCA) was developed. PCA was electropolymerized on preanodized screen‐printed carbon electrode (SPCE*‐PCA) through repetitive cyclic voltammetry and characterized by XPS and FESEM. Electron transfer involved intermediate phenomenon of diffusion‐controlled redox process and surface bound redox reaction. At pH 8 (optimum), SPCE*‐PCA had a detection limit of 0.51±0.04 μM, a quantification limit of 1.7±0.13 μM, linearity of up to 50 µM, a repeatability of 15.5 % and a reproducibility of 1.7 %. PCA secreted by Pseudomonas chlororaphis subsp. aureofaciens BCRC 11057^T was investigated successfully using present single run approach.     

Voltammetric Determination of Urinary 1‐Hydroxypyrene Using Molecularly Imprinted Polymer‐Modified Screen‐Printed Carbon Electrodes

A two step non‐competitive affinity method for the trace determination of 1‐hydroxypyrene (1‐OHP) using a disposable molecularly imprinted polymer (MIP) modified screen‐printed carbon electrode (MIP‐SPCE) has been developed. The MIP was synthesized according to a novel strategy, which is described, and is capable of rebinding the phenolic analyte, 1‐hydroxypyrene (1‐OHP), from high pH aqueous organic media, via ionic interactions. In the first step of our method 1‐OHP was accumulated at the MIP‐SPCE from 35% aqueous methanol containing 0.014 M NaOH and 0.14 M NaCl, at open circuit. In the second step, the resulting SPCE with accumulated 1‐OHP was then transferred to fresh, clean phosphate buffered aqueous methanol, and subjected to cyclic voltammetry (CV) or differential pulse voltammetry (DPV). The latter technique proved to be more sensitive at detecting 1‐OHP, with a limit of detection of 182 nM and a linear range to 125 μM on unmodified electrodes. The possible effects of interference by related phenolic compounds in the MIP‐SPCE of 1‐OHP were investigated. Finally the method was evaluated by carrying out 1‐OHP determinations on spiked human urine samples; the recovery of 1‐OHP was 79.4% and the coefficient of variation was found to be 7.7% (n= 4) using a separate MIP‐SPCE for each determination. Therefore, the performance data suggests that the method is reliable at the concentrations examined in this study. The method was found to be superior to the direct determination of 1‐OHP in human urine by DPV alone, which was greatly affected by interference from uric acid.     

Heavy metal-free electrochemical detection of pyrophosphate ions by Nafion/carbon dots decorated screen printed carbon electrodes

We employ Nafion-mixed carbon dots (CDs) and low-cost screen-printed carbon electrodes (SPCEs) as foundation matrices for the fabrication of electrochemical biosensors. The  NH₂ and  COOH functional groups present on the SPCE surface after Nafion/CDs deposition allow for pyrophosphate ions (PPis) collection. Using Fe(CN)₆³⁻ as the electrochemical mediator, the SPCE-Nafion/CDs are applied to the detection of aqueous PPi by square wave voltammetry. Between 50 and 1 μM, a linear connection is established between the square wave voltammetry current and the PPi concentration. The limit of detection is determined to be 1.01 μM, and recoveries of 113% (±1.9%) and 108% (±3.9%) are achieved for human urine samples spiked with 6 and 3 μM of PPi, respectively. Furthermore, this PPi assay is suitable for the usage of complicated urine matrices without the inclusion of heavy metals. We anticipate that this unique approach will be beneficial for PPi level monitoring in urine during therapeutic treatments of illnesses and malignancies.     

Polyaniline Sheathed Black Phosphorous: A Novel,Advanced Platform for Electrochemical Sensing Applications

Despite its excellent properties, the inherent unstable nature of black phosphorus (BP) in ambient atmosphere has severely restricted its use in electrochemical sensing applications. In this work, polyaniline (PANI) sheathed BP was prepared via the electrochemical polymerisation of aniline on BP coated screen printed carbon electrode (i. e., SPCE/BP) which resulted in an efficient, stable electrochemical platform (i. e., SPCE/BP@PANI) with improved properties which was evaluated for electrochemical detection of two model bioanalytes namely, ascorbic acid (AA) and Hydrazine (Hy). The formation of PANI on the SPCE/BP exhibited a pair of stable and well‐defined redox peaks indicating the better adsorption energy and fast electron transfer nature of BP as compared to other 2D materials like graphene and transitional metal dichalcogenides. FESEM and XPS studies revealed the formation and uniform growth of PANI on BP surface without any aggregation. Electrochemical impedance spectroscopy analyses revealed that SPCE/BP@PANI can act as a suitable electrocatalyst material for the sensing of AA and Hy. Thus, SPCE/BP@PANI electrode exhibited low limit of detection (D_L; 1.69 μM), excellent reproducibility and better selectivity towards AA oxidation over glucose, sucrose, urea, citric acid, sodium, nitrate, nitrite and magnesium with a sensitivity of 3.38 A M^?1 cm^?2 (R²=0.98) in the dynamic range of 10–1100 μM. The excellent analytical performance of the BP@PANI is plausible due to better adsorption energy and fast electron transfer of BP. Further, SPCE/BP@PANI was also used for successful detection of AA in processed fruit juice with good recovery. Under the optimal DPV conditions, the modified electrode was extended for detection of Hy in a linear range of 100–1500 μM with sensitivity of 0.09 A M^?1 cm^?2 (R²=0.99) and D_L=89 μM validating the potential of BP based composites in wide range of electrochemical applications.     

Amperometric Biosensors for Tyramine Determination Based on Graphene Oxide and Polyvinylferrocene Modified Screen‐printed Electrodes

A comparison of the analytical characteristics of two tyramine biosensors, based on graphene oxide (GRO) and polyvinylferrocene (PVF) modified screen‐printed carbon electrodes (SPCE), is reported. Diamine oxidase (DAOx) or monoamine oxidase (MAOx) was immobilized onto the PVF/GRO modified SPCE to fabricate the biosensors. Surface characteristics and electrochemical behaviour of the modified SPCEs were investigated by atomic force microscopy (AFM), scanning electron microscopy (SEM), energy dispersive X‐ray spectroscopy (EDX) and cyclic voltammetry (CV). Electrode surface composition and experimental variables such as pH and working potential were optimized in order to ensure a high performance. Under optimum experimental conditions, both DAOx/PVF/GRO/SPCE and MAOx/PVF/GRO/SPCE biosensors exhibited wide linear dynamic ranges for tyramine from 9.9×10^?7 to 1.2×10^?4 M and from 9.9×10^?7 to 1.1×10^?4 M, respectively. MAOx/PVF/GRO/SPCE biosensor showed higher sensitivity (11.98 μA mM^?1) for tyramine determination than the DAOx/PVF/GRO/SPCE biosensor (7.99 μA mM^?1). The substrate specifity of the biosensors to other biogenic amines namely histamine, putrescine, spermine, spermidine, tryptamine, β‐phenylethylamine and cadaverine was also investigated. The developed biosensors were successfully used for tyramine determination in cheese sample.     

Electrochemical Determination of Tartrazine in Foods by Voltammetry with a Screen-printed Carbon/Chitosan-MnO2 Microcomposite Electrode

This paper presents a new application for a screen-printed carbon electrode (SPCE) modified with chitosan (Cs) and manganese oxide (II). This new electrode (Cs-Mn_OX/SPCE) was applied in the detection of tartrazine (TZ) by linear scan voltammetry (LSV). The anodic peak current for TZ increased by nearly 500 % compared with Cs/SPCE and unmodified SPCE. The surface of the electrode was characterized by cyclic voltammetry. The detection limit was 0.06 μmol/L. The relative standard deviations (RSDs) were between 1.0 and 6.0 % (n=15). The accuracy of the new method was evaluated with real samples spiked with known quantities of TZ.     

Facile preparation of a cellulose microfibers–exfoliated graphite composite: a robust sensor for determining dopamine in biological samples

A simple and robust dopamine (DA) sensor was developed using a cellulose microfibers (CMF)–exfoliated graphite composite-modified screen-printed carbon electrode (SPCE) for the first time. The graphite-CMF composite was prepared by sonication of pristine graphite in CMF solution and was characterized by high-resolution scanning electron microscopy, Fourier transform, infrared, and Raman spectroscopy. The cyclic voltammetry results reveal that the graphite-CMF composite modified SPCE has superior electrocatalytic activity against oxidation of dopamine than SPCE modified with pristine graphite and CMF. The presence of large edge plane defects on exfoliated graphite and abundant oxygen functional groups of CMF enhance electrocatalytic activity and decrease potential to oxidize DA. Differential pulse voltammetry was used to quantify DA using the graphite-CMF composite-modified SPCE and demonstrated a linear response for DA detection in the range of 0.06–134.5 µM. The sensor shows a detection limit at 10 nM with an appropriate sensitivity and displays appropriate recovery of DA in human serum samples with good repeatability. Sensor selectivity is demonstrated in the presence of 50-fold concentrations of potentially active interfering compounds including ascorbic acid, uric acid, and dihydroxybenzene isomers.     

Graphene Oxide‐Modified Electrode Coated with in‐situ Antimony Film for the Simultaneous Determination of Heavy Metals by Sequential Injection‐Anodic Stripping Voltammetry

The proposed chemically modified electrode was graphene oxide that was synthesized via Hummer's method followed by reduction of antimony film by in‐situ electrodeposition. The experimental process could be concluded in three main steps: preparation of antimony film, reduction of analyte ions on the electrode surface and stripping step under the conditions of square wave anodic stripping voltammetry (SWASV). A simple and rapid approach was developed for the determination of heavy metals simultaneously based on a sequential injection (SI), an automated flow‐based system, coupled with voltammetric method using antimony‐graphene oxide modified screen‐printed carbon electrode (SbF‐GO‐SPCE). The effects of main parameters involved with graphene oxide, antimony and measurement parameters were also investigated. Using SI‐SWASV under the optimal conditions, the proposed electrode platform has exhibited linear range from 0.1 to 1.5 M. Calculated limits of detection were 0.054, 0.026, 0.060, and 0.066 μM for Cd(II), Pb(II), Cu(II) and Hg(II), respectively. In addition, the optimized method has been successfully applied to determine heavy metals in real water samples with acceptable accuracy of 94.29 – 113.42 % recovery.     

CuAg nanoparticles formed in situ on electrochemically pre‐anodized screen‐printed carbon electrodes for the detection of nitrate and nitrite anions

CuAg nanoparticles (CuAgNPs) were electrochemically formed in situ on pre‐anodized, screen‐printed carbon electrodes (SPCEs) that possessed many oxygen‐containing functional groups capable of adsorbing metal ions, namely Cu²⁺ and Ag⁺. Pre‐anodization was achieved using continuous cyclic voltammetry in the range of potential 0.3–2.0 V under a scan rate of 50 mV/s. Cu²⁺ and Ag⁺ ions were adsorbed on the pre‐anodized SPCE by immersing the electrode in solutions containing both metal ions, and then CuAgNPs were formed in situ via electrochemical reduction in a deaerated, neat NaClO₄ solution after the electrode was ultrasonicated to remove physically adsorbed metal ions. Although CuNPs showed higher activity than AgNPs toward both nitrate (NO₃⁻) and nitrite (NO₂⁻) ions, the instability of CuNPs hindered the application, so CuAgNPs were employed to achieve a compromise between sensitivity and stability. The SPCE/anodized/CuAgNP electrodes showed activity toward the electrochemical reduction of NO₃⁻ and NO₂⁻, respectively, with the limit of detection (LOD) of 15.6 μM (0.97 ppm) and 11.1 μM (0.51 ppm), which is sufficient to fit the allowed values (50 and 3 ppm, respectively) in drinking water as suggested by the World Health Organization (WHO).     

Disposable Amperometric Biosensor Based on Poly‐L‐lysine and Fe3O4 NPs‐chitosan Composite for the Detection of Tyramine in Cheese

An amperometric tyramine biosensor based on poly‐L‐lysine (PLL) and Fe₃O₄ nanoparticles (Fe₃O₄NP) modified screen printed carbon electrode (SPCE) was developed. PLL was formed on the SPCE by the electropolymerization of L‐lysine. Subsequently, Fe₃O₄NP suspension prepared in chitosan (CH) solution was casted onto the PLL/SPCE. Tyrosinase (Ty) enzyme was immobilized onto the modified Fe₃O₄?CH/PLL/SPCE and the electrode was coated with Nafion to fabricate the Ty/Fe₃O₄?CH/PLL/SPCE. Different techniques including scanning electron microscopy, chronoamperometry (i–t curve), cyclic voltammetry and electrochemical impedance spectroscopy were utilized to study the fabrication processes, electrochemical characteristics and performance parameters of the biosensor. The analytical performance of the tyramine biosensor was evaluated with respect to linear range, sensitivity, limit of detection, repeatability and reproducibility. The response of the biosensor to tyramine was linear between 4.9×10^?7–6.3×10^?5 M with a detection limit of 7.5×10^?8 M and sensitivity of 71.36 μA mM^?1 (595 μA mM^?1 cm^?2). The application of the developed biosensor for the determination of tyramine was successfully tested in cheese sample and mean analytical recovery of added tyramine in cheese extract was calculated as 101.2±2.1 %. The presented tyramine biosensor is a promising approach for tyramine analysis in real samples due to its high sensitivity, rapid response and easy fabrication.     

Immobilization of CoII-(N,N′-bis(salicylidene)-2-aminobenzylamine) on Poly(pyrrole-co-o-anisidine)/Chitosan Composite Films: Application to Electrocatalytic Oxidation of Catechol

In this study, poly (pyrrole-co-o-anisidine)/chitosan composite (Cs) films were prepared by cyclic voltammetry technique on platinum electrode using different pyrrole and o-anisidine mole ratios. Immobilization process was accomplished in Co^II-(N,N′-bis(salicylidene)-2-aminobenzylamine)(CoL) dissolved 0.15 M acetonitrile-LiClO₄ solution by cyclic voltammetry technique at 0.2–2.0 V potential range. Three electrode methods were applied in all electrochemical studies. After immobilization process, the characterizations of the electro catalytic surfaces (Cs−CoL−Pt) were carried out by cyclic voltammetry and SEM images. The SEM images clearly indicated that the [CoL] complex is immobilized onto composite films. The electrocatalytic activity of the modified electrodes on the catechol was investigated using buffer solutions of different pH values. The results of catalytic studies revealed that, pH=10 buffer solution was the optimal solution and 1 : 1 Cs−CoL−Pt electrode was the best electrode for catechol oxidation. In square wave voltammetry measurements using this electrode, two linear working ranges were determined. The linear response ranges for catechol determination were found as 3.0 μM–6.0 μM and 16 μM–80 μM for the first and the second linear working ranges, respectively, with 1.1 μM detection limit.     

Determination of hydroxylamine using a carbon paste electrode modified with graphene oxide nano sheets

A carbon paste electrode that was chemically modified with 3-(4'-amino-3'-hydroxy-biphenyl-4-yl)-acrylic acid (3,4-AA) was used as a selective electrochemical sensor for the detection of hydroxylamine. Cyclic voltammetry (CV), choronoamperometry (CHA) and square wave voltammetry (SWV) were used to investigate oxidation of hydroxylamine in aqueous solution. Under optimized concentration the electrocatalytic oxidation current peak for hydroxylamine increased linearly with concentration in the range of 0.025–10.0 μM. The detection limits for hydroxylamine was 0.012 μM. Finally, the modified electrode was applied to detection hydroxylamine in water samples.     

Sensitive determination of diuron on zinc oxide nanoparticles modified carbon paste electrode in soil and water samples

An electrochemical sensor based on Zinc oxide nanoparticles (ZnONPs) modified carbon paste electrode was designed for the toxic diuron pesticide detection. The ZnONPs were synthesized through the hydrothermal route and their structural properties were investigated via scanning electron microscopy (SEM) and X-ray diffraction powder (XRD). The designed ZnONPs-modified carbon paste electrode (ZnONPs-CPE) was characterized using cyclic voltammetry and electrochemical impedance spectroscopy. The sensor showed significantly enhanced sensitivity on the diuron oxidation peak current, compared to the bare carbon paste electrode. Qualitative and quantitative analysis were performed using cyclic voltammetry (CV) and square wave voltammetry (SWV). Experimental parameters such as pH, amount of ZnONPs and frequency were evaluated and the optimized conditions were obtained with 0.1 M phosphate buffer solution at pH=8, a frequency of 50 Hz and a quantity of 5 mg of ZnONPs. Under these conditions, linear responses ranging from 1.3 to 7.7 μM and 8.6 to 30 μM of diuron were obtained, with correlation coefficients of R²=0.994 and 0.996 respectively. Detection and quantification limits of 0.22 μM and 0.84 μM (S/N=3) were respectively achieved based on the 3σ method. The interference of some ions on the oxidation peak of diuron on ZnONPs-CPE was also evaluated and no interference was observed, therefore demonstrating the selectivity of the sensor. The proposed sensor, designed with ecofriendly materials, is sensitive, selective and was effectively used for diuron determination in soils and water samples with recoveries ranging from 98 % to 101.5 %.     

Silica‐modified Electrodes for Electrochemical Detection of Malachite Green

New silica‐modified glassy carbon electrodes prepared with three different sorts of ordered mesoporous silica (OMS) were characterized and tested for the electrochemical detection of Malachite Green (MG). The electrodes were prepared by drop casting using silica suspensions and, for stability sake, a Nafion coating was deposited on the electrode top by the same technique. Square wave anodic stripping voltammetry was used to investigate the effect of various experimental parameters (deposition time, solution pH, silica type and concentration) on the performance of the modified electrodes. The best electrode (GC/MCM‐41‐NH₂/Nafion) with detection limit 0.36 μM, sensitivity 0.164±0.003 A/M; linear domain 1–6 μM was applied to detect MG in a commercial product commonly used as biocide in aquaria for ornamental fish.     

A Sensitive Electrochemical Approach for Melamine Detection Using a Disposable Screen Printed Carbon Electrode

We report here a simple and easy electrochemical approach for sensitive detection of non‐electroactive melamine using a disposable screen printed carbon electrode (SPCE) with uric acid as the recognition element. It is based on the competitive adsorptive behavior of melamine at the preanodized SPCE causing suppression in the oxidation current of uric acid. A linear range up to 126 ppb with a detection limit of 1.6 ppb (S/N=3) is achieved at the preanodized SPCE by differential pulse voltammetry. The electrochemical method is successfully applied to detect the melamine content in tainted milk powder and dog food.     

Electrochemically Degraded Dopamine Film for the Determination of Dopamine

A dopamine (DA) polymer was deposited electrochemically on to a glassy carbon (GC) surface until the electrode surface was passivated. The DA film on the GC surface was re‐formed for high sensitivity and reproducibility by electrochemical degradation. The re‐formed electrode was sensitive and selective in the determination of DA in the presence of ascorbic acid. The linear range obtained by square‐wave voltammetry was between 0.1 and 2.1 μM (R=0.996, n=6) with a sensitivity of 1.2 μA μM^?1 and a detection limit (S/N=3) of 0.04 μM. The electropolymerized DA film was stable and the re‐formed electrode was reproducible for DA determination.     

Sensitive Electrochemical Detection of Thiabendazole in Fruits Using Ag−MoS2 Electrode

Herein, Ag nanoparticles (NPs) modified MoS₂ (Ag−MoS₂) was applied to the surface of glassy carbon (GC) to produce a robust electrochemical sensor for the detection of thiabendazole, a common antifungal in the post-harvesting of fruits. Cyclic voltammetry studies confirmed thiabendazole exhibited an irreversible, diffusion-controlled process on Ag−MoS₂ with a two-fold increase in peak current than the pristine MoS_2. A square wave voltammetry was used for the detection of TBZ. The developed sensor exhibited a linear range between 1–10 μM with LOD down to 0.1 μM (S/N>3). Analysis of TBZ in mango and banana matrices gave a recovery of 91.6–100.4 % indicating the suitability of the sensor for food safety monitoring.     

Voltammetric Determination of Uric Acid at a Fullerene‐C60‐Modified Glassy Carbon Electrode

Glassy carbon electrode modified by microcrystals of fullerene‐C₆₀ mediates the voltammetric determination of uric acid (UA) in the presence of ascorbic acid (AA). Interference of AA was overcome owing to the ability of pretreated fullerene‐C₆₀‐modified glassy carbon electrode. Based on its strong catalytic function towards the oxidation of UA and AA, the overlapping voltammetric response of uric acid and ascorbic acid is resolved into two well‐defined voltammetric peaks with lowered oxidation potential and enhanced oxidation currents under conditions of both linear sweep voltammetry (LSV) and Osteryoung square‐wave voltammetry (OSWV). At pH 7.2, a linear calibration graph is obtained for UA in linear sweep voltammetry over the range from 0.5 μM to 700 μM with a correlation coefficient of 0.9904 and a sensitivity of 0.0215 μA μM^?1 . The detection limit (3σ) is 0.2 μM for standard solution. AA in less than four fold excess does not interfere. The sensitivity and detection limit in OSWV were found as 0.0255 μA μM^?1 and 0.12 μM, for standard solution respectively. The presence of physiologically common interferents (i.e. adenine, hypoxanthine and xanthine) negligibly affects the response of UA. The fullerene‐C₆₀‐modified electrode exhibited a stable, selective and sensitive response to uric acid in the presence of interferents.     

Electrochemical Properties of Ag@iron Oxide Nanocomposite for Application as Nitrate Sensor

Ag@iron oxide nanocomposite powders were synthesized via a two‐step chemical method. Characterization by UV‐Vis, XRD, SEM‐EDX and TEM revealed they are composed of nanosized crystalline silver particles in strict contact with amorphous iron oxide(s). The electrochemical behavior of the synthesized Ag@iron oxide composite was investigated by cyclic voltammetry. Compared with the single phase‐modified electrodes, the Ag@iron oxide/SPCE electrode exhibits an enhanced cathodic current in response to the target analyte, due to a synergistic effect between Ag crystallites and amorphous iron oxide nanoparticles. An amperometric sensor for detection of nitrate based on Ag@iron oxide modified screen‐printed electrode (Ag@iron oxide/SPCE) has been fabricated, showing a good sensitivity (663 µA mM^?1 cm^?2) and a detection limit of 30 µM.     

Development of an Aluminium Doped TiO2 Nanoparticles‐modified Screen Printed Carbon Electrode for Electrochemical Sensing of Vanillin in Food Samples

A new chemically modified electrode based on titanium dioxide nanoparticles (TiO₂‐NPs) has been developed. Aluminium was incorporated into the TiO₂‐NPs to prepare aluminium doped TiO₂ nanoparticles (Al‐TiO₂‐NPs). Aluminium doped TiO₂ nanoparticles‐modified screen printed carbon electrode (Al‐TiO₂‐NPs/SPCE) was employed as easy, efficient and rapid sensor for electrochemical detection of vanillin in various types of food samples. Al‐TiO₂‐NPs were characterized by energy‐dispersive X‐ray (EDX), transmission electron microscopy (TEM), and X‐ray diffraction (XRD) and analyses showing that the average particle sizes varied for the Al‐NPs (7.63 nm) and Al‐TiO₂‐NPs (7.47 nm) with spherical crystal. Cyclic voltammetry (CV) and linear sweep voltammetry (LSV) were used to optimize the analytical procedure. A detection limit of vanillin was 0.02 μM, and the relative standard deviation (RSD) was 3.50 %, obtained for a 5.0 μM concentration of vanillin. The electrochemical behaviour of several compounds, such as vanillic acid, vanillic alcohol, p‐hydroxybenzaldehyde and p‐hydroxybenzoic, etc., generally present in natural vanilla samples, were also studied to check the interferences with respect to vanillin voltammetric signal. The applicability was demonstrated by analysing food samples. The obtained results were compared with those provided by a previous method based on liquid chromatography for determination of vanillin.