Screen-printed carbon electrode for choline based on MnO2 nanoparticles and choline oxidase/polyelectrolyte layers

This paper presents the amperometric biosensor that determines choline and cholinesterase activity using a screen printed graphite electrode. In order to detect H₂O₂ we have blanket modified the electrode material with manganese dioxide nanoparticles layer. Using layer-by-layer technique on the developed hydrogen peroxide sensitive electrode surface choline oxidase was incorporated into the interpolyelectrolyte nanofilm. Its ability to serve as a detector of choline in bulk analysis and cholinesterase assay was investigated. We examined the interferences from red-ox species and heavy metals in the blood and in the environmental sample matrixes. The sensor exhibited a linear increase of the amperometric signal at the concentration of choline ranging from 1.3 × 10⁻⁷ to 1.0 × 10⁻⁴ M, with a detection limit (evaluated as 3σ) of 130 nM and a sensitivity of 103 mA M⁻¹ cm⁻² under optimized potential applied (480 mV vs. Ag/AgCl). The biosensor retained its activity for more than 10 consecutive measurements and kept 75% of initial activity for three weeks of storage at 4 °C. The R.S.D. was determined as 1.9% for a choline concentration of 10⁻⁴ M (n = 10) with a typical response time of about 10 s. The developed choline biosensor was applied for butyrylcholinesterase assay showing a detection limit of 5 pM (3σ). We used the biosensor to develop the cholinesterase inhibitor assay. Detection limit for chlorpyrifos was estimated as 50 pM.     

Electrochemical behaviors and determination of isoniazid at ordered mesoporous carbon modified electrode

In this work, an electrochemical sensor based on ordered mesoporous carbon (OMC) for the amperometric detection of isoniazid was developed. OMC was dispersed in a solution of Nafion, and the suspension was modified onto the surface of glassy carbon (GC) electrode. Cyclic voltammetry and amperometry were used to investigate the electrochemical behaviors of isoniazid on Nafion-OMC modified electrode (Nafion-OMC/GC). The results indicate that OMC can facilitate the electrochemical oxidation of isoniazid with a great decrease of overpotential in pH 7.0 phosphate buffer solution. The proposed biosensor provides excellent performance towards the determination of isoniazid with a high sensitivity of 0.031 μA/μM, a low detection limit of 8.4 × 10⁻⁸ M and wide linear range from 1.0 × 10⁻⁷ M to 3.7 × 10⁻⁴ M at +0.20 V vs. Ag/AgCl. The method was successfully applied to the determination of isoniazid tablets with satisfying results. All the results suggest that Nafion-OMC/GC electrode is a potential candidate for a stable and efficient electrochemical sensor to detect isoniazid.     

A sensitive hydrazine electrochemical sensor based on electrodeposition of gold nanoparticles on choline film modified glassy carbon electrode

A highly sensitive hydrazine sensor was developed based on the electrodeposition of gold nanoparticles onto the choline film modified glassy carbon electrode (GNPs/Ch/GCE). The electrochemical experiments showed that the GNPs/Ch film exhibited a distinctly higher activity for the electro-oxidation of hydrazine than GNPs with 3.4-fold enhancement of peak current. The kinetic parameters such as the electron transfer coefficient (α) and the rate of electron exchange (k) for the oxidation of hydrazine were determined. The diffusion coefficient (D) of hydrazine in solution was also calculated by chronoamperometry. The sensor exhibited two wide linear ranges of 5.0 × 10⁻⁷-5.0 × 10⁻⁴ and 5.0 × 10⁻⁴-9.3 × 10⁻³ M with the detection limit of 1.0 × 10⁻⁷ M (s/n = 3). The proposed electrode presented excellent operational and storage stability for the determination of hydrazine. Moreover, the sensor showed outstanding sensitivity, selectivity and reproducibility properties. All the results indicated a good potential application of this sensor in the detection of hydrazine.     

Development of molecularly imprinted electrochemical sensor with titanium oxide and gold nanomaterials enhanced technique for determination of 4-nonylphenol

4-Nonylphenol (4-NP) was reported to affect the health of wildlife and humans through altering endocrine function. A novel electrochemical sensor for sensitive and fast determination of 4-NP was developed. Titanium oxide (TiO₂) nanoparticles and gold nanoparticles (AuNPs) were introduced for the enhancement of electron conduction and sensitivity. 4-NP-imprinted functionalized AuNPs composites with specific binding sites for 4-NP was modified on electrode. The resulting electrodes were characterized by cyclic voltammetry (CV). Rebinding experiments were carried out to determine the specific binding capacity and selective recognition. The linear range was over the range from 4.80 × 10⁻⁴ to 9.50 × 10⁻⁷ mol L⁻¹, with the detection limit of 3.20 × 10⁻⁷ mol L⁻¹ (S/N = 3). The sensor was successfully employed to detect 4-NP in real samples.     

Electrocatalytic reduction of hydrogen peroxide and its determination in antiseptic and soft-glass cleaning solutions at phosphotungstate-doped-glutaraldehyde-cross-linked poly-l-lysine film electrodes

The present work describes the electrocatalytic behavior of phosphotungstate-doped glutaraldehyde-cross-linked poly-l-lysine (PLL-GA-PW) film electrode towards reduction of hydrogen peroxide (H₂O₂) in acidic medium. The modified electrode was prepared by means of electrostatically trapping the phosphotungstate anion into the cationic PLL-GA coating on glassy carbon electrode. The PLL-GA-PW film electrode showed excellent electrocatalytic activity towards H₂O₂ reduction in 0.1 M H₂SO₄. Under the optimized conditions, the electrochemical sensor exhibited a linear response for H₂O₂ concentration over the range 2.5 × 10⁻⁶ to 6.85 × 10⁻³ M with a sensitivity of 1.69 μA mM⁻¹. The curvature in the calibration curve at high concentration is explained in terms of Michaelis-Menten (MM) saturation kinetics, and the kinetics parameters calculated by three different methods were compared. The PLL-GA-PW film electrode did not respond to potential interferents such as dopamine, ascorbic acid and uric acid. This unique feature of PLL-GA-PW film electrode allowed selective determination of H₂O₂. Finally, the proposed electrochemical sensor was successfully applied to determine H₂O₂ in commercially available antiseptic solution and soft-contact lenses cleaning solution and the method has been validated using independent estimation by classical potassium permanganate titration method. Major advantages of the method are simple electrode fabrication, stability and high selectivity towards hydrogen peroxide.     

Analyte selective response in solution-deposited tetrabenzoporphyrin thin-film field-effect transistor sensors

Organic thin film transistor (OTFT) chemical sensors rely on the specific electronic structure of the organic semiconductor (OSC) film for determining sensor stability and response to analytes. The delocalized electronic structure is influenced not only by the OSC molecular structure, but also the solid state packing and film morphology. Phthalocyanine (H₂Pc) and tetrabenzoporphyrin (H₂TBP) have similar molecular structures but different film microstructures when H₂Pc is vacuum deposited and H₂TBP is solution deposited. The difference in electronic structures is evidenced by the different mobilities of H₂TBP and H₂Pc OTFTs. H₂Pc has a maximum mobility of 8.6 × 10⁻⁴ cm² V⁻¹ s⁻¹ when the substrate is held at 250 °C during deposition and a mobility of 4.8 × 10⁻⁵ cm² V⁻¹ s⁻¹ when the substrate is held at 25 °C during deposition. Solution deposited H₂TBP films have a mobility of 5.3 × 10⁻³ cm² V⁻¹ s⁻¹, which is consistent with better long-range order and intermolecular coupling within the H₂TBP films compared to the H₂Pc films. Solution deposited H₂TBP also exhibits a textured film morphology with large grains and an RMS roughness 3-5 times larger than H₂Pc films with similar thicknesses. Despite these differences, OTFT sensors fabricated from H₂TBP and H₂Pc exhibit nearly identical analyte sensitivity and analyte response kinetics. The results suggest that while the interactions between molecules in the solid state determine conductivity, localized interactions between the analyte and the molecular binding site dominate analyte binding and determine sensor response.     

Development of an optical sensor for determination of zinc by application of PC-ANN

A very sensitive and reversible optical chemical sensor based on dithizone as chromoionophore immobilized within a plasticized carboxylated PVC film for Zn²⁺ determination is described. At optimum conditions (i.e. pH 5.0), the proposed sensor displays a linear response to Zn²⁺ over 5.0 × 10⁻⁸-5.0 × 10⁻⁶ mol L⁻¹ range. This range was improved to 2.5 × 10⁻⁸-5.8 × 10⁻⁵ mol L⁻¹ range by applying principle component-feed forward artificial neural network with back-propagation training algorithm (PC-ANNB). Detection limit of 8.0 × 10⁻⁹ mol L⁻¹ was obtained. The sensor is fully reversible within the dynamic range and the response time (t_95%) is approximately 4 min under batch conditions. In addition to its high stability and reproducibility, the sensor shows good selectivity towards Zn²⁺ ion with respect to common metal cations. The sensor was successfully applied for determination of Zn²⁺ ion in hair sample.     

Electrochemical behavior of graphene doped carbon paste electrode and its application for sensitive determination of ascorbic acid

In present paper, the graphene doped carbon paste electrode (CPE) was firstly prepared with the addition of graphene into the carbon paste mixture. Compared with conventional CPE, an improved electrochemical response of graphene doped CPE toward the redox couple of Fe(CN)₆^3−/4− was demonstrated owing to the excellent electrical conductivity of graphene. The graphene doped CPE was further used for the successful determination of ascorbic acid (AA), and it showed an excellent electrocatalytic oxidation activity toward AA with a lower overvoltage, pronounced current response, and good sensitivity. Under the optimized experimental conditions, the proposed electrochemical AA sensor exhibited a rapid response to AA within 5 s and a linear calibration plot ranged from 1.0 × 10⁻⁷ to 1.06 × 10⁻⁴ M was obtained with a detection limit of 7.0 × 10⁻⁸ M.     

High sensitive simultaneous determination of hydroquinone and catechol based on graphene/BMIMPF6 nanocomposite modified electrode

A novel nanocomposite, comprising of graphene sheet (GS) and ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF₆), was developed on the glassy carbon electrode (GCE) for the simultaneous determination of hydroquinone and catechol in 0.10 M acetate buffer solution (pH 5.0). At the GS/BMIMPF₆/GCE, both hydroquinone and catechol can cause a pair of quasi-reversible and well-defined redox peaks. In comparison with bare GCE and GS modified electrode, GS/BMIMPF₆/GCE showed larger peak currents, which was related to the higher specific surface area of graphene and high ionic conductivity of BMIMPF₆. Under the optimized condition, the cathodic peak current were linear over ranges from 5.0 × 10⁻⁷ M to 5.0 × 10⁻⁵ M for hydroquinone and from 5.0 × 10⁻⁷ M to 5.0 × 10⁻⁵ M for catechol, with the detection limits of 1.0 × 10⁻⁸ M and 2.0 × 10⁻⁸ M, respectively. The proposed method was successfully applied to the simultaneous determination of hydroquinone and catechol in artificial sample, and the results are satisfactory.     

An electrochemical biosensor for determination of hydrogen peroxide using nanocomposite of poly(methylene blue) and FAD hybrid film

An electrochemical biosensor for determination of hydrogen peroxide (H₂O₂) has been developed by the hybrid film of poly(methylene blue) and FAD (PMB/FAD). The PMB/FAD hybrid film was performed in PBS (pH 7) containing methylene blue and FAD by cyclic voltammetry. Repeatedly scanning potential range of −0.6-1.1 V, FAD was immobilized on the electrode surface by electrostatic interaction while methylene blue was electropolymerized on electrode surface. This modified electrode was found surface confined and pH dependence. It showed good electrocatalytic reduction for H₂O₂, KBrO₃, KIO₃, and NaClO as well as electrocatalytic oxidation for NADH. At an applied potential of −0.45 V vs. Ag/AgCl, the sensor showed a rapid and linear response to H₂O₂ over the range from 0.1 μM to 960 μM, with a detection limit of 0.1 μM and a significant sensitivity of 1109 μA mM⁻¹ cm⁻² (S/N = 3). It presented excellent stability at room temperature, with a variation of response current less than 5% over 30 days.     

An All-solid-state Cd-selective electrode with a low detection limit

A new all-solid-state Cd²⁺-selective electrode with a low detection limit was prepared by using conjugated thiophene oligomer α-sexithiophene (α-6T) as solid contact deposited between an ionophore-doped poly(vinyl chloride) membrane and a gold disc substrate. The electrode exhibited a Nernstian response for Cd²⁺ ions over a wide concentration range of 10⁻³-10⁻⁷ M with a detection limit as low as 1.3 × 10⁻⁸ M. Results showed that the fabricated potentiometric sensor was suitable for use within the pH range of 2.0-9.0 and exhibited good reproducibility for long-term measurements.     

Two-dimensional molecular imprinting approach for the electrochemical detection of trinitrotoluene

In this work, we demonstrated a sensitive and selective electrochemical sensing protocol for the detection of TNT prepared from alkanethiols self-assembled on AuNPs modified glassy carbon (GC) electrode with preadsorbed templates of TNT. It demonstrated that the 2D molecular imprinting monolayers (MIMs) can provide a better site accessibility and lower mass-transfer resistance, while the AuNPs can enhance electrode conductivity, facilitate the electron transfer and increase the amount of TNT-imprinted sites. The prepared sensor showed not only high selectivity toward TNT in comparison to other similar nitroaromatic compounds (NACs), but also a wide linear range over TNT concentration from 4.0 × 10⁻⁸ to 3.2 × 10⁻⁶ M with a detection limit of 1.3 × 10⁻⁸ M (S/N = 3). Moreover, the imprinted sensor has been applied to the determination of TNT in spiked environmental water samples and shows promise for fast and sensitive measurement of trace levels of TNT in real samples.     

Electrocatalytic determination of hydrazine by a glassy carbon electrode modified with PEDOP/MWCNTs-Pd nanoparticles

The electrocatalysis of hydrazine oxidation by poly-ethylenedioxy pyrrole (PEDOP)-coated MWCNTs-palladium nanoparticles [PEDOP/MWCNTs-Pd] was investigated as an electrochemical sensor on the surface of glassy carbon electrode (GCE) in aqueous medium. Electrochemical oxidation of hydrazine in phosphate buffer (pH 7.4) was performed using cyclic voltammetry (CV) and chronoamperometry (CA) methods. Using the proposed electrode, the catalytic oxidation peak current of hydrazine was high and the overpotential of its oxidation decreased. Based on the obtained results, a mechanism for electrooxidation of hydrazine at [PEDOP/MWCNTs-Pd/GCE] demonstrated an irreversible diffusion-controlled electrode process and a four-electron transfer involved in the overall reaction. The experimental results showed that the mediated oxidation peak currents of the hydrazine were linearly dependent on the concentration of hydrazine in the range of 1.0 × 10⁻⁷ to 5.0 × 10⁻³ M. The detection limit (S/N = 3) was found to be 4 × 10⁻⁸ M with a fast response time of 10 s.     

Synthesis of Ag2Se nanomaterial by electrodeposition and its application as cataluminescence gas sensor material for carbon tetrachloride

In this paper, we presented a carbon tetrachloride gas sensor with strong cataluminescence response based on Ag₂Se nanomaterial, which was synthesized via the electrodeposition on the surface of Al foil by directly using a non-aqueous dimethyl sulfoxide (DMSO) solution with CH₃COOAg and SeCl₄. The deposited Ag₂Se material was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Then, the prepared Ag₂Se material along with the Al foil substrate was employed to design the carbon tetrachloride gas sensor. Under the optimized conditions, the present gas sensor exhibited a broad linear range of 0.9-228 μg mL⁻¹, with a limit of detection of 0.3 μg mL⁻¹ (S/N = 3). The proposed gas sensor showed good characteristics with high selectivity, fast response and long lifetime.     

Direct electrochemistry and electrocatalysis of hemoglobin immobilized into poly (lactic-co-glycolic acid)/room temperature ionic liquid composite film

A promising material of poly(lactic-co-glycolic acid) (PLGA) and, room temperature ionic liquid (ILs) (1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF₄) was firstly used as an immobilization matrix to entrap proteins and its bioelectrochemical properties were studied. Direct electrochemistry and electrocatalytic behaviors of hemoglobin (Hb) entrapped in the PLGA/ILs composite film on the surface of glass carbon electrode were investigated. UV-vis spectroscopy, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used to characterize the composite film. The obtained results demonstrated that the Hb molecule in the film kept its native structure and showed its good electrochemical behavior. A pair of well-defined redox peaks of Hb was obtained at the Hb/PLGA/ILs composite film-modified GC electrode through direct electron transfer between the protein and the underlying electrode. The proposed biosensor showed good reproducibility and high sensitivity to H₂O₂ with the detection limit of 2.37 × 10⁻⁷ M (S/N = 3). In the range of 5.0 × 10⁻⁶ to 8.05 × 10⁻³ M, the catalytic reduction current of H₂O₂ was proportional to its concentration. The apparent Michaelis-Menten constant of Hb in the PLGA/ILs composite film was estimated to be 0.069 mM, showing its high affinity.     

Enhanced H2S sensing characteristics of Pt doped SnO2 nanofibers sensors with micro heater

Gas sensors were designed and fabricated using oxide nanofibers as the sensing materials on micro platforms using micromachining technology. Pure and Pt doped SnO₂ nanofibers were prepared by electrospinning and their H₂S gas sensing characteristics were subsequently investigated. The sensing temperatures of 300 and 500 °C could be attained at the heater powers of 36 and 94 mW, respectively, and the sensors showed high and fast responses to H₂S. The responses of 0.08 wt% Pt doped SnO₂ nanofibers to 4-20 ppm H₂S, were 25.9-40.6 times higher than those of pure SnO₂ nanofibers. The gas sensing characteristics were discussed in relation to the catalytic promotion effect of Pt, nano-scale morphology of electrospun nanofibers, and sensor platform using micro heater.     

Lead (II) carbon paste electrode based on derivatized multi-walled carbon nanotubes: Application to lead content determination in environmental samples

For the first time a novel derivatized multi-walled carbon nanotubes-based Pb²⁺ carbon paste electrode is reported. The electrode with optimum composition, exhibits an excellent Nernstian response to Pb²⁺ ion ranging from 5.9 × 10⁻¹⁰ to 1.0 × 10⁻² M with a detection limit of 3.2 × 10⁻¹⁰ M and a slope of 29.5 ± 0.3 mV dec⁻¹ over a wide pH range (2.5-6.5) with a fast response time (25 s) at 25 °C. Moreover, it also shows a high selectivity and a long life time (more than 3 months). Importantly, the response mechanism of the proposed electrode was investigated using AC impedance technique. Finally, the electrode was successfully applied for the determination of Pb²⁺ ion concentration in environmental samples, e.g. soils, waste waters, lead accumulator waste and black tea, and for potentiometric titration of sulfate anion.     

Potentiometric solid-state sensor for DO measurement in water using sub-micron Cu0.4Ru3.4O7 + RuO2 sensing electrode

The dissolved oxygen (DO) sensing electrode (SE) concept utilizing sub-micron-sized ruthenium oxide (RuO₂), doped with other nanostructured oxides, has been extended to investigate the possibility of employing copper (II) oxide (Cu₂O) as a dopant in order to improve sensor's characteristics and meet long term antifouling needs for SEs. In this work, a thin-film SE made of RuO₂ was constructed on the alumina sensor substrate, and a range of dopants and their concentrations was added to it in order to optimize SE properties. The Cu₂O-doped RuO₂ SE had shown a linear response to DO between 0.5 and 8.0 ppm at various temperatures, with two sensitivity maxima of 47.4 and 46.0 mV per decade for Cu₂O concentrations of 10 and 20 mol%, respectively. The maximum sensitivity for Cu_0.4Ru_3.4O₇ + RuO₂-SE was obtained at a dopant concentration of 10%. Selectivity measurements revealed that the presence of Ca²⁺, Mg²⁺, Li⁺, Na⁺, NO³⁻, PO₄³⁻, SO₄²⁻, F⁻, K⁺ and Cl⁻ in the solution had no significant effect on the sensor's emf. The sensor allows overcoming the problem of an insufficient selectivity of semiconductor-based water sensors. It was also found that the doping of RuO₂-SE by Cu₂O allowed it to function at full capacity in a natural outdoor water body with no obvious effects of biofouling.     

Enhanced room temperature response of SnO2 thin film sensor loaded with Pt catalyst clusters under UV radiation for LPG

The room temperature response characteristics of SnO₂ thin film sensor loaded with platinum catalyst clusters are investigated for LPG under the exposure of ultraviolet radiation. The SnO₂-Pt cluster sensor structures have been prepared using rf sputtering. Combined effect of UV radiation exposure (λ = 365 nm) and presence of Pt catalyst clusters (10 nm thick) on SnO₂ thin film sensor surface is seen to lead to an enhanced response (4.4 × 10³) for the detection of LPG (200 ppm) at room temperature whereas in the absence of UV illumination a comparable response (∼5 × 10³) could be obtained but only at an elevated temperature of 220 °C. The present study therefore investigates the effect of UV illumination on LPG sensing characteristics of SnO₂ sensors loaded with Pt clusters of varying thickness values. Results indicate the possibility of utilizing the sensor structure with novel dispersal of Pt catalyst clusters on SnO₂ film surface for efficient detection of LPG at room temperature under the illumination of UV radiations.     

Cu chemosensing behaviour of self-organized micro-array structures of a donor-acceptor bichromophoric compound anchored onto Ag nanoisland films

This work reports on the Cu²⁺ chemosensing behaviour of self-organized micro-array structures of a novel donor-acceptor bichromophoric compound anchored onto Ag nanoisland films. The system exhibits quenching of the fluorescence in the presence of Cu²⁺ ions, with detection range extending from 2 × 10⁻⁸ M up to 3 × 10⁻⁶ M and limit of detection (LOD) of 8 × 10⁻⁹ M. The quenching of fluorescence is accompanied by a quenching of SERS signal from the metal-organic structure, which is consistent with an electron transfer between the copper cation and the organic moiety. The self-organization property of the sensing complexes into micrometric arrays offers great potential for miniaturization and future development of Cu²⁺ detection systems based on real-time observation of fluorescence or SERS quenching by fluorescence microscopy or microRaman spectroscopy.