Electrodeposited Graphene and Silver Nanoparticles Modified Electrode for Direct Electrochemistry and Electrocatalysis of Hemoglobin

By using a 1‐butylpyridinium hexafluorophosphate based carbon ionic liquid electrode (CILE) as the working electrode, graphene (GR) nanosheets and silver nanoparticles (Ag NPs) were step by step electrodeposited on the surface of the CILE with potentiostatic method. The fabricated Ag/GR/CILE was used as a new platform for protein electrochemistry and hemoglobin (Hb) was immobilized on its surface with chitosan (CTS) as film forming material. In 0.1 mol/L phosphate buffer solution, a pair of well‐defined and quasi‐reversible redox peaks appeared on the CTS/Hb/Ag/GR/CILE with a formal peak potential of ?0.202 V (vs. SCE) and a peak‐to‐peak separation (ΔE_p) of 68 mV, which indicated that direct electrochemistry of Hb was realized on the modified electrode. The results could be attributed to the synergistic effects of Ag NPs and GR nanosheets on the electrode surface, which provided a specific three‐dimensional structure with high conductivity and good biocompatibility. The Hb modified electrode showed excellent electrocatalysis to the reduction of trichloroacetic acid in the concentration range from 0.8 to 22.0 mmol/L with a detection limit of 0.42 mmol/L (3σ). Moreover, the modified electrode exhibited favorable reproducibility, long term stability and accuracy, with potential applications in the third‐generation electrochemical biosensor.     

Electrodeposited nanogold decorated graphene modified carbon ionic liquid electrode for the electrochemical myoglobin biosensor

In this paper, a carbon ionic liquid electrode (CILE) was fabricated using ionic liquid 1-hexylpyridinium hexafluorophosphate as modifier, which was further in situ electrodeposited with graphene (GR) and gold nanoparticles step by step to get an Au/GR nanocomposite modified CILE. Myoglobin (Mb) was further immobilized on the Au/GR/CILE surface with Nafion film to get the modified electrode denoted as Nafion/Mb/Au/GR/CILE. Cyclic voltammetric experiments indicated that a pair of well-defined quasi-reversible redox peaks appeared in pH 3.0 phosphate buffer solution with the formal potential (E ^0′) located at ?0.197 V (vs. saturated calomel electrode), which was the typical characteristics of Mb heme Fe(III)/Fe(II) redox couples. Thus, the direct electron transfer rate between Mb and the modified electrode was promoted due to the high conductivity and increased surface area of Au/GR nanocomposite present on electrode surface. Based on the cyclic voltammetric data, the electrochemical parameters of Mb on the modified electrode were calculated. The Mb-modified electrode showed excellent electrocatalytic activities towards the reduction of trichloroacetic acid and H₂O₂ with wider linear range and lower detection limit. Using GR and Au nanoparticles modified CILE, a new third-generation electrochemical Mb biosensor was constructed with good stability and reproducibility.     

Direct electrochemistry and electrocatalysis of hemoglobin on gold nanoparticle decorated carbon ionic liquid electrode

In this paper a carbon ionic liquid electrode (CILE) was fabricated by using ionic liquid 1-ethyl-3-methylimidazolium ethylsulfate ([EMIM]EtOSO₃) as modifier and further gold nanoparticles were in situ electrodeposited on the surface of CILE. The fabricated Au/CILE was used as a new platform for the immobilization of hemoglobin (Hb) with the help of a Nafion film. Electrochemical experimental results indicated that direct electron transfer of Hb was realized on the surface of Au/CILE with a pair of well-defined quasi-reversible redox peaks appeared. The formal peak potential (E⁰′) was obtained as −0.210 V (vs. SCE) in pH 7.0 phosphate buffer solution (PBS), which was the characteristic of Hb heme Fe(III)/Fe(II) redox couple. The fabricated Nafion/Hb/Au/CILE showed excellent electrocatalytic activity to the reduction of trichloroacetic acid (TCA) and the reduction peak current was in proportional to TCA concentration in the range from 0.2 to 18.0 mmol/L with the detection limit as 0.16 mmol/L (S/N = 3). The proposed electrode showed good stability and reproducibility, and it had the potential application as a new third-generation electrochemical biosensor.     

Electrochemical Design of Ultrathin Palladium Coated Gold Nanoparticles as Nanostructured Catalyst for Amperometric Detection of Formaldehyde

An underpotential deposition (UPD) replacement tactic was employed to design a Pd overlayer on gold (Au) nanoparticles electrodeposited on a carbon ionic liquid electrode (CILE). Pd/Au/CILE was applied as an amperometric sensor for the determination of formaldehyde in aqueous solutions. The sensor displayed two linear ranges from 15 µM–1.4 mM and 1.4–56.7 mM of formaldehyde. The limit of detection was 3 µM of formaldehyde and the sensitivity of the sensor was 2.35 µA mM^?1, using the calibration graph in the lower range. The presence of 20 mM of formic acid and methanol and 10 mM ethanol did not interfere with the determination of formaldehyde solution.     

Silver‐Palladium Nanoalloys Modified Carbon Ionic Liquid Electrode with Enhanced Electrocatalytic Activity Towards Formaldehyde Oxidation

Electrocatalysis of the oxidation of formaldehyde on silver‐palladium‐modified carbon ionic liquid electrode (AgPd/CILE) was investigated in 0.1 M NaOH. The electrochemical performance of the AgPd/CILE was compared with those of Pd/CILE and Ag/CILE. Ag plays an important role in the catalytic performance of AgPd nanocatalyst and yields an excellent antifouling effect. Amperometric measurements showed that AgPd/CILE is a promising sensor for the detection of formaldehyde in the range of 10.0 µM–70.0 mM with a sensitivity of 240.6 µA mM^?1 cm^?2 and a detection limit of 2 µM. The method is free from interference of methanol, ethanol and formic acid.     

Comparison of Insulin Determination on NiNPs/chitosan‐ MWCNTs and NiONPs/chitosan‐MWCNTs Modified Pencil Graphite Electrode

The rising amount of patients suffering for diabetes mellitus increases the requirements for effective insulin sensors. Carbon materials are a suitable choice for the development of insulin sensors due to their electrochemical characteristics. Pencil graphite electrodes (PGE) represent the trade‐off between price and excellent conductive properties. The modification of PGE by NiO and Ni nanoparticles fixed by chitosan results in surface area enlargement and improved electrocatalytic properties. This paper is focused on the comparison of different properties of Ni and NiO nanoparticles and their effect on redox reaction mechanism of insulin and detection characteristics. The electrode modified by Ni nanoparticles displays linear range of 1 μM–5 μM (R² 0.80), limit of detection (LOD) of 4.34 μM and sensitivity of 0.12 μA/μM. On the other hand, the electrode modified by NiO nanoparticles displays enhanced electrochemical characteristics such as linear range of 0.05 μM–5 μM (R² 0.99), limit of detection of 260 nM and sensitivity of 0.64 μA/μM. These properties make the NiO nanoparticles modified PGE the appropriate candidate for insulin determination.     

Direct Electron Transfer and Electrocatalysis of Myoglobin Based on its Direct Immobilization on Carbon Ionic Liquid Electrode

Direct electron transfer of myoglobin (Mb) was achieved by its direct immobilization on carbon ionic liquid electrode (CILE) with a conductive hydrophobic ionic liquid, 1‐butyl pyridinium hexaflourophosphate ([BuPy][PF₆]) as binder for the first time. A pair of well‐defined, quasi‐reversible redox peaks was observed for Mb/CILE resulting from Mb redox of heme Fe(III)/Fe(II) redox couple in 0.1 M phosphate buffer solution (pH 7.0) with oxidation potential of ?0.277 V, reduction potential of ?0.388 V, the formal potential E°′ (E°′=(E_pa+E_pc)/2) at ?0.332 V and the peak‐to‐peak potential separation of 0.111 V at 0.5 V/s. The average surface coverage of the electroactive Mb immobilized on the electrode surface was calculated as 1.06±0.03×10^?9 mol cm^?2. Mb retained its bioactivity on modified electrode and showed excellent electrocatalytic activity towards the reduction of H₂O₂. The cathodic peak current of Mb was linear to H₂O₂ concentration in the range from 6.0 μM to 160 μM with a detection limit of 2.0 μM (S/N=3). The apparent Michaelis–Menten constant (K and the electron transfer rate constant (k_s) were estimated to be 140±1 μM and 2.8±0.1 s^?1, respectively. The biosensor achieved the direct electrochemistry of Mb on CILE without the help of any supporting film or any electron mediator.     

Facile synthesis of a porous network-like silver film for electrocatalytic detection of nitrate

We have developed a method for in-situ construction of a porous network-like silver film on the surface of a glassy carbon electrode (GCE). It is based on a galvanic replacement reaction where a layer of copper nanoparticles is first electrodeposited as a sacrificial template. The silver film formed possesses a porous network-like structure and consists of an assembly of numerous nanoparticles with an average size of 200 nm. The electrode displays excellent electrocatalytic activity, good stability, and fast response (within 2 s) toward the reduction of nitrate at a working potential of −0.9 V. The catalytic currents linearly increase with the nitrate concentrations in the range of 0.08–6.52 mM, with a detection limit of 3.5 μM (S/N = 3) and a repeatability of 3.4 % (n = 5).

A facile method was developed for in situ construction of a porous network-like Ag film on a glassy carbon electrode by a galvanic replacement reaction, where a layer of Cu nanoparticles previously electrodeposited as a sacrificial template. Thus-formed Ag film displays excellent electrocatalytic activity, good stability, and fast response (within 2 s) toward nitrate reduction.

     

Square Wave Voltammetry for Selective Detection of Dopamine Using Polyglycine Modified Carbon Ionic Liquid Electrode

The electrochemical polymerization of glycine on carbon ionic liquid electrode (CILE) was described. The presence of ionic liquid on the surface of CILE facilitated the electropolymerization of glycine. The polyglycine modified CILE provided a valid and simple approach to selectively detect dopamine in the presence of AA in physiological environment. The proposed sensor not only decreased the voltammetric responses of AA but also dramatically enhanced the oxidation peak current of DA compared to bare CILE. Using square wave voltammetry, the modified CILE showed good electrochemical behavior to DA, a linear range of 1.0×10^?7–3.0×10^?4 M in the presence of 1 mM ascorbic acid (AA) and a detection limit of 5.0×10^?9 M was estimated (S/N=3).     

Facile synthesis of a porous network-like silver film for electrocatalytic detection of nitrate

We have developed a method for in-situ construction of a porous network-like silver film on the surface of a glassy carbon electrode (GCE). It is based on a galvanic replacement reaction where a layer of copper nanoparticles is first electrodeposited as a sacrificial template. The silver film formed possesses a porous network-like structure and consists of an assembly of numerous nanoparticles with an average size of 200 nm. The electrode displays excellent electrocatalytic activity, good stability, and fast response (within 2 s) toward the reduction of nitrate at a working potential of ?0.9 V. The catalytic currents linearly increase with the nitrate concentrations in the range of 0.08–6.52 mM, with a detection limit of 3.5 μM (S/N?=?3) and a repeatability of 3.4 % (n?=?5).

Prussian Blue Modified Carbon Ionic Liquid Electrode: Electrochemical Characterization and Its Application for Hydrogen Peroxide and Glucose Measurements

Prussian blue modified carbon ionic liquid electrodes (PB‐CILEs) were fabricated using chemical and electrochemical procedures. Chemically fabricated PB‐CILE exhibited an excellent sensitivity (0.0866 μA μM^?1), low detection limit (0.01 μM) and two linear ranges (0.01–1 and 1–600 μM) toward hydrogen peroxide. Then, glucose oxidase (GOx) was immobilized on the surface of PB‐CILE to fabricate glucose biosensor using three different procedures involving cross linking with glutaraldehyde (GLU) and bovine serum albumin (BSA), entrapment into the Nafion matrix and covering with a sol‐gel layer. Glucose biosensor fabricated using cross linking procedure showed the best sensitivity (0.0019 μA μM^?1) and operational stability for glucose.     

Oxygen reduction on electrodeposited silver catalysts in alkaline solution

In this study, silver was electrochemically deposited onto glassy carbon (GC) substrate using constant potential regime and tested for oxygen reduction reaction (ORR) in alkaline media. The surface morphology of Ag/GC electrodes was studied by scanning electron microscopy (SEM). It was established that after 10 s of deposition, a number of Ag nanoparticles with the size of 15 nm are produced that grow to about 45 nm after 300 s of electrodeposition. The ORR studies were conducted in 0.1 M KOH solution employing the rotating disk electrode (RDE) method. The Tafel slope at low current densities for electrodeposited silver is in the range from ?70 to ?80 mV. The RDE measurements showed that the electron transfer number (n) is 3.5 for smaller amounts of electrodeposited Ag, and it increases with increasing the loading of Ag on the GC surface. These n values suggest that the electroreduction of oxygen on Ag/GC electrodes proceeds mainly to water.     

An Arrayed Micro‐glutamate Sensor Probe Integrated with On‐probe Ag/AgCl Reference and Counter Electrodes

Complete all‐in‐one multi‐arrayed glutamate (Glut) sensors have been constructed on a silicon‐based micromachined probe composed of micro‐platinum (Pt) working electrodes, a micro‐silver/silver chloride (Ag/AgCl) reference electrode (RE), and a micro‐Pt counter electrode (CE). The OCP shift of the electrodeposited Ag/AgCl on‐probe micro‐reference electrode compared with a Ag/AgCl wire is <0.1 mV/h. The composition ratio of Ag, Cl, and Pt on the electrodeposited on‐probe micro‐reference electrode is observed to be 1.00 : 0.48 : 0.02 analyzed by EDS. The miniaturized amperometric Glut biosensors were constructed on working electrode sites (electrode area: ∼8.5×10⁻⁵ cm²) of the microprobe modified with glutamate oxidase (GlutOx) enzyme layers for the selective, fast, and continuous detection of L‐glutamate. The sensor selectivity towards common electroactive interferents has been improved significantly by coating the electrode surface with perm‐selective polymer layers, overoxidized polypyrrole (PPY) and Nafion®. The sensitivity, detection range, and response time of the proposed all‐in‐one Glut biosensors are 204.7±5.8 nA μM⁻¹ cm⁻² (N=5), 4.99–109 μM, and 2.7±0.3 sec, respectively and no interferent signals of AA and DA were observed. The sensor can be reused over 19 times of continuous repetitive operation (total measurement time: ∼4 hours) and the sensor sensitivity can retain up to four weeks of storage.     

Voltammetric Determination of 4‐Nitrophenol Using a Novel Type of Silver Amalgam Paste Electrode

A differential pulse voltammetric (DPV) method was developed for the determination of 4‐nitrophenol (4‐NP) at a newly developed silver amalgam paste electrode (AgA‐PE) in Britton–Robinson buffer pH 3.0. The electrode is based on a disposable plastic pipette tip filled with paste amalgam based on a mixture of mercury and fine silver powder (9 : 1, w/w). The experimental parameters, such as pH of Britton–Robinson buffer and activation and regeneration potential of the electrode surface were optimized. The reduction peak current dependences were linear for the concentration of 4‐NP from 0.2 to 100 μM. The method showed reproducible results with RSD (n=45) of 1.7%. The limit of determination (LOD) was 0.3 μM. The method was successfully applied for the direct determination of 4‐NP in drinking water.     

l‐Cysteine‐modified silver‐functionalized silica‐based material as an efficient solid‐phase extraction adsorbent for the determination of bisphenol A

A new silver‐functionalized silica‐based material with a core–shell structure based on silver nanoparticle‐coated silica spheres was synthesized, and silver nanoparticles were modified using strongly bound l‐ cysteine. l‐ Cysteine‐silver@silica was characterized by scanning electron microscopy and FTIR spectroscopy. Then, a solid‐phase extraction method based on l‐ cysteine‐silver@silica was developed and successfully used for bisphenol A determination prior to HPLC analysis. The results showed that the l‐ cysteine‐silver@silica as an adsorbent exhibited good enrichment capability for bisphenol A, and the maximum adsorption saturation was 20.93 mg/g. Moreover, a short adsorption equilibrium time was obtained due to the presence of silver nanoparticles on the surface of the silica. The extraction efficiencies were then optimized by varying the eluents and pH. Under the optimized conditions, good linearity for bisphenol A was obtained in the range from 0.4 to 4.0 μM (R² > 0.99) with a low limit of detection (1.15 ng/mL). The spiked recoveries from tap water and milk samples were satisfactory (85–102%) with relative standard deviations below 5.2% (n = 3), which indicated that the method was suitable for the analysis of bisphenol A in complex samples.     

Electrochemical behavior and differential pulse voltammetric determination of paracetamol at a carbon ionic liquid electrode

The electrochemical behavior of paracetamol in 0.1 M acetate buffer solution (pH 4.6) was investigated at a traditional carbon paste electrode (TCPE) and a carbon ionic liquid electrode (CILE) fabricated by replacing nonconductive organic binders with a conductive hydrophobic room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate (BmimPF₆). The results showed that the CILE exhibited better reversibility for the electrochemical redox of paracetamol. The oxidation potential of paracetamol at the CILE is +0.462 V, which is approximately 232 mV lower than that at the TCPE; the oxidation peak current response is nine times higher than that at the TCPE. The differential pulse voltammetric determination of paracetamol at the CILE was established based on this behavior. After optimizing several important parameters controlling the performance of paracetamol at the CILE, the oxidation peak current versus paracetamol concentration at the CILE showed linearity in the range from 1.0 μM to 2.0 mM (R ²  = 0.9992) with a detection limit of 0.3 μM (S/N = 3). The method has been applied to the determination of paracetamol in tablets and urine samples and the average recovery of paracetamol was 98.5% and 99.3%, respectively. The proposed CILE showed good sensitivity and reproducible response without influence of interferents commonly existing in pharmaceutical and urine samples. Figure CV curves of paracetamol illustrate the enhanced electrochemical behavior of paracetamol at the CILE (b), which forms the basis for the differential pulse voltammetric determination of paracetamol     

Direct electrochemistry of myoglobin based on electrodeposition of Pd nanoparticles with carbon ionic liquid electrode as basic electrode

We report on the direct electrochemistry and electrocatalytic properties of myoglobin (Mb) immobilized on a carbon ionic liquid electrode covered with a matrix composed of an ionic liquid, gellan gum, and Pd nanoparticles. UV-vis and FT-IR spectroscopy confirm that Mb retains its native structure in the composite film on the electrode. Scanning electron microscopy reveals that the nanoparticles are deposited on the surface of the Pd electrode. Cyclic voltametry gives a pair of well-defined and quasireversible redox peaks with a formal potential (E ^0′) of ?332 mV and a peak-to-peak separation of 64 mV at near-neutral pH value. The modified electrode shows good electrocatalytic activity towards the reduction of hydrogen peroxide, with a linear range between 5.0 μM and 0.27 mM and a detection limit of 1.7 μM (S/N = 3). The apparent Michaelis-Menten constant is 88 μM.

Direct electrochemistry of glucose oxidase based on its direct immobilization on carbon ionic liquid electrode and glucose sensing

Direct electrochemistry of glucose oxidase (GOx) has been achieved by its direct immobilization on carbon ionic liquid electrode (CILE) with a conductive hydrophobic ionic liquid, 1-butyl pyridinium hexafluophosphate ([BuPy][PF₆]) as binder for the first time. A pair of reversible peaks is exhibited on GOx/CILE by cyclic voltammetry. The peak-to-peak potential separation (ΔE_P) of immobilized GOx is 0.056 V in 0.067 M phosphate buffer solution (pH 6.98) with scan rate of 0.1 V/s. The average surface coverage and the apparent Michaelis–Menten constant are 6.69 × 10⁻¹¹ mol·cm⁻² and 2.47 μM. GOx/CILE shows excellent electrocatalytic activity towards glucose determination in the range of 0.1–800 μM with detection limit of 0.03 μM (S/N = 3). The biosensor has been successfully applied to the determination of glucose in human plasma with the average recoveries between 95.0% and 102.5% for three times determination. The direct electrochemistry of GOx on CILE is achieved without the help of any supporting film or any electron mediator. GOx/CILE is inexpensive, stable, repeatable and easy to be fabricated.     

Manganese Oxide Nanoparticles/Reduced Graphene Oxide as Novel Electrochemical Platform for Immobilization of FAD and its Application as Highly Sensitive Persulfate Sensor

In this study, manganese oxide nanoparticles/reduced graphene oxide(MnOxNPs/rGO) was used as support for strong immobilization of flavin adenine dinucleotide(FAD). A thin film of rGO cast on the electrode surface, followed by performing electrodeposition of MnOxNPs at applied constant potential of +1.4 V vs. Ag/AgCl for 200 s. Finally, FAD was electrodeposited onto the rGO/MnOxNPs film by potential cycling between 1.0 to ?1.0 V in solution containing 1 mg ml^?1 FAD. Electrochemical properties and catalytic activity of GCE/rGO‐MnOxNPs/FAD toward persulfate (S₂O₈^2?) reduction was investigated. Under optimized condition, the concentration calibration range, detection limit, and sensitivity were 0.1 μM–2 mM, 90 nM and 125.8 nA/μM, respectively, using hydrodynamic amperometry technique.     

Green synthesis of colloidal silver nanoparticles using natural rubber latex extracted from Hevea brasiliensis

Colloidal silver nanoparticles were synthesized by an easy green method using thermal treatment of aqueous solutions of silver nitrate and natural rubber latex (NRL) extracted from Hevea brasiliensis. The UV–Vis spectra detected the characteristic surface plasmonic absorption band around 435 nm. Both NRL and AgNO₃ contents in the reaction medium have influence in the Ag nanoparticles formation. Lower AgNO₃ concentration led to decreased particle size. The silver nanoparticles presented diameters ranging from 2 nm to 100 nm and had spherical shape. The selected area electron diffraction (SAED) patterns indicated that the silver nanoparticles have face centered cubic (fcc) crystalline structure. FTIR spectra suggest that reduction of the silver ions are facilitated by their interaction with the amine groups from ammonia, which is used for conservation of the NRL, whereas the stability of the particles results from cis-isoprene binding onto the surface of nanoparticles. Therefore natural rubber latex extracted from H. brasiliensis can be employed in the preparation of stable aqueous dispersions of silver nanoparticles acting as a dispersing and/or capping agent. Moreover, this work provides a new method for the synthesis of silver nanoparticles that is simple, easy to perform, pollutant free and inexpensive.