Electrocatalytic Nitrite Determination Using Iron Phthalocyanine Modified Gold Nanoparticles

Electrochemical detection of nitrite was achieved via electrodeposition of gold nanoparticles (AuNPs) onto glassy carbon electrodes, followed by 3‐mercaptopropionic acid (MPA) self‐assembly, enabling attachment of an iron(III) monoamino‐phthalocyanine (FeMAPc) catalyst via amide bond formation. The use of scanning electron microscopy, energy dispersive X‐ray spectroscopy and ultraviolet‐visible spectroscopy realised surface characterisation while cyclic voltammetry and electrochemical impedance spectroscopy techniques were applied for electrochemical interrogation. The electrochemical behaviour of nitrite at the bare (GCE), AuNPs/GCE, FeMAPc/GCE and FeMAPc‐MPA/AuNPs/GCE was further scrutinised using differential pulse voltammetry in phosphate buffer solution (0.1 M PBS, pH 5.8). Overall the FeMAPc‐MPA/AuNPs/GCE resulted in sensitivity 14.5 nA/µM, which was double that of AuNPs/GCE, 2.4 times FeMAPc/GCE and 3.5 times the response at a bare GCE, with linear range 1.9 µM–2.04 mM (PBS, pH 5.8) and LOD 0.21 µM. An interference study revealed that the proposed sensor (FeMAPc‐MPA/AuNPs/GCE) exhibited a selective response in the presence of interfering anions and the analytical capability of the sensor was demonstrated via nitrite ion determination in real water samples.     

A Sensitive and Selective Nitrite Detection in Water Using Graphene/Platinum Nanocomposite

A glassy carbon electrode modified with reduced graphene oxide and platinum nanocomposite film was developed simply by electrochemical method for the sensitive and selective detection of nitrite in water. The electrochemical reduction of graphene oxide (GO) efficiently eliminates oxygen‐containing functional groups. Pt nanoparticles were electrochemically and homogeneously deposited on the ErGO surface. Field emission scanning electron microscopy (FE‐SEM), Raman spectroscopy, attenuated total reflectance‐fourier transform infrared spectroscopy (ATR‐FTIR), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV) were used to examine the surface morphology and electrocatalytic properties of the Pt‐ErGO nanocomposite film‐modified electrode surface. The fabricated nitrite sensor showed good electrochemical performance with two linear ranges; one from 5 to 100 µM (R²=0.9995) and the other from 100 to 1000 µM (R²=0.9972) and a detection limit of 0.22 µM. The proposed sensor was successfully applied for the detection of nitrite in tap water samples which proves performance of the Pt‐ErGO nanocomposite films.     

Nanoporous Gold Leaf for Amperometric Determination of Nitrite

Ultra‐thin free‐standing nanoporous gold leaf made by dealloying exhibits excellent electrocatalytic activities toward nitrite oxidation. The electrochemical responses of nitrite ions on this novel nano‐electrode is found not dependent on pH over a wide range from 4.5 to 8.0, which is markedly different from that of gold oxidation, a process known to be highly pH‐sensitive. Amperometric study shows a linear relationship for nitrite determination in a concentration range from 1 µM to 1 mM. This nanostructured gold electrode displays good stability, repeatability and selectivity which suggests its potential for the development of new electrochemical sensors.     

A Nitrite Electrochemical Sensor Based on Boron‐Doped Diamond Planar Electrochemical Microcells Modified with a Monolacunary Silicotungstate Polyoxoanion

A new boron doped diamond microcells (BDD) was modified, for rapid, selective and highly sensitive determination of nitrite, using a coating film of polyoxometalates (POMs), formed by cyclic voltammetry on the molecular p‐phenylenediamine (PPD) functionalized BDD. The scanning electron microscopy (SEM) technique was used to examine the morphology of (PPD/SiW₁₁) modified (BDD) electrode. It was found that (SiW₁₁) layer was uniformly formed on the electrode surface. It was observed that (BDD/PPD/SiW₁₁) showed excellent electrocatalytic activities towards nitrite ion. Under the selected conditions, the anodic peak maximum at ?0.6 V was linear versus nitrite concentration in the 40 µM–4 mM range, and the detection limit obtained was 20 µM. The newly developed electrode has been successfully applied to the determination of nitrite content in real river water samples.     

Preparation of Polyelectrolyte Nanotubes by a Pressure filter-template Technique Using Microporous Anodic Aluminum Oxide (AAO) as the Template

Polyelectrolyte nanotubes of poly(sodium 4‐styrene‐sulfonate) (PSS) with cationic poly(diallyl dimethyl ammonium chloride) (PDDA) (PSS/PDDA) were fabricated by a pressure‐filter‐template technique using microporous anodic aluminum oxide (AAO) as the template. UV‐Vis spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD) and infrared spectroscopy (FT‐IR) were applied to characterize the obtained PSS/PDDA nanotubes. The results have shown that the PSS/PDDA nanotubes exhibit an amorphous structure and have the outer diameter of 200 nm and length of 25 µm respectively, which are in good agreement with the dimensions of the AAO template pores. The wall thickness of the nanotubes may be controlled by the number of the self‐assembled layers. Formation of the nanotubes follows a layer‐by‐layer (LbL) mechanism due to the electrostatic interactions, where the SO^?₃ groups of PSS are first adsorbed on the Lewis acid sites of AAO template pores.     

The Use of Ultrasound for the Analytical Determination of Nitrite on Diamond Electrodes by Square Wave Voltammetry

Abstract

This work describes an analytical methodology for the determination of nitrite ions in aqueous solutions using boron‐doped diamond electrodes and square wave voltammetry associated with ultrasound radiation. The nitrite ions were oxidized to nitrate ions in Britton‐Robinson buffer solutions 0.1 M, pH 2.0 at 1.0 V versus Ag/AgCl. The voltammetric response of nitrite in the presence of ultrasound showed a peak current five times higher than the obtained in silent conditions. Thus, the detection limit obtained in the presence of radiation was 17 nM (0.782 µg l^?1), a small value if compared with that obtained in the absence of ultrasound: 140 nM (6.44 µg l^?1).     

Palladium Nanoparticles Embedded into Graphene Nanosheets: Preparation,Characterization, and Nonenzymatic Electrochemical Detection of H2O2

A novel nonenzymatic H₂O₂ sensor based on a palladium nanoparticles/graphene (Pd‐NPs/GN) hybrid nanostructures composite film modified glassy carbon electrode (GCE) was reported. The composites of graphene (GN) decorated with Pd nanoparticles have been prepared by simultaneously reducing graphite oxide (GO) and K₂PdCl₄ in one pot. The Pd‐NPs were intended to enlarge the interplanar spacing of graphene nanosheets and were well dispersed on the surface or completely embedded into few‐layer GN, which maintain their high surface area and prevent GN from aggregating. XPS analysis indicated that the surface Pd atoms are negatively charged, favoring the reduction process of H₂O₂. Moreover, the Pd‐NPs/GN/GCE could remarkably decrease the overpotential and enhance the electron‐transfer rate due to the good contact between Pd‐NPs and GN sheets, and Pd‐NPs have high catalytical effect for H₂O₂ reduction. Amperometric measurements allow observation of the electrochemical reduction of H₂O₂ at 0.5 V (vs. Ag/AgCl). The H₂O₂ reduction current is linear to its concentration in the range from 1×10^?9 to 2×10^?3 M, and the detection limit was found to be 2×10^?10 M (S/N=3). The as‐prepared nonenzymatic H₂O₂ sensor exhibits excellent repeatability, selectivity and long‐term stability.     

Novel Uric Acid Sensor Based on Enzyme Electrode Modified by ZnO Nanoparticles and Multiwall Carbon Nanotubes

Abstract

In this work, we report the development of a highly sensitive and stable uric acid sensor based on the synergic action of multiwalled carbon nanotubes (MWNTs) and ZnO nanoparticles. MWNTs were first cast on pyrolytic graphite (PG) wafers. ZnO nanoparticles were then decorated onto the negatively charged MWNTs via the Vapor Liquid Solid (VLS) growth. Uricase was immobilized on the ZnO nanoparticles surface because of their large differences in the isoelectric point (IEP). Last, a cationic polydiallyldimethylammonium chloride (PDDA) layer was coated onto the uricase-contained ZnO nanoparticle layer and resulted in the PDDA/uricase/ZnO/MWNTs multilayer structure. The unique multilayer structure provides a favorable microenvironment to keep the bioactivity of uricase, which led to rapid amperometric response toward uric acid. Amperometric detection of uric acid was carried out at 320 mV (vs. SCE) in 0.05 mol/L (M) phosphate buffer solution (pH 6.8). For the sensor, a wide linear response range of 5.0 µM to 1 mM with a linear sensitivity of 393 mA cm^?2M^?1, a detection limit of 2.0 µM (3σ), and a long-term stability of 160 days can be obtained by using differential pulse voltammetry (DPV). Testing results in human urine obtained from the sensors were also compared with the data obtained by spectrometry. For five samples with different concentrations of urine, the relative deviations between them were smaller than 3.8%. The recovery was between 96.5 and 104.0%.     

Pencil Lead Electrode Modified with Hemoglobin Film as a Novel Biosensor for Nitrite Determination

In the present paper, the electrochemical reduction of nitrite at a hemoglobin modified pencil lead electrode (Hb/PLE) is described. The electrochemical properties of nitrite were studied by cyclic voltammetry and chronoamperometry. Results showed that the hemoglobin film has an excellent electrochemical activity towards the reduction of nitrite. By using voltammetric and chronoamperometric methods, α, n_α and n were calculated. Then the ability of the electrode for nitrite determination was investigated using differential pulse voltammetry. The electrocatalytic reduction peak currents were found to be linear with the nitrite concentration in the range from 10 to 220 µM with a detection limit of 5 µM. The relative standard deviation is 2 % for 3 successive determinations of a 100 µM nitrite solution. This modified electrode was successfully used for the detection of low amounts of NO₂^? in spinach sample and a spiked sample of tap water.     

Detection of Uric Acid in the Presence of Dopamine and High Concentration of Ascorbic Acid Using PDDA Modified Graphite Electrode

The properties of graphite electrode (Gr) modified with poly(diallyl dimethyl ammonium chloride) (PDDA) for the detection of uric acid (UA) in the presence of dopamine (DA) and high concentration of ascorbic acid (AA) have been investigated by cyclic voltammetry, differential pulse voltammetry and chronoamperometry. The polymer modified graphite electrode was prepared by a very simple method just by immersing the graphite electrode in PDDA solution for 20 minutes. The PDDA/Gr modified electrode displayed excellent electrocatalytic activity towards the oxidation of UA, DA and AA compared to that at the bare graphite electrode. The electrochemical oxidation signals of UA, DA and AA are well resolved into three distinct peaks with peak potential separations of 220 mV, 168 mV and 387 mV between AA‐DA, DA‐UA and AA‐UA respectively in cyclic voltammetry studies and the corresponding peak potential separations are 230 mV, 130 mV and 354 mV respectively in differential pulse voltammetry. The lowest detection limits obtained for UA, DA and AA were 1×10^?7 M, 2×10^?7 M and 800×10^?9 M respectively. The PDDA/Gr electrode efficiently eliminated the interference of DA and a high concentration of AA in the determination of UA with good selectivity, sensitivity and reproducibility. The modified electrode was also successfully applied for simultaneous determination of UA, DA and AA in their ternary mixture.     

Electrochemical Behavior of Caffeic Acid Assayed with Gold Nanoparticles/Graphene Nanosheets Modified Glassy Carbon Electrode

A gold nanoparticle (AuNP) and graphene nanosheet (GN) modified glassy carbon electrode (GCE) is proposed as voltammetric sensor for caffeic acid assay. The sensor exhibits a surface‐confined and reversible process for oxidation of caffeic acid revealed by cyclic voltammetry. The results show more favorable electron transfer kinetics than the bare GCE. The linear response of the sensor is from 5×10^?7 to 5×10^?5 M with a detection limit of 5×10^?8 M (S/N=3). The AuNP/GN nanocomposite shows more favorable electrochemical activity and should be a kind of more robust and advanced functional material, which provides a promising platform for electrochemical sensors and biosensors. The method was successfully applied to detect caffeic acid in pharmaceutical tablets with satisfactory results.     

A Novel Electroactive Polymer for pH‐independent Oxygen Sensing

Methylene blue (MB⁺) and pyrrole were copolymerised to electrodeposit a novel electroactive polymer on a Au electrode which was assessed for O₂ sensing. The electroactive polymer exhibits diffusion‐limited behaviour and an electrochemical, followed by catalytic (EC′) mechanism in the presence of dissolved O₂. Notably, it is pH‐insensitive in both N₂‐purged and air‐equilibrated phosphate buffered saline (PBS) from pH 4 to 8. It is stable over 18 days, possesses a good sensitivity of 256.335 µA mM^?1 cm^?2, wide linear range of 15 µM to 285 µM and detection limit of 1.47 µM (S/N=3) for dissolved O₂. It is highly promising for use in biological investigations where pH fluctuations are expected.     

Immobilization and Characterization of Glucose Oxidase on Single-Walled Carbon Nanotubes and Its Application to Sensing Glucose

The negatively charged （at pH 8.2） glucose oxidase （GOx, pI ca. 4.2） was assembled onto the surface of single-walled carbon nanotubes （SWNT）, which was covered （or wrapped） by a layer of positively charged polyelectrolyte poly（dimethyldiallylammonium chloride） （PDDA）, via the electrostatic interaction forming GOx-PDDASWNT nanocomposites. Fourier transform infrared （FTIR）, UV-Vis and electrochemical impedance spectroscopy （EIS） were used to characterize the growth processes of the nanocomposites. The results indicated that GOx retained its native secondary conformational structure after it was immobilized on the surface of PDDA-SWNT. A biosensor （Nafion-GOx-PDDA-SWNT/GC） was developed by immobilization of GOx-PDDA-SWNT nanocomposites on the surface of glassy carbon （GC） electrode using Nafion （5%） as a binder. The biosensor showed the electrocatalytic activity toward the oxidation of glucose under the presence of ferrocene monocarboxylic acid （FcM） as an electroactive mediator with a good stability, reproducibility and higher biological affinity. Under an optimal condition, the biosensor could be used to detection of glucose, presenting a typical characteristic of Michaelis-Menten kinetics with the apparent Michaelis-Menten constant of KM^app ca. 4.5 mmol/L, with a linear range of the concentration of glucose from 0.5 to 5.5 mmol/L （with correlation coefficient of 0.999） and the detection limit of ca. 83 μmol/L （at a signal-to-noise ratio of 3）. Thus the biosensor was useful in sensing the glucose concentration in serum since the normal glucose concentration in blood serum was around 4.6 mmol/L. The facile procedure of immobilizing GOx used in present work would promote the developments of electrochemical research for enzymes （proteins）, biosensors, biofuel cells and other bioelectrochemical devices.     

Cysteine combined with carbon black as support for electrodeposition of poly (1,8-Diaminonaphthalene): Application as sensing material for efficient determination of nitrite ions

Poly 1,8-Diaminonaphtahlene/cysteine (poly 1,8-DAN/Cys) combined with carbon black (CB) nanoparticles are proposed as an excellent sensor for the detection of nitrite ions. To design the electrocatalyst, a simple approach consisting on drop-casting method was applied to disperse carbon black on the surface of glassy carbon electrode, followed by the immobilization of cysteine on the surface of CB nanoparticles. The electrochemical polymerization of 1,8-Diaminonaphthalene was conducted in acidic medium by using cyclic voltammetry. The prepared hybrid material was denoted poly 1,8-DAN /Cys/CB. Several methods were used to characterize the structural and electrochemical behavior of the reported hybrid material including Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), amperometry and differential pulse voltammetry (DPV). The prepared electrode displayed an outstanding electroactivity towards nitrite ions reflected by an enhancement in the intensity of the current and a decrease of the charge transfer resistance. Poly 1,8-DAN/Cys/CB displayed an excellent sensing performance towards the detection of nitrite with a very low detection limit of 0.25 µM. Two linear ranges of 1–40 µM and 20–210 µM when using amperometry and differential pulse voltammetry (DPV) were obtained respectively. This work highlights the simple preparation of a polymeric film rich in amine and thiol groups for nitrite detection.     

Study of Cobalt(III) Corrole as the Neutral Ionophore for Nitrite and Nitrate Detection via Polymeric Membrane Electrodes

Cobalt(III) 5,10,15‐tris(4‐tert‐butylphenyl) corrole was synthesized and incorporated into plasticized poly(vinyl chloride) membranes and studied as a neutral carrier ionophore via potentiometry. This cobalt(III) complex has binding affinity to nitrite, and the resulting membrane electrode yields reversible and Nernstian response toward nitrite. Enhanced nitrite selectivity is observed over other anions, including lipophilic anions such as thiocyanate and perchlorate when an appropriate amount of lipophilic cationic sites are added to the membrane phase. Detection limit to nitrite is ca. 5 µM. Using tributylphosphate as the plasticizer with the cobalt(III) corrole species yields electrodes with enhanced nitrate selectivity.     

Electrochemical Sensor for Sensitive Determination of Capsaicin Using Pd Decorated Reduced Graphene Oxide

In this work, the reduced graphene oxide functionalized with poly dimethyl diallyl ammonium chloride (PDDA) modified palladium nanoparticles (PDDA‐rGO/Pd) had been facile synthesized and used as the sensing layer for sensitive determination of capsaicin. The prepared composite was characterized by transmission electron microscopy, UV‐visible absorption spectroscopy. The image demonstrated that Pd nanoparticles were uniformly distributed on the graphene surface. The electrochemical properties of the prepared sensor were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results showed that the nanocomposite exhibits attractive electrocatalytic activity towards the oxidation of capsaicin. This attributed to the synergistic action of the excellent properties of Pd nanoparticles and graphene nanosheets. Under optimized conditions, the electrochemical sensor possessed a dynamic linear range from 0.32 μM to 64 μM with a detection limit of 0.10 μM (S/N=3) for capsaicin detection. Moreover, the cost‐effective and simple fabrication procedure, good reproducibility and stability as well as acceptable accuracy for capsaicin determination in actual samples are also the main advantages of this method, which might have broad application in other amide alkaloid detection.     

Electrochemical Determination of Phenolic Acids at a Zn/Al Layered Double Hydroxide Film Modified Glassy Carbon Electrode

A stable sensor for the determination of gallic acid (GA) and caffeic acid (CA) was fabricated by electrodeposition of Zn‐Al‐NO₃ layered double hydroxide film on a glassy carbon electrode (LDHf/GCE). A sensitive electrochemical method was achieved for the determination of GA and CA in a phosphate buffer solution (pH 3). The differential pulse voltammetry response of the LDHf/GCE to GA has a linear concentration range from 4 µM to 600 µM with a correlation coefficient of 0.9985 and the calculated detection limit of 1.6 µM at a signal‐to‐noise ratio of 3. The differential pulse voltammetry response of the LDHf/GCE to CA has a linear concentration range from 7 µM to 180 µM with a correlation coefficient of 0.9969 and the calculated detection limit of 2.6 µM at a signal‐to‐noise ratio of 3. The constructed sensor was applied to the determination of GA in commercial green tea samples.     

Electrochemical Detection of Nitrite in Meat and Water Samples Using a Mesoporous Carbon Ceramic SiO2/C Electrode Modified with In Situ Generated Manganese(II) Phthalocyanine

Mesoporous carbon ceramic SiO₂/50 wt % C (S_BET=170 m² g^?1), where C is graphite, were prepared by the sol‐gel method. The materials were characterized using N₂ sorption isotherms, scanning electron microscopy, and conductivity measurements. The matrix was used as support for the in situ immobilization of Mn(II) phthalocyanine (MnPc) on their surface. XPS was used to determine the Mn/Si atomic ratios of the MnPc‐modified materials. Pressed disk electrodes were prepared with the MnPc‐modified matrix, and tested as an electrochemical sensor for nitrite oxidation. The linear response range, sensitivity, detection limit and quantification limit were 0.79–15.74 µmol L^?1, 17.31 µA L µmol^?1, 0.02 µmol L^?1 and 0.79 µmol L^?1, respectively, obtained using cyclic voltammetry. The repeatability of the proposed sensor, evaluated in terms of relative standard deviation was 1.7 % for 10 measurements of a solution of 12.63 µmol L^?1 nitrite. The sensor employed to determine nitrite in sausage meat, river and lake water samples showed to be a promising tool for this purpose.     

Selective and Sensitive Nitrite Sensor Based on Glassy Carbon Electrode Modified by Silver Nanochains

Herein, we report a facile method for the synthesis of silver nanochains (Ag nanochains) using pyridine as growth directing agent and citrate ions as capping agents in alkaline medium. The characterization of the synthesized high aspect ratio Ag nanochains was accomplished with the help of Transmission Electron Microscopy (TEM) and High Resolution Transmission Electron Microscopy (HRTEM) which demonstrates the thickness below 100 nm. Crystalline nature of the synthesized Ag nanochains was investigated using X‐ray diffractrometry. A sensitive electrochemical nitrite sensor was assembled using synthesized Ag nanochains as electrode modifier. An improved cyclic voltammetric response for the oxidation of nitrite ions was witnessed at the modified GCE surface in comparison to bare GCE in Britton Robinson (BR) buffer (pH 4). The influence of pH on the oxidation peak current of nitrite ions was also examined using cyclic voltammetry. The electrocatalytic oxidation currents attained through amperometric measurements at Ag nanochains modified GCE were linearly dependent on the concentration of nitrite ions in the two ranges of 0.5–7.5 µM, 5–480 µM. Linear calibration plots of Ip vs. concentration of nitrite were also constructed at the proposed sensor using square wave voltammetry and differential pulse voltammetry. The proposed sensing strategy was successfully employed for the determination of nitrite in water samples with excellent recoveries.     

Au‐TiO2/Graphene Nanocomposite Film for Electrochemical Sensing of Hydrogen Peroxide and NADH

We describe a simple method for preparing Au‐TiO₂/graphene (GR) nanocomposite by deposition of Au nanoparticles (NPs) on TiO₂/GR substrates. The as‐prepared Au‐TiO₂/GR was characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The presence of Au NPs on TiO₂/GR surface remarkably improves the electrocatalytic activity towards the oxidation of hydrogen peroxide (H₂O₂) and β‐nicotinamide adenine dinucleotide (NADH). The Au‐TiO₂/GR modified glassy carbon (GC) electrode exhibits good amperometric response to H₂O₂ and NADH, with linear range from 10 to 200 µM and 10 to 240 µM, and detection limit of 0.7 and 0.2 µM, respectively.