Nonenzymatic amperometric sensor of hydrogen peroxide and glucose based on Pt nanoparticles/ordered mesoporous carbon nanocomposite

A simple and facile synthetic method to incorporate Pt nanoparticles inside the mesopores of ordered mesoporous carbons (OMCs) is reported. The Pt/OMCs nanocomposite was characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and nitrogen adsorption-desorption. The results show that the incorporation of Pt nanoparticles inside the pores of OMCs does not change the highly ordered two-dimensional hexagonal mesostructure of OMCs matrix. Nonenzymatic amperometric sensor of hydrogen peroxide and glucose based on the Pt/OMCs nanocomposite-modified glassy carbon (GC) electrode is developed. Compared with the original OMCs-modified electrode, the Pt/OMCs-modified electrode displays improved current response towards hydrogen peroxide and gives linear range from 2 to 4212 μM. At an applied potential of −0.08 V, the Pt/OMCs nanocomposite gives linearity in the range of 0.5-4.5 mM glucose in neutral buffered saline solution. This glucose sensor also exhibits good ability of anti-interference to electroactive molecules. The combination the unique properties of Pt nanoparticles and the ordered mesostructure of OMCs matrix guarantees the enhanced response for hydrogen peroxide and glucose.     

Amperometric morphine sensing using a molecularly imprinted polymer-modified electrode

This study incorporates morphine into a molecularly imprinted polymer (MIP) for the amperometric detection of morphine. The polymer, poly(3,4-ethylenedioxythiophene), PEDOT, is an electroactive film that catalyzes morphine oxidation and lowers the oxidization potential on an indium tin oxide (ITO) electrode. The MIP-PEDOT modified electrode is prepared by electropolymerizing PEDOT onto an ITO electrode in a 0.1 M LiClO₄ solution with template addition (morphine). After template molecule extraction, the oxidizing current of the MIP-PEDOT modified electrode is measured in a 0.1 M KCl solution (pH = 5.3) at 0.75 V (versus Ag/AgCl/sat’d KCl) with the morphine concentration varying in the 0.1-5 mM range. A linear range, displaying the relationship between steady-state currents and morphine concentrations, from 0.1 to 1 mM, is obtained. The proposed amperometric sensor could be used for morphine detection with a sensitivity of 91.86 μA/cm² per mM. A detection limit of 0.2 mM at a signal-to-noise ratio of 3 is achieved. Moreover, the proposed method can discriminate between morphine and its analogs, such as codeine.     

A simple method for fabrication of sole composition nickel hexacyanoferrate modified electrode and its application

Nickel hexacyanoferrate film modified gold electrode was prepared by a simple chemical deposition procedure from a fresh prepared solution containing ferricyanide, Ni²⁺, and sodium nitrate. The resultant films have solo composition and are significantly stable as compared to the electrochemically deposited NiHCF films. For different concentrations of Na⁺ in the solution, the formal potential values of NiHCF shift according to the Nernstian behavior with a slope of 48 mV in the range of 10⁻⁴ to 1.0 M. The NiHCF film was also used for the electrocatalytic oxidation of ascorbic acid. The anodic peak current observed in cyclic voltammetry increased with the ascorbic acid concentration. At a fixed potential under hydrodynamic conditions, the calibration plot was linear over the ascorbic acid concentration range 0.1-12 mM.     

An ultrasensitive iron(III)-complex based hydrogen peroxide electrochemical sensor based on a nonelectrocatalytic mechanism

In this communication, the first nonelectrocatalysis-type hydrogen peroxide electrochemical sensor is reported. The electroactive iron(III) diethylenetriaminepentaacetic acid (DTPA-Fe^III) complex is immobilized on the cysteamine (cys) modified nanoporous gold (NPG) films by covalent method. The immobilized DTPA-Fe^III complex quickly communicates an electron with the electrode. Upon addition of hydrogen peroxide, however, hydrogen peroxide inhibits the direct electron transfer of the DTPA-Fe^III complex due to the generation of nonelectroactive DTPA-Fe^III–H₂O₂ complex. Based on quenching mechanism, the first hydrogen peroxide electrochemical sensor based on a nonelectrocatalytic mechanism is developed. The novel hydrogen peroxide electrochemical sensor has the ultralow detection limit (1.0 × 10^–14 M) and wide linear range (1.0 × 10^–13 to 1.0 × 10^–8 M) with excellent reproducibility and stability.     

Rapid determination of hydrogen peroxide in the wood pulp bleaching streams by a dual-wavelength spectroscopic method

This study has demonstrated a spectrophotometric method for residual hydrogen peroxide analysis in wood pulp bleaching streams. In an acidic medium, hydrogen peroxide can instantly associate with molybdate to form a peroxomolybdic acid complex that has an absorption peak at 330 nm. To avoid the spectral interference from excess molybdate ion, 350 nm is used for spectroscopic quantification. A linear relationship between the absorbance at 350 nm and peroxide concentration was found up to a peroxide concentration of ca. 0.2 mmol l⁻¹. It was discovered that 297 nm was an isosbestic point that could be used to develop a dual-wavelength method to account for the spectral interference from dissolved lignin in pulp bleaching streams, a critical procedure for the success of the present method. This method is simple, rapid, sensitive, accurate, and has the potential for on-line applications.     

Simultaneous flow-injection assay of creatinine and creatine in serum by the combined use of a 16-way switching valve, some specific enzyme reactors and a highly selective hydrogen peroxide electrode

Creatine and creatinine in serum were assayed simultaneously in a noble flow-injection system made up by a 16-way switching valve with two sample loops, three enzyme reactors positioned in a serial way, and a delay coil needed to separate two peaks corresponding to two sample portions injected simultaneously. A Nafion/poly(1,2-diaminobenzene) bilayer modified electrode was used to selectively detect the hydrogen peroxide generated as one of the end products in the last enzyme reactor, without any interferences from electroactive species (such as l-ascorbate and urate) and proteins present in the serum. Because two sample portions passed through the flow line with different residence time, two peaks were obtained. The first peak corresponded to creatine and the second peak to the total of creatine and creatinine. The maximum currents of both peaks were linearly related to the concentration of creatine and total of creatine and creatinine in the range of 1-100 μM, respectively; 20 samples h⁻¹ could be processed with an R.S.D. <1.6%.     

Redox protein-polymer films for simultaneous determination of ascorbic Acid and hydrogen peroxide

Layer by layer films of protein and redox polymer were constructed and used to simultaneously analyze ascorbic acid and hydrogen peroxide. The films were made using hemoglobin and poly[4-vinylpyridine Os(bipyridine)(2)Cl]-co-ethylamine (Pos-Ea). The film growth was monitored using cyclic voltammetry, quartz crystal microbalance (QCM) and atomic force microscopy (AFM). Reversible pairs of oxidation-reduction peaks were observed using cyclic voltammetry corresponding to the Os(II)/Os(III) from redox polymer and HbFe(III)/HbFe(II) redox couples at 0.35 and -0.25 V vs. Ag/AgCl, respectively. The two redox centers were independent of each other. This enabled the simultaneous and independent determination of ascorbic acid and hydrogen. Peak currents were linearly related to concentration for both analytes in a mixture. The linear range of ascorbic acid was 0 - 1 mM (R(2) = 0.9996, n = 5) at scan rate of 50 mV s(-1) (sensitivity 3.5 microA/mM) while hydrogen peroxide linear range was 1.0 - 10.0 microM (R(2) = 0.991, n = 6) with sensitivity of 1.85 microA/microM.     

A gold@silica core–shell nanoparticle-based surface-enhanced Raman scattering biosensor for label-free glucose detection

The gold nanostar@silica core–shell nanoparticles conjugated with glucose oxidase (GOx) enzyme molecules have been developed as the surface-enhanced Raman scattering (SERS) biosensor for label-free detection of glucose. The surface-immobilized GOx enzyme catalyzes the oxidation of glucose, producing hydrogen peroxide. Under laser excitation, the produced H₂O₂ molecules near the Au nanostar@silica nanoparticles generate a strong SERS signal, which is used to measure the glucose concentration. The SERS signal of nanostar@silica∼GOx nanoparticle-based sensing assay shows the dynamic response to the glucose concentration range from 25 μM to 25 mM in the aqueous solution with the limit of detection of 16 μM. The sensing assay does not show any interference when glucose co-exists with both ascorbic acid and uric acid. The sensor can be applied to a saliva sample.     

Enzymatic rotating biosensor for cysteine and glutathione determination in a FIA system

The high sensitivity that can be attained using an enzymatic system and mediated by catechols has been verified by on-line interfacing of a rotating biosensor and continuous flow/stopped-flow/continuous-flow processing. Horseradish peroxidase, HRP, [EC 1.11.1.7], immobilized on a rotating disk, in presence of hydrogen peroxide catalyzed the oxidation of catechols, whose back electrochemical reduction was detected on glassy carbon electrode surface at −150 mV. Thus, when l-cysteine (Cys) or glutathione (GSH) was added to the solution, these thiol-containing compounds participate in Michael addition reactions with catechols to form the corresponding thioquinone derivatives, decreasing the peak current obtained proportionally to the increase of its concentration. Cys was used as the model thiol-containing compound for the study. The highest response for Cys was obtained around pH 7. This method could be used to determine Cys concentration in the range 0.05-90 μM (r = 0.998) and GSH concentration in the range 0.04-90 μM (r = 0.999). The determination of Cys and GSH were possible with a limit of detection of 0.7 and 0.3 nM, respectively, in the processing of as many as 25 samples per hour. Current response of the HRP-rotating biosensor is not affected by the oxidized form of GSH and Cys (glutathione disulfide, GSSG, and l-cystine, respectively), by sulfur-containing and alkyl-amino compounds such as methionine and lysine, respectively. The interferences from easily oxidizable species such as ascorbic acid and uric acid are lowest.     

Improving the detection of hydrogen peroxide of screen-printed carbon paste electrodes by modifying with nonionic surfactants

Nonionic surfactants, such as Triton X-100 and Tween-20, were shown in this study to improve the electrocatalytic activity of screen-printed carbon paste electrodes (SPCE). The electrochemical response of SPCE to hydrogen peroxide increased 8-10-fold with the modification of nonionic surfactants. In addition, the glucose biosensors fabricated from nonionic surfactant-modified SPCE exhibited 6.4-8.6-fold higher response to glucose than that fabricated from unmodified SPCE. A concentration effect is proposed for nonionic surfactant to bring neutral reactants to the surface of electrode. Moreover, nonionic surfactant-modified SPCE exhibits a capability of repetitive usage and good reproducibility (R.S.D. < 5%) in the measurement of H₂O₂. Interestingly, the nonionic surfactant-modified SPCE exhibited an opposite effect to ascorbic acid, a common electroactive agent, which causes interference during clinical diagnosis. The differential responses of nonionic surfactant-modified SPCE to H₂O₂ and ascorbic acid suggest its potential in the development of biosensors for clinical diagnosis.     

Use of hydrogen peroxide to achieve interference-free stripping voltammetric determination of copper at the bismuth-film electrode

In this work, a new approach is presented to allow interference-free determination of Cu (II) by stripping voltammetry using the bismuth-film electrode. The addition of hydrogen peroxide to the electroanalytical cell has promoted complete resolution between re-dissolution peaks of Bi (III) and Cu (II). The absence of interference could be evaluated by the correlation coefficient (r > 0.99) between Cu (II) concentration and its shifted current peak (at +212 mV) while achieving a slightly fluctuation of the bismuth current peak at −180 mV. Studies were performed aiming towards the optimum conditions for trace determination of Cu (II) using hydrogen peroxide. The methodology was applied to a real sample (sugarcane spirits) and the results were compared to those from graphite furnace atomic absorption spectrometry. The analytical parameters of merit and the results of the analysis indicated that the analytical methodology could be readily used for trace determination of Cu (II).     

Electrochemical sensing platform based on covalent immobilization of thionine onto gold electrode surface via diazotization-coupling reaction

A novel electrochemical sensing platform by modification of electroactive thionine (Th) onto gold electrode surface was constructed, which was realized by diazotization of 4-aminothiophenol (ATP) self-assembled monolayer, followed by coupling of Th with the diazonium group to form a covalent diazo bond. A pair of well-defined redox peaks of Th was observed in the cyclic voltammetric measurement. The resulting diazo-ATP monolayer displayed superior electrical conductivity, which contributed to the sensitive detection of hydrogen peroxide (H₂O₂). The immobilized Th also showed a remarkable stability, which may benefit from the π-π stacking force and the covalent diazo bond between diazo-ATP and Th molecules. Under the optimized experimental conditions, the current fabricated non-enzyme and reagentless sensor could show a rapid response to H₂O₂ within 3 s and a linear calibration plot ranged from 1.0 × 10⁻⁶ to 6.38 × 10⁻³ M with a detection limit of 6.7 × 10⁻⁷ M. The current fabrication strategy of electroactive interface is expected to be used as a versatile route for the immobilization of more electroactive molecules and offer more opportunities for the applications in electrochemical sensor, biosensor, electrocatalysis, etc.     

Localized surface plasmon resonance sensor for simultaneous kinetic determination of peroxyacetic acid and hydrogen peroxide

A new sensor for simultaneous determination of peroxyacetic acid and hydrogen peroxide using silver nanoparticles (Ag-NPs) as a chromogenic reagent is introduced. The silver nanoparticles have the catalytic ability for the decomposition of peroxyacetic acid and hydrogen peroxide; then the decomposition of them induces the degradation of silver nanoparticles. Hence, a remarkable change in the localized surface plasmon resonance absorbance strength could be observed. Spectra-kinetic approach and artificial neural network was applied for the simultaneous determination of peroxyacetic acid and hydrogen peroxide. Linear calibration graphs were obtained in the concentration range of (8.20 × 10⁻⁵ to 2.00 × 10⁻³ mol L⁻¹) for peroxyacetic acid and (2.00 × 10⁻⁵ to 4.80 × 10⁻³ mol L⁻¹) for hydrogen peroxide. The analytical performance of this sensor has been evaluated for the detection of simultaneous determination of peroxyacetic acid and hydrogen peroxide in real samples.     

Determination of hydrogen peroxide using glassy carbon and graphite/polyester composite electrodes modified by vanadium-doped zirconias

Synthetic monoclinic and tetragonal vanadium-doped zirconias (VZrO₂) with vanadium loading ranging from 0.5 to 15 mol% are used to modify glassy carbon and graphite/polyester composite electrodes able to detect oxygen and hydrogen peroxide in neutral aqueous media. Electrodes modified by monoclinic VZrO₂ decrease the overpotential for the reduction of oxygen and hydrogen peroxide in neutral and alkaline media and enhance their reduction currents with respect to unmodified carbon electrodes. This is associated to seven-coordinated vanadium centers isomorphously substituting zirconium ones in the ZrO₂ lattice. The catalytic effect shows site-selectivity, since it is almost entirely absent in tetragonal VZrO₂ in which eight-coordinated vanadium sites exists. Under optimized conditions using differential pulse detection mode, the height of the cathodic catalytic current peak is directly proportional to the hydrogen peroxide concentration over the concentration range 5-400 μM with a sensitivity of 170 μA/mM at pH 10.0. The detection limit (3σ) is calculated as 0.9 μM.     

Electrochemistry and scanning electron microscopy of polyaniline/peroxidase-based biosensor

An amperometric biosensor was prepared by in situ deposition of horseradish peroxidase (HRP) enzyme on a polyaniline (PANI)-doped platinum disk electrode. The PANI film was electrochemically deposited on the electrode at 100 mV s⁻¹/Ag-AgCl. Cyclic voltammetric characterization of the PANI film in 1 M HCl showed two distinct redox peaks, which prove that the PANI film was electroactive and exhibited fast reversible electrochemistry. The surface concentration and film thickness of the adsorbed electroactive species was estimated to be 1.85×10⁻⁷ mol cm⁻² and approximately 16 nm, respectively. HRP was electrostatically immobilized onto the surface of the PANI film, and voltammetry was used to monitor the electrocatalytic reduction of hydrogen peroxide under diffusion-controlled conditions. Linear responses over the concentration range 2.5×10⁻⁴ to 5×10⁻³ M were observed. Spectroelectrochemistry was used to monitor the changes in UV-vis properties of HRP, before and after the catalysis of H₂O₂. The biosensor surface morphology was characterized by scanning electron microscopy (SEM) using PANI-doped screen-printed carbon electrodes (SPCEs) in the presence and absence of (i) peroxidase and (ii) peroxide. The SEM images showed clear modifications of the conducting film surface structure when doped with HRP, as well as the effect of hydrogen peroxide on the morphology of biosensor.     

Facile fabrication of nanoporous PdFe alloy for nonenzymatic electrochemical sensing of hydrogen peroxide and glucose

Nanoporous (NP) PdFe alloy is easily fabricated through one step mild dealloying of PdFeAl ternary source alloy in NaOH solution. Electron microscopy characterization demonstrates that selectively dissolving Al from PdFeAl alloy generates three-dimensional bicontinuous nanospongy architecture with the typical ligament size around 5 nm. Electrochemical measurements show that the NP-PdFe alloy exhibits the superior electrocatalytic activity and durability towards hydrogen peroxide (H₂O₂) detection compared with NP-Pd and commercial Pd/C catalysts. In addition, NP-PdFe performs high sensing performance towards H₂O₂ in a wide linear range from 0.5 to 6 mM with a low detection limit of 2.1 μM. This nanoporous structure also can sensitively detect glucose over a wide concentration range (1–32 mM) with a low detection limit of 1.6 μM and high resistance against chloride ions. Along with these attractive features, the as-made NP-PdFe alloy also has a good anti-interference towards ascorbic acid, uric acid, and dopamine.     

Automatic sequential determination of the hydrogen peroxide scavenging activity and evaluation of the antioxidant potential by the 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) radical cation assay in wines by sequential injection analysis

An automatic system that performs two analytical procedures, allowing the evaluation of the relative antioxidant capacity of wine samples, was developed. Automation was carried out using a sequential injection analysis (SIA) system that allowed, thanks to its versatility, the development of two methodologies. One is based on the decolorization assay of the 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical, using a spectrophotometric detector. A second methodology allowed the evaluation of the hydrogen peroxide scavenging activity by measuring the oxidation of homovanylic acid (HVA) to its fluorescent dimer, using a fluorescent detector.The developed automatic methodologies were evaluated using trolox as standard and subsequently using other antioxidant substances as gallic acid, caffeic acid, ascorbic acid, catechin and taxifolin which are abundant in wine and whose antioxidant activities were compared to that shown by trolox. The spectrophotometric and fluorimetric assays showed linearity intervals between 0.001 and 0.01 mM, and 0.001 and 0.008 mM of trolox, respectively.The evaluation of the antioxidant power of 20 white and red wine samples, from different Portuguese wine producing regions, was carried out sequentially, in the automatic system. The results were expressed in trolox equivalent antioxidant capacity (TEAC) and presented, for the ABTS and hydrogen peroxide scavenging activity methodologies, detection limits of 8.4 × 10⁻⁷ and 1.4 × 10⁻⁴ mM and relative standard deviation (R.S.D. (%)) in the range 0.6-2.4 and 1-1.8, respectively.     

Electrode modified with a composite film of ZnO nanorods and Ag nanoparticles as a sensor for hydrogen peroxide

A conducting fluorine-doped tin oxide (FTO) electrode, first modified with zinc oxide nanorods (ZnONRs) and subsequently attached with photosynthesized silver nanoparticles (AgNPs), designated as AgNPs/ZnONRs/FTO electrode, was used as an amperometric sensor for the determination of hydrogen peroxide. The first layer (ZnONRs) was obtained by chemical bath deposition (CBD), and was utilized simultaneously as the catalyst for the photoreduction of Ag ions under UV irradiation and as the matrix for the immobilization of AgNPs. The aspect ratio of ZnONRs to be deposited was optimized by controlling the number of their CBDs to render enough surface area for Ag deposition, and the amount of AgNPs to be attached was controlled by adjusting the UV-irradiation time. The immobilized AgNPs showed excellent electrocatalytic response to the reduction of hydrogen peroxide. The resultant amperometric sensor showed 10-fold enhanced sensitivity for the detection of H₂O₂, compared to that without AgNPs, i.e., only with a layer of ZnONRs. Amperometric determination of H₂O₂ at −0.55 V gave a limit of detection of 0.9 μM (S/N = 3) and a sensitivity of 152.1 mA M⁻¹ cm⁻² up to 0.983 mM, with a response time (steady-state, t₉₅) of 30-40 s. The selectivity of the sensor was investigated against ascorbic acid (AA) and uric acid (UA). Energy dispersive X-ray (EDX) analysis, transmission electron microscopic (TEM) image, X-ray diffraction (XRD) patterns, cyclic voltammetry (CV), and scanning electron microscopic (SEM) images were utilized to characterize the modified electrode. Sensing properties of the modified electrode were studied both by CV and amperometric analysis.     

Synthesis of silver nanowires and their applications in the electrochemical detection of halide

A silver nanowires modified platinum (Ag NWs/Pt) electrode was developed for simultaneous and selective determination of chloride, bromide and iodide ions by cyclic voltammetry in aqueous solutions. Silver nanowires were synthesized by an l-cysteine-assisted poly (vinyl pyrrolidone) (PVP)-mediated polyol route. X-ray diffraction (XRD) and scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) were employed to investigate the prepared nanowires. The intrinsic high surface area and the fast electron transfer rate ascribed from the nanowire structure could further improve halide detection performance. The determination was based on measurement of the well-separated oxidation peak currents of respective silver halides formed on the surface of silver during an anodic potential sweep. The concentration range was linear from 50 μM to 20.2 mM for bromide and iodide and 200 μM to 20.2 mM for chloride, and the sensitivity was 0.059 μA/mM, 0.042 μA/mM and 0.032 μA/mM for chloride, bromide and iodide, respectively. The correlation coefficient was 0.999 in each case. The Ag NWs/Pt electrode offered a useful platform for the development of a highly sensitive halide sensor.     

Composite film of carbon nanotubes and chitosan for preparation of amperometric hydrogen peroxide biosensor

A new amperometric biosensor for hydrogen peroxide was developed based on cross-linking horseradish peroxidase (HRP) by glutaraldehyde with multiwall carbon nanotubes/chitosan (MWNTs/chitosan) composite film coated on a glassy carbon electrode. MWNTs were firstly dissolved in a chitosan solution. Then the morphology of MWNTs/chitosan composite film was characterized by field-emission scanning electron microscopy. The results showed that MWNTs were well soluble in chitosan and robust films could be formed on the surface. HRP was cross-linked by glutaraldehyde with MWNTs/chitosan film to prepare a hydrogen peroxide biosensor. The enzyme electrode exhibited excellent electrocatalytic activity and rapid response for H₂O₂ in the absence of a mediator. The linear range of detection towards H₂O₂ (applied potential: −0.2 V) was from 1.67 × 10⁻⁵ to 7.40 × 10⁻⁴ M with correction coefficient of 0.998. The biosensor had good repeatability and stability for the determination of H₂O₂. There were no interferences from ascorbic acid, glucose, citrate acid and lactic acid.