Investigation of the direct electrochemistry and electrocatalysis of myoglobin on gold nanorods modified electrode

Direct electrochemistry and electrocatalysis of myoglobin (Mb) on a gold nanorod (AuNR)‐decorated carbon ionic liquid electrode (CILE) were studied in this article. The fabricated Nafion/Mb/AuNRs/CILE was used as an electrochemical biosensor for determining trichloroacetic acid (TCA) and sodium nitrite (NaNO₂). AuNRs exhibited high metal conductivity, and acted as the bridge between electrochemical active centers of Mb and the substrate electrode with the electron transfer rate accelerated. Electrochemical performances of Nafion/Mb/AuNRs/CILE were checked in pH 3.0 phosphate buffer solution with the electrochemical parameters calculated. Low detection limits and wide linear ranges were obtained in electrocatalytic investigations of different catalytic substrates including TCA and NaNO₂, which exhibited potential applications in actual sample detection.     

Cu-Doped ZnO Nanoparticles for Non-Enzymatic Glucose Sensing

Copper-doped zinc oxide nanoparticles (NPs) Cu_xZn_1−xO (x = 0, 0.01, 0.02, 0.03, and 0.04) were synthesized via a sol-gel process and used as an active electrode material to fabricate a non-enzymatic electrochemical sensor for the detection of glucose. Their structure, composition, and chemical properties were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared (FTIR) and Raman spectroscopies, and zeta potential measurements. The electrochemical characterization of the sensors was studied using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and differential pulse voltammetry (DPV). Cu doping was shown to improve the electrocatalytic activity for the oxidation of glucose, which resulted from the accelerated electron transfer and greatly improved electrochemical conductivity. The experimental conditions for the detection of glucose were optimized: a linear dependence between the glucose concentration and current intensity was established in the range from 1 nM to 100 μM with a limit of detection of 0.7 nM. The proposed sensor exhibited high selectivity for glucose in the presence of various interfering species. The developed sensor was also successfully tested for the detection of glucose in human serum samples.     

A 1-Hydroxy-2,4-Diformylnaphthalene-Based Fluorescent Probe and Its Detection of Sulfites/Bisulfite

A novel 1-hydroxy-2,4-diformylnaphthalene-based fluorescent probe L was synthesized by a Knoevenagel reaction and exhibited excellent sensitivity and selectivity towards sulfite ions (SO₃²⁻) and bisulfite ions (HSO₃⁻). The detection limits of the probe L were 0.24 μM using UV-Vis spectroscopy and 9.93 nM using fluorescence spectroscopy, respectively. Furthermore, the fluorescent probe L could be utilized for detection in real water samples with satisfactory recoveries in the range 99.20%~104.30% in lake water and 100.00%~104.80% in tap water by UV-Vis absorption spectrometry, and in the range 100.50%~108.60% in lake water and 102.70%~103.80% in tap water by fluorescence spectrophotometry.     

Comparative Permeation Study of Different Types of Myoglobin Layer‐by‐Layer Films and the Effect of Film Permeability on Their Electrochemistry and Electrocatalysis

Three different types of myoglobin (Mb) layer‐by‐layer films were assembled respectively with TiO₂ sol‐gel by vapor‐surface deposition, TiO₂ nanoparticles, and poly(styrenesulfonate), designated as {SG‐TiO₂/Mb}_n, {NP‐TiO₂/Mb}_n, and {PSS/Mb}_n. The permeability of the films was studied and compared by rotating disk voltammetry (RDV) and electrochemical impedance spectroscopy (EIS) with different electroactive probes, showing a general permeability sequence of {SG‐TiO₂/Mb}_n>{NP‐TiO₂/Mb}_n>{PSS/Mb}_n. The electrochemical and electrocatalytic activity of Mb in these films were also investigated and compared by cyclic voltammetry (CV), RDV, and amperometry, indicating that among the three Mb films, {SG‐TiO₂/Mb}_n films demonstrated the highest maximum surface concentration of electroactive Mb and the best electrocatalytic performances toward reduction of H₂O₂. All these advantages could be attributed to the unique architecture and porous structure of {SG‐TiO₂/Mb}_n films, which could greatly facilitate the mass transport of small counterions and catalytic substrates within the films. The various influencing factors on the permeability, electrochemistry, and electrocatalysis of the Mb films were also investigated in detail.     

Fabrication of multilayer-film-modified gold electrode composed of myoglobin,chitosan, and polyelectrolyte-wrapped multi-wall carbon nanotubes by layer-by-layer assembled technique and electrochemical catalysis for hydrogen peroxide and trichloroacetic acid

Electroactive multilayer film of myoglobin (Mb)-, chitosan (CS)-, and poly(dimethyldiallylammonium chloride) (PDDA)-wrapped multi-wall carbon nanotubes (MWNTs) is fabricated on a gold electrode via layer-by-layer (LBL) technique. The assembled multilayer films is characterized by scanning electron microscopy (SEM), UV-vis spectroscopy, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). UV-vis spectroscopy showed that Mb in the films retained its near-native structure. The stable multilayerfilm-modified gold electrodes showed good electroactivity in protein-free buffer solution, which is originated from protein heme Fe(III)/Fe(II) redox couple. The modified electrode exhibited good electrocatalytic property toward reduction of H₂O₂ and trichloroacetic acid, indicating the potential application as amperometric biosensor. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 11, pp. 1366–1376. The text was submitted by the authors in English.     

An Electrochemical Immunosensor Based on SPA and rGO-PEI-Ag-Nf for the Detection of Arsanilic Acid

A sensitive electrochemical immunosensor was prepared for rapid detection of ASA based on arsanilic acid (ASA) monoclonal antibody with high affinity. In the preparation of nanomaterials, polyethyleneimine (PEI) improved the stability of the solution and acted as a reducing agent to generate reduced graphene oxide (rGO) with relatively strong conductivity, thereby promoting the transfer of electrons. The dual conductivity of rGO and silver nanoparticles (AgNPs) improved the sensitivity of the sensor. The synthesis of nanomaterials were confirmed by UV-Vis spectroscopy, X-ray diffraction, transmission electron microscopy and scanning electron microscopy. In the optimal experiment conditions, the sensor could achieve the detection range of 0.50–500 ng mL⁻¹ and the limit of detection (LOD) of 0.38 ng mL⁻¹ (S/N = 3). Moreover, the sensor exhibited excellent specificity and acceptable stability, suggesting that the proposed sensor possessed a good potential in ASA detection. Thus, the as-prepared biosensor may be a potential way for detecting other antibiotics in meat and animal-derived foods.     

Binary Metal Oxide Adsorbed Graphene Modified Glassy Carbon Electrode for Detection of Riboflavin

Tungsten oxide (W) decorated titanium oxide (T) adsorbed onto a graphene (Gr) and modified the glassy carbon electrode for the electrochemical quantification of riboflavin (RF) in edible food and pharmaceuticals. For comparison, nanocomposites are formed using graphene oxide (GO), reduced graphene oxide (rGO) and pure graphite (G) sheets to study the electrochemical activities towards riboflavin. The ternary WTGr modified GCE shows the highest electrocatalytic activity due to synergetic interactions between the metal oxide and graphene. The electrochemical observations are supported by the SEM, HRTEM, XRD, UV-Vis, Zeta potential (ζ) and size data. The sensor shows a wide linear range 20 nM–2.5 μM with a detection limit 25.24 nM and sensitivity (4.249×10⁻⁸ A/nM). The fabricated sensor is validated in real samples.     

Salt Stress Mitigation via the Foliar Application of Chitosan-Functionalized Selenium and Anatase Titanium Dioxide Nanoparticles in Stevia (Stevia rebaudiana Bertoni)

High salt levels are one of the significant and major limiting factors on crop yield and productivity. Out of the available attempts made against high salt levels, engineered nanoparticles (NPs) have been widely employed and considered as effective strategies in this regard. Of these NPs, titanium dioxide nanoparticles (TiO₂ NPs) and selenium functionalized using chitosan nanoparticles (Cs–Se NPs) were applied for a quite number of plants, but their potential roles for alleviating the adverse effects of salinity on stevia remains unclear. Stevia (Stevia rebaudiana Bertoni) is one of the reputed medicinal plants due to their diterpenoid steviol glycosides (stevioside and rebaudioside A). For this reason, the current study was designed to investigate the potential of TiO₂ NPs (0, 100 and 200 mg L⁻¹) and Cs–Se NPs (0, 10 and 20 mg L⁻¹) to alleviate salt stress (0, 50 and 100 mM NaCl) in stevia. The findings of the study revealed that salinity decreased the growth and photosynthetic traits but resulted in substantial cell damage through increasing H₂O₂ and MDA content, as well as electrolyte leakage (EL). However, the application of TiO₂ NPs (100 mg L⁻¹) and Cs–Se NPs (20 mg L⁻¹) increased the growth, photosynthetic performance and activity of antioxidant enzymes, and decreased the contents of H₂O₂, MDA and EL under the saline conditions. In addition to the enhanced growth and physiological performance of the plant, the essential oil content was also increased with the treatments of TiO₂ (100 mg L⁻¹) and Cs–Se NPs (20 mg L⁻¹). In addition, the tested NPs treatments increased the concentration of stevioside (in the non-saline condition and under salinity stress) and rebaudioside A (under the salinity conditions) in stevia plants. Overall, the current findings suggest that especially 100 mg L⁻¹ TiO₂ NPs and 20 mg L⁻¹ Cs–Se could be considered as promising agents in combating high levels of salinity in the case of stevia.     

Photocatalytically Renewable Micro‐electrochemical Sensor for Real‐Time Monitoring of Cells

Electrode fouling and passivation is a substantial and inevitable limitation in electrochemical biosensing, and it is a great challenge to efficiently remove the contaminant without changing the surface structure and electrochemical performance. Herein, we propose a versatile and efficient strategy based on photocatalytic cleaning to construct renewable electrochemical sensors for cell analysis. This kind of sensor was fabricated by controllable assembly of reduced graphene oxide (RGO) and TiO₂ to form a sandwiching RGO@TiO₂ structure, followed by deposition of Au nanoparticles (NPs) onto the RGO shell. The Au NPs‐RGO composite shell provides high electrochemical performance. Meanwhile, the encapsulated TiO₂ ensures an excellent photocatalytic cleaning property. Application of this renewable microsensor for detection of nitric oxide (NO) release from cells demonstrates the great potential of this strategy in electrode regeneration and biosensing.     

Electroanalysis of myoglobin and hemoglobin with a boron-doped diamond electrode

The electrochemical behavior of myoglobin (Mb) and hemoglobin (Hb) was investigated with a boron-doped diamond (BDD) electrode by cyclic voltammetry. In acetate buffer solutions, the oxygen reduction at the BDD electrode showed a very high overpotential while the reduction of Mb or Hb was observed in the more positive potential region. Owing to the electrocatalytic reaction of O₂ and the participation of H⁺ following the electrochemical reduction of ferric proteins, the voltammetric responses for Mb and Hb on the BDD electrode in the negative going scans became remarkable in acidic buffer solutions in air. The peak current was linearly proportional to the concentration of Mb in the range 1×10⁻⁶–2×10⁻⁵ M or the concentration of Hb from 1×10⁻⁶ to 1×10⁻⁵ M.     

Exploiting multi-function Metal-Organic Framework nanocomposite Ag@Zn-TSA as highly efficient immobilization matrixes for sensitive electrochemical biosensing

A novel multi-function Metal-Organic Framework composite Ag@Zn-TSA (zinc thiosalicylate, Zn(C₇H₄O₂S), Zn-TSA) was synthesized as highly efficient immobilization matrixes of myoglobin (Mb)/glucose oxidase (GOx) for electrochemical biosensing. The electrochemical biosensors based on Ag@Zn-TSA composite and ionic liquid (IL) modified carbon paste electrode (CPE) were fabricated successfully. Furthermore, the properties of the sensors were discussed by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and amperometric current-time curve, respectively. The results showed the proposed biosensors had wide linear response to hydrogen peroxide (H₂O₂) in the range of 0.3–20,000 μM, to nitrite (NO₂⁻) for 1.3 μM–1660 μM and 2262 μM–1,33,000 μM, to glucose for 2.0–1022 μM, with a low detection limit of 0.08 μM for H₂O₂, 0.5 μM for NO₂⁻, 0.8 μM for glucose. The values of the apparent heterogeneous electron transfer rate constant (k_s) for Mb and GOx were estimated as 2.05 s⁻¹ and 2.45 s⁻¹, respectively. Thus, Ag@Zn-TSA was a kind of ideal material as highly efficient immobilization matrixes for sensitive electrochemical biosensing. In addition, this work indicated that MOF nanocomposite had a great potential for constructing wide range of sensing interface.     

An amperometric biosensor based on acetylcholinesterase immobilized onto iron oxide nanoparticles/multi-walled carbon nanotubes modified gold electrode for measurement of organophosphorus insecticides

An acetylcholinesterase (AChE) purified from maize seedlings was immobilized covalently onto iron oxide nanoparticles (Fe₃O₄NP) and carboxylated multi walled carbon nanotubes (c-MWCNT) modified Au electrode. An organophosphorus (OP) biosensor was fabricated using this AChE/Fe₃O₄/c-MWCNT/Au electrode as a working electrode, Ag/AgCl as standard and Pt wire as an auxiliary electrode connected through a potentiostat. The biosensor was based on inhibition of AChE by OP compounds/insecticides. The properties of nanoparticles modified electrodes were studied by scanning electron microscopy (SEM), Fourier transform infrared (FTIR), cyclic voltammograms (CVs) and electrochemical impedance spectroscopy (EIS). The synergistic action of Fe₃O₄NP and c-MWCNT showed excellent electrocatalytic activity at low potential (+0.4 V). The optimum working conditions for the sensor were pH 7.5, 35 °C, 600 μM substrate concentration and 10 min for inhibition by pesticide. Under optimum conditions, the inhibition rates of OP pesticides were proportional to their concentrations in the range of 0.1–40 nM, 0.1–50 nM, 1–50 nM and 10–100 nM for malathion, chlorpyrifos, monocrotophos and endosulfan respectively. The detection limits were 0.1 nM for malathion and chlorpyrifos, 1 nM for monocrotophos and 10 nM for endosulfan. The biosensor exhibited good sensitivity (0.475 mA μM⁻¹), reusability (more than 50 times) and stability (2 months). The sensor was suitable for trace detection of OP pesticide residues in milk and water.     

Signal Amplification Strategy Based on TiO2-Nanotube Layers and Nanobeads Carrying Quantum Dots for Electrochemiluminescent Immunosensors

Self-organized TiO₂-nanotube layers can be used for immunoassay-type sensing in combination with amplifying CdTe labels in a direct and very sensitive electrochemiluminescent (ECL) configuration. Key properties for this method are the conductivity of the TiO₂ nanotubes, and their transparency for light emitted from the CdTe labels at approximately 2.4 eV. To demonstrate the potential of this platform, we constructed a sandwich-type immunoassay onto the TiO₂-nanotube wall with a layer of (3-aminopropyl)triethoxysilane as the cross-linker for antibody immobilization. For the counter part of the sandwich, we created an amplification system consisting of TiO₂ nanobeads carrying the secondary antibody and multiple CdTe quantum dots (multiQD). For antigen (IgG) detection, we find that this combination of 3D transparent electrode with multiQD labels allows for an ECL detection limit of 0.05 pg mL⁻¹ and a linearity of the signal in the range of 0.1–10⁸ pg mL⁻¹.     

魔芋多糖固定化肌红蛋白的直接电化学与电催化

用魔芋多糖(KGM)和N,N-二甲基甲酰胺(DMF)的加合物,将肌红蛋白(Mb)固定在玻碳电极(GCE)上,制备了稳定的Mb-KGM-DMF/GCE修饰电极,并研究了Mb在修饰电极上的直接电化学行为和电催化性能。该电极在pH=7.0的磷酸盐缓冲溶液(PBS)中,-0.38 V(E0′)处有一对氧化还原峰,峰电位差ΔEp=70 mV,该峰正是Mb中血红素辅基FeⅢ/FeⅡ电对的氧化还原特征峰。在0.2~9.0 V/s扫速的范围内,氧化还原峰峰电流大小和扫描速率成正比,呈现出表面控制行为。在pH为5.0~12.0的范围内,式电位和pH值呈线性关系,表明电子传递过程伴随着质子转移。同时,Mb-KGM-DMF/GCE修饰电极表现出良好的电催化性能,对氧、H2O2有显著的催化作用。在4.70~75.0μmol/L的范围内,其催化峰电流大小与H2O2的浓度有良好的线性关系,其线性回归方程i=0.127 0.093C,r=0.9989,表观米氏常数为80.8μmol/L。     

The Facile Preparation of PBA-GO-CuO-Modified Electrochemical Biosensor Used for the Measurement of α-Amylase Inhibitors’ Activity

Element doping and nanoparticle decoration of graphene is an effective strategy to fabricate biosensor electrodes for specific biomedical signal detections. In this study, a novel nonenzymatic glucose sensor electrode was developed with copper oxide (CuO) and boron-doped graphene oxide (B-GO), which was firstly used to reveal rhubarb extraction’s inhibitive activity toward α-amylase. The 1-pyreneboronic acid (PBA)-GO-CuO nanocomposite was prepared by a hydrothermal method, and its successful boron doping was confirmed by transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS), in which the boron doping rate is unprecedentedly up to 9.6%. The CuO load reaches ~12.5 wt.%. Further electrochemical results showed that in the enlarged cyclic voltammograms diagram, the electron-deficient boron doping sites made it easier for the electron transfer in graphene, promoting the valence transition from CuO to the electrode surface. Moreover, the sensor platform was ultrasensitive to glucose with a detection limit of 0.7 μM and high sensitivity of 906 μA mM⁻¹ cm⁻², ensuring the sensitive monitoring of enzyme activity. The inhibition rate of acarbose, a model inhibitor, is proportional to the logarithm of concentration in the range of 10⁻⁹–10⁻³ M with the correlation coefficient of R² = 0.996, and an ultralow limit of detection of ~1 × 10⁻⁹ M by the developed method using the PBA-GO-CuO electrode. The inhibiting ability of Rhein-8-b-D-glucopyranoside, which is isolated from natural medicines, was also evaluated. The constructed sensor platform was proven to be sensitive and selective as well as cost-effective, facile, and reliable, making it promising as a candidate for α-amylase inhibitor screening.     

An Electrochemical Sensor Fabricated by Sonochemical Approach for Determination of the Antipsychotic Drug Haloperidol

A nanocomposite (Ho₂O₃NPs/BNT) was synthesized by decorating holmium(III)oxide nanoparticles (H₂O₃NPs) on bentonite (BNT) through a realizable sonochemical approach for the electrochemical detection of haloperidol (Hlp). A glassy carbon electrode was modified with this nanocomposite. The Ho₂O₃NPs/BNT modified electrode outperformed bare and other modified electrodes in terms of electrochemical performance for Hlp detection in a pH 8.0 phosphate buffer. The proposed electrochemical platform showed a wide linear range (0.01 μM–24 μM), low detection limit (2.4 nM), and high sensitivity by square wave voltammetry. In addition, the proposed electrochemical sensor met the clinical criteria in terms of stability, selectivity, and repeatability.     

Adsorptive Cathodic Stripping Voltammetry for Quantification of Alprazolam

A simple and highly sensitive electrochemical sensor was developed for adsorptive cathodic stripping voltammetry of alprazolam. Based on an electrochemically pretreated glassy carbon electrode, the sensor demonstrated good adsorption and electrochemical reduction of alprazolam. The morphology of the glassy carbon electrode and the electrochemically pretreated glassy carbon electrode were characterized by scanning electron microscopy/energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. The electrochemical behaviors of alprazolam were determined by cyclic voltammetry, and the analytical measurements were studied by adsorptive cathodic stripping voltammetry. Optimized operational conditions included the concentration and deposition time of sulfuric acid in the electrochemical pretreatment, preconcentration potential, and preconcentration time. Under optimal conditions, the developed alprazolam sensor displayed a quantification limit of 0.1 mg L⁻¹, a detection limit of 0.03 mg L⁻¹, a sensitivity of 67 µA mg⁻¹ L cm⁻² and two linear ranges: 0.1 to 4 and 4 to 20 mg L⁻¹. Sensor selectivity was excellent, and repeatability (%RSD < 4.24%) and recovery (82.0 ± 0.2 to 109.0 ± 0.3%) were good. The results of determining alprazolam in beverages with the developed system were in good agreement with results from the gas chromatography–mass spectrometric method.     

金@氧缺陷二氧化钛核壳纳米颗粒的制备及光催化产氢

通过水解TiCl_3在金纳米颗粒外表生长TiO_2,然后在Ar/H2气氛中高温煅烧成功地合成了核壳形貌的Au@H-TiO_2缺陷结构。采用XRD、TEM、XPS、UV-Vis测试方法对产物的物相结构、形貌及光吸收能力做了系统的分析。与不存在缺陷态的TiO_2和Au@A-TiO_2相比,Au@H-TiO_2表现出最高的产氢速率,这可以归因于其电荷分离效率的提高和电荷转移阻抗的降低,瞬态光电流测试以及电化学阻抗数据证实了这一结论。这些性能的改进可能与Au@H-TiO_2中的Ti~(3+)自掺杂和Au修饰有关。     

Au-TiO2/Chit modified sensor for electrochemical detection of trace organophosphates insecticides

In this paper, Au–TiO₂/Chit modified electrode was prepared with Au–TiO₂ nanocomposite (Au–TiO₂) and Chitosan (Chit) as a conjunct. The Au–TiO₂ nanocomposite and the films were characterized by electrochemical and spectroscopy methods. A set of experimental conditions was also optimized for the film's fabrication. The electrochemical and electrocatalytic behaviors of Au–TiO₂/Chit modified electrode to trace organophosphates (OPs) insecticides such as parathion were discussed in this work. By differential pulse voltammetry (DPV) measurement, the current responses of Au–TiO₂/Chit modified electrode were linear with parathion concentration ranging from 1.0 ng/ml to 7.0 × 10³ ng/ml with the detection limit of 0.5 ng/ml. In order to evaluate the performance of the detection system, we also examined the real samples successfully in this work. It exhibited a sensitive, rapid and easy-to-use method for the fast determination of trace OPs insecticides.     

Highly Active Nickel Nanoparticles Supported on TiO2 Nanotube Electrodes for Methanol Electrooxidation

Nickel nanoparticles/TiO₂ nanotubes/Ti electrodes were prepared by galvanic deposition of nickel nanoparticles on the TiO₂ nanotubes layer on titanium substrates. Titanium oxide nanotubes were fabricated by anodizing titanium foil in a DMSO fluoride‐containing electrolyte. The morphology and surface characteristics of titanium dioxide nanotubes and Ni/TiO₂/Ti electrodes were investigated using scanning electron microscopy and energy‐dispersive X‐ray spectroscopy, respectively. The results indicated that nickel nanoparticles were homogeneously deposited on the surface of TiO₂ nanotubes. The electrocatalytic behaviour of nickel nanoparticles/TiO₂/Ti electrodes for the methanol electrooxidation was studied by electrochemical impedance spectroscopy, cyclic voltammetry, differential pulse voltammetry and chronoamperometry methods. The results showed that Ni/TiO₂/Ti electrodes exhibit a considerably higher electrocatalytic activity toward the oxidation of methanol.