Electrochemical behavior of pyrroloquinoline quinone immobilized on silica gel modified with zirconium oxide

Pyrroloquinoline quinone (PQQ) was immobilized on the silica gel surface modified with zirconium oxide, designated as Si:Zr, by the carboxylic groups of the PQQ molecule and the zirconium oxide on the silica surface. The electrochemistry of PQQ immobilized on the Si:Zr matrix, incorporated in a carbon paste electrode, was evaluated using the cyclic voltammetry technique. The Si:Zr:PQQ-modified electrode showed a redox couple at E(m)=(E(pa1)+E(pc))/2=-0.150 V vs SCE at pH 7, close to that observed in aqueous solution, and another oxidation peak, E(pa2)=-0.100 V vs SCE. Studies in different pH solutions in the range of 3-7 showed that the first oxidation peak, E(pa1), is highly dependent on the solution pH shifting from to -0.175 to 0.100 V vs SCE, while E(pa2) remains practically constant at 0.100 V as the pH decreases from 7 to 3. The immobilized PQQ electrode presented the property to electrocatalyze the NADH at 150 mV vs SCE. The effect of addition of Ca(2+) ions on the electrode electroactivity for the NADH oxidation was also verified. Different from that observed for the PQQ immobilized on other electrode materials, the Ca(2+) ions did not influence the electrocatalytical response; however, the electrode stability was considerably improved in the presence of Ca(2+) ions, indicating that the matrix surface has a great influence on the electrochemical behavior of PQQ.     

芦丁修饰电极的电化学特性及其催化性能

研究了芦丁修饰玻碳电极的制备及其电化学性质,探讨了电极反应的机理为ECE过程。研究了它对抗坏血酸和KMnO4的电催化作用:在pH6.0的磷酸盐缓冲溶液(PBS)中,此修饰电极对抗坏血酸有良好的催化氧化作用,而对KMnO4有良好的催化还原作用。     

Tetracyanoquinodimethanide adsorbed on a silica gel modified with titanium oxide for electrocatalytic oxidation of hydrazine

The electrocatalytical oxidation of hydrazine at low potential using tetracyanoquinodimethanide adsorbed on silica modified with titanium oxide was investigated by cyclic voltammetry and amperometry. The modified electrode was prepared modifying a carbon paste electrode employing lithium tetracyanoquinodimethanide adsorbed onto silica gel modified with titanium oxide. This electrode showed an excellent catalytic activity and stability for hydrazine oxidation. With this modified electrode, the oxidation potential of hydrazine was shifted toward less positive value, presenting a peak current much higher than those observed on a bare GC electrode. The linear response range, sensitivity and detection limit were, respectively, 2 up to 100 μmol l⁻¹, 0.36 μA l μmol⁻¹, and 0.60 μmol l⁻¹. The repeatability of the modified electrode evaluated in term of relative standard deviation was 4.2% for 10 measurements of 100 μmol l⁻¹ hydrazine solution. The number of electrons involved in hydrazine oxidation (4), the heterogenous electron transfer rate constant (1.08 × 10³ mol⁻¹ l s⁻¹), and diffusion coefficient (5.9 × 10⁻⁶ cm² s⁻¹) were evaluated with a rotating disk electrode.     

Electrochemical behavior of horseradish peroxidase on WS2 nanosheet‐modified electrode and electrocatalytic investigation

In this paper, a WS₂ nanosheet was modified on the surface of a carbon ionic liquid electrode (CILE), and horseradish peroxidase (HRP) was further fixed on the electrode with a Nafion film. Direct electrochemistry and bioelectrocatalysis of HRP incorporated on the modified electrode were investigated in detail. On Nafion/HRP/WS₂/CILE, a pair of well‐defined quasi‐reversible redox peaks appeared on the cyclic voltammogram, indicating that the presence of the WS₂ nanosheet on the electrode surface could provide a specific interface with large surface area for HRP and its direct electron transfer rate was greatly enhanced. The formal potential (E⁰) obtained was –0.179 V, which was the typical feature of heme Fe(III)/Fe(II) in HRP. The electron transfer coefficient (α) and the heterogeneous electron transfer rate constant (k_s) of HRP were calculated as 0.44 and 1.01 s^–1, respectively. This HRP‐modified electrode showed excellent electrocatalytic activity for the reduction of trichloroacetic acid and NaNO₂ with a wide linear range and low detection limit. Real samples were detected by this proposed method, indicating the successful fabrication of a new third‐generation electrochemical enzyme sensor utilizing the WS₂ nanosheet.     

Electrochemical and catalytic investigation of carbon paste modified with Toluidine Blue O covalently immobilised on silica gel

Toluidine Blue O (TBO) was covalently bound on silica gel and mixed with graphite powder and paraffin oil to produce modified carbon paste electrodes. The formal potential (E°′) of the covalently bound TBO was found to be −100 mV versus Ag|AgCl (KCl sat.) at pH 7.0 and the E°′ varied less than anticipated for a 2-electron-proton type mediator with pH. The bound TBO was found to act as an efficient electron acceptor for NADH as well as electron donor for oxidised horseradish peroxidase (HRP). The kinetics and the mechanism of the reaction between NADH and TBO were investigated with cyclic voltammetry and using a rotating disc electrode. Further experiments were done in the flow injection mode injecting different concentrations of NADH. Similar studies were done in the presence of hydrogen peroxide when HRP was adsorbed onto the TBO modified silica gel carbon paste electrodes.     

An amperometric sensor based on hemin adsorbed on silica gel modified with titanium oxide for electrocatalytic reduction and quantification of artemisinin

The present work describes the development of an amperometric sensor based on hemin immobilized on a titanium oxide modified silica toward detection of artemisinin (ARN) in neutral medium at an applied potential of −0.5 V vs. Ag/AgCl. The sensor presented its best performance in 0.1 mol L⁻¹ phosphate buffer solution, at pH 7.0. After optimizing the operational conditions, the sensor provided a linear response range for ARN reduction from 50 nmol L⁻¹ to 1000 nmol L⁻¹ with a sensitivity, detection and quantification limits of 24.66 A L mol⁻¹, 15 nmol L⁻¹ and 52 nmol L⁻¹, respectively. The proposed sensor showed a stable response for at least 80 successive determinations. The repeatability of the measurements with the sensor and the preparation of a series of electrodes, evaluated in terms of relative standard deviation, were 4.1% and 5.0%, respectively, for n = 10. The developed sensor was applied for the determination of ARN in the crude extracts of A. vulgaris L and the average recovery for these samples is 101.4 (± 3.1)%.     

Photoacoustic spectroscopic studies of methylene blue and malachite green adsorbed on silica

Spectra and calibration curves of methylene blue and malachite green adsorbed on silica show that photoacoustic spectroscopy can be used for the determination of these compounds. The problem of the existence of an equilibrium between monomer and dimer for methylene blue is considered.     

Electrochemical performance and electrocatalytic behavior of myoglobin on graphene tube-modified electrode

A new protein biosensing strategy based on a graphene tube (GT)-modified electrode was developed in this article. GT as a fixed material and signal amplifier was loaded on the carbon ionic liquid electrode (CILE) surface, which could provide a suitable environment for myoglobin (Mb) immobilization and promote electron transfer between Mb and the electrode. Fourier-transform infrared spectroscopy (FT-IR) of Mb before and after mixing with GT was checked and showed that the native structure of Mb was maintained. The direct electrochemistry of Mb was investigated with a pair of obtained well-defined and quasireversible redox peaks. The modified electrode (Nafion/Mb/GT/CILE) also showed excellent electrocatalytic activity for the reduction of trichloroacetic acid (TCA) and NaNO₂, which could be utilized to determine the concentrations of TCA and NaNO₂ with wide detection range and low detection limit. The biosensor was further applied to the detection of a real sample and obtained satisfactory experimental results.     

Sorption behavior of gamma-irradiated silica gel

The effect of Pb(II) and non-ionic surfactants (oxyethylate alcohols OS-10 and ALM-10) on the rate of intraparticle diffusion and on to the equilibrium sorption on Purolite C 106 cation exchanger in hydrogen form was investigated. The sorption of Pb(II) cations and in free state and bonded to the surfactant was measured. The coefficients of intraparticle diffusion were also calculated.     

Sorption behavior of vanadium on silica gel modified with tetrakis(4-carboxyphenyl)porphyrin.

Tetrakis(4-carboxyphenyl)porphyrin (TCPP) has been loaded on aminopropyl-silica gel by physical adsorption and by direct immobilization through formation of an amide bond to obtain chelating sorbents. These sorbents have been studied for preconcentration and separation of vanadium prior to its determination by atomic absorption spectrometry. Several parameters, such as sorption capacity of the chelating resin, pH for retention of V(IV) and V(V), volume of sample and eluent, were evaluated. Both vanadium species sorbed on TCPP-modified resin could be eluted using 2 mol L(-1) nitric acid solution. The recovery values were > 94% and preconcentration factor of 160 was obtained. For speciation analysis, cyclohexane-1,2-diaminetetraacetic acid (CDTA) was added to the sample for complexation of vanadium(IV), which was not retained on the microcolumn. The proposed method was examined for reference standard materials (TM-25.2 and CAAS-3) as well as for river water samples.     

亚甲基蓝与酵母核糖核酸相互作用的电化学研究

亚甲基蓝(methylene blue,MB)是一种具有平面结构(结构式见图1)的碱性生物染色剂,在医学临床诊断及化学分析中已有较长的应用历史,可用于亚硝酸盐、磺氨类、氰化物及一氧化碳等中毒的解毒药。电分析化学中常被用作氧化还原指示剂或电子媒介体,其在水溶液中的电化学行为曾被深入地研究[1-2]。在水溶液中,MB的还原态为无色中性分子,而氧化态MB 为一价阳离子,由于分子中环平面和氮杂原子上甲基的存在而具有一定的疏水性。水溶液中MB容易形成二聚体,在电极上发生两个连续的1电子转移反应(EE mechanism)[1],其氧化还原电位的峰距ΔEp介于1电…     

Keggin结构过渡金属取代硼钨酸盐的电化学及电催化还原

采用循环伏安法,研究了Keggin结构过渡金属取代硼钨酸盐K7[MBW11(H2O)O39].H2O(简写为MBW11,M=Cu,Co,Ni)的电化学性质及电催化活性.结果表明,CuBW11在水溶液中表现出较为特殊的电化学性质,MBW11(M=Cu,Co,Ni)对亚硝酸根及碘酸根离子的还原反应具有较好的催化作用,取代金属对该体系的电催化活性有很大影响.     

Chemisorption of vapors of organic substances on a modified silica gel

Experimental data on the equilibrium and dynamics of chemisorption of vapors of organic substances on a silica gel modified with color reagents are presented.     

Multitracer study on the effect of humate formation on the adsorption behavior of metal ions on kaolinite and silica gel

The multitracer technique was applied to elucidate of influence of humate formation on adsorption behavior of ultratrace elements. Dissolved fractions of Co, As, Rb, Sr, Y, Zr, Ba, Ce, Eu, Gd, Tb, Yb, Lu, Hf, Re and Pt in contact with kaolinite or silica gel were determined simultaneously either in the presence or absence of humic acid, which was partly adsorbed on the solid. Percentage of dissolved fraction of rare earth elements was identical to that of humic acid, indicating high stability of the rare earth-humate complex. Hydrolysis was the most important factor controlling the behavior of Zr and Hf. Both hydrolysis and humate complexation influenced the adsorption of Co, Sr, Ba and Pt, whereas neither affected the distribution of As, Rb and Re.     

Amino modified mesostructured silica nanoparticles for efficient adsorption of methylene blue

In this work, mesostructured silica nanoparticles (MSN(AP)) with high adsorptivity were prepared by a modification with 3-aminopropyl triethoxysilane (APTES) as a pore expander. The performance of the MSN(AP) was tested by the adsorption of MB in a batch system under varying pH (2-11), adsorbent dosage (0.1-0.5gL(-1)), and initial MB concentration (5-60mgL(-1)). The best conditions were achieved at pH 7 when using 0.1gL(-1) MSN(AP) and 60mgL(-1)MB to give a maximum monolayer adsorption capacity of 500.1mgg(-1) at 303K. The equilibrium data were evaluated using the Langmuir, Freundlich, Temkin, and Harkins-Jura isotherms and fit well to the Freundlich isotherm model. The adsorption kinetics was best described by the pseudo-second order model. The results indicate the potential for a new use of mesostructured materials as an effective adsorbent for MB.     

Adsorption of midmolecular peptides by fullerene modified silica gel

The adsorption properties of raw and processed silica gels and of silica gels modified with fullerene (fullerene-silica gel nanosystems) toward serum midmolecular peptides of ischemic origin were examined. A high adsorption capacity of the nanosorbents was found. The influence of fullerenes on the condition of silica gel was studied by solid-state NMR, and an increase in the silanol fraction at the adsorbent surface was demonstrated. It was shown that presence of fullerene C₆₀ in nanosorbents enables oxidation reaction of the adsorbed peptides, i.e., sorption of metabolites.     

Ion-exclusion chromatography of carboxylic acids on silica gel modified with aluminium

The modification of silica gel with aluminium by a coating method was effective for the preparation of a silica-based stationary phase, which acted as a cation exchanger under strongly acidic conditions. In order to expand the utility of the laboratory-made aluminium-adsorbing silica gel it was applied as a stationary phase to the ion-exclusion chromatography of various carboxylic acids. Good separations for both aliphatic carboxylic acids and benzenecarboxylic acids with a hydrophobic nature under acidic eluent conditions were achieved in 25 min.     

The bifunctionality of silica gel modified with Congo red

Silica gel was chemically modified with Congo red and characterized by Fourier transform infrared spectroscopy, elemental and thermogravimetric analysis. The pH-sensitive immobilized Congo red retains the same properties as its solution counterpart and could be applied as solid indicator. The functionalized silica gel was also employed to extract different cations from water solutions. The concentration of cations extracted was determined by inductively coupled plasma optical emission spectrometry. The solid support is able to selectively extract silver and copper from water solutions and retains its properties after treatment with different organic and inorganic solvents.      

丁香酚在改性蒙脱土修饰电极上的电化学行为及测定

制备了十八烷基三甲基溴化铵( STMAB)改性蒙脱土修饰电极,用循环伏安法和差分脉冲伏安法(DPV)研究了丁香酚在该电极上的电化学行为.在pH6.0 PBS电解液中,丁香酚在该电极上的电极反应受扩散控制,转移电子数等于质子数n=m=2,电极有效面积Aeff=0.034cm2,扩散系数D =2.58×10-6cm2/s....     

Electrochemical behavior of methyl viologen at graphite electrodes modified with Nafion sol–gel composite

Electrodes were prepared by spin-coating spectroscopic graphite rods with a Nafion doped sol. Coating solutions consisting of Nafion:TEOS (tetraethoxysilane) ratios of 3:1 and 4:1 gave smooth films on the electrode surface. These modified electrodes were evaluated and compared with Nafion modified and bare spectroscopic graphite electrodes using methyl viologen (MV²⁺) as a representative cationic electroactive probe. Substantial partitioning of MV²⁺ into the Nafion:sol–gel matrix to the electrode surface was observed by cyclic voltammetry and square wave voltammetry. Cyclic voltammograms of MV²⁺ in 0.1 M NaCl at Nafion:sol–gel 4:1 modified electrodes showed a reversible reduction to MV⁺ with E^0′=−0.695 V vs. Ag/AgCl. Results of scan rate variation showed the wave to be characterized by semi-infinite diffusion for scan rates in the range 50–500 mV/s. Slowing the scan rate below 50 mV/s resulted in a transition to thin-layer behavior. MV²⁺ partitioned much more quickly into the sol–gel-Nafion modified electrodes compared to pure Nafion modified electrodes. Reversibility of the MV²⁺-loaded modified Nafion-doped sol–gel coatings on electrodes was obtained by soaking in 1 M NaCl solution. Concentration calibration plots for MV²⁺ at the sol–gel-Nafion modified electrodes were nonlinear. Substantial enhancement of current signal at low concentrations was observed by square wave voltammetry.