溶菌酶在裸金电极和疏基乙酸或正十二疏烷基醇修饰电极上的吸附

电化学石英晶体阻抗系统;疏基乙酸;溶菌酶在裸金电极和疏基乙酸或正十二疏烷基醇修饰电极上的吸附     

In Situ Monitoring of the Generation of Monodisperse Silica Particles during the Hydrolysis of Tetraethyl Orthosilicate with Piezoelectric Quartz Crystal Impedance Analyzer

The piezoelectric quartz crystal(PQC)impedance analyzer was used to monitor in situ the generation of monodisperse silica particles during the hydrolysis of tetraethyl orthosilicate (TEOS) and their adsorption onto and Au electrode in alcohol solutions containing water(6-15mol/L)and ammonia(0.2-2.0 mol/L).The equivalent circuit parameters,the resonance frequencies and the half-peak width values of the conductance spectra of the PQC resonance were obtained.The resonant frequency decreased notably while the motional resistance changed very slightly(within 1Ω during the hydrolysis reaction,suggesting that the mass effect dominated the adsorption of generated monodisperse silica particles on the gold electrode in this system.Changes in f0 indicated that the ammonia concentration affected the hydrolytic reaction obviously,and the influence of water concentration on the reaction was small while the water was significantly excessive.Kinetics of monodisperse silica particle adsorption occurring at the electrode i solution interface was analyzed using a first-order reaction scheme.In addition,the electrolyte-induced precipitation of the monodisperse silica of adsorbed particles per area and the converge of monodisperse silica particles were obtained from scanning electron nicroscope(SEM)observations.     

An electrochemical quartz crystal impedance study on the rising of an aqueous solution meniscus for a partially immersed gold electrode during the electrochemical reduction of oxygen.

An electrochemical quartz crystal impedance system (EQCIS) was used to study the resonance behavior of an AT-cut 9-MHz piezoelectric quartz crystal (PQC) with its Au electrode partially immersed in KCl, Na2SO4 and NaClO4 aqueous solutions, respectively. An in situ determination of the immersed area and the height of the electrode was achieved by simultaneous measurements of the PQC electroacoustic admittance and the electrochemical impedance. The rising of the solution meniscus for a gold electrode partially immersed in aqueous solutions was found at oxygen reduction potentials and evaluated versus the electrolyte, electrolyte concentration, solution pH and oxygen concentration. The solution meniscus rising was explained based on a lowering of the contact-angle hysteresis and a continued collection of the water product at the solid-gas-solution interface during oxygen reduction.     

A comparative study on the viscoelasticity and morphology of polyaniline films galvanostatically grown on bare and 4-aminothiophenol-modified gold electrodes using an electrochemical quartz crystal impedance system and SEM.

The equivalent-circuit parameters of the 9-MHz piezoelectric quartz crystal (PQC) resonance were measured in situ during the galvanostatic polymerization of aniline on 4-aminothiophenol(4-ATP)-modified and bare Au electrodes for ca. 2000 s, respectively. Two polymerization media, 0.100 mol L-1 aniline in 1.0 mol L-1 H2SO4 and in 2.0 mol L-1 HClO4 aqueous solutions, and two values of the current density, 12 and 36 microA cm-2, were used. At identical levels of the resonant frequency shifts in the solutions, obviously greater increases in the motional resistance (R1) were found after aniline polymerization on bare Au electrodes, though the absolute values of delta f0/delta R1 were all large; also, the resonant frequency shifts in air (delta f0g) were considerably smaller for PANI films grown on bare Au electrodes. It is thus concluded that, under identical polymerization conditions, (1) the PANI film grown on a bare gold electrode is rougher, less compact, and can entrap solution more notably; (2) the deposition efficiency of PANI is higher on a 4-ATP-modified Au electrode, owing to a significantly greater observed "dry" frequency shift, and thus a greater "net" mass value of the polyaniline backbone. SEM observations have confirmed that PANI films on 4-ATP-modified Au electrodes were smoother and more compact than those grown on bare Au ones under identical polymerization conditions. In addition, a technique of simultaneous measurements of the electroacoustic admittance of the PQC resonance and the electrochemical impedance was used to monitor the adsorption of 4-ATP onto a PQC gold electrode.     

Study of fibrinogen adsorption on hydroxyapatite and TiO2 surfaces by electrochemical piezoelectric quartz crystal impedance and FTIR-ATR spectroscopy

The electrochemical piezoelectric quartz crystal impedance (EQCI), a combined technique of piezoelectric quartz crystal impedance (PQCI), electrochemical impedance (EI), and Fourier transform infrared spectroscopy-attenuated total internal reflectance spectroscopy (FTIR-ATR) were used to in situ study the adsorption process of fibrinogen onto the surface of biomaterials—TiO₂ and hydroxyapatite (Ca₅(PO₄)₃OH, HAP). The equivalent circuit parameters, the resonance frequencies and the half peak width of the conductance spectrum of the two biomaterial-modified piezoelectric quartz crystal (PQC) resonances as well as the FTIR-ATR spectra of fibrinogen during fibrinogen adsorption on TiO₂ and HAP particles modified electrode surface were obtained. The adsorption kinetics and mechanism of fibrinogen were investigated and discussed as well. The results suggested that two consecutive steps occurred during the adsorption of fibrinogen onto TiO₂ and hydroxyapatite (HAP) surface. The fibrinogen molecules were firstly adsorbed onto the surface, and then the rearrangement of adsorbed fibrinogen or multi-layered adsorption occurred. The FTIR-ATR spectroscopy investigations showed that the secondary structure of fibrinogen molecules was altered during the adsorption and the adsorption kinetics of fibrinogen related with the variety of biomaterials. These experimental results suggest a way for enriching biological analytical science and developing new applications of analytical techniques, such as PQCI, EI, and FTIR-ATR.     

Simultaneous quartz crystal microbalance-electrochemical impedance spectroscopy study on the adsorption of anti-human immunoglobulin G and its immunoreaction at nanomaterial-modified Au electrode surfaces.

The quartz crystal microbalance method (QCM), in combination with electrochemical impedance spectroscopy (EIS), has been utilized to monitor in situ anti-human IgG adsorption on several Au-based surfaces, bare Au, nanogold/4-aminothiophenol (4AT)/Au, and multi-walled carbon nanotubes (MWCNT)/Au, and succeeding human IgG reactions. Also, the immobilization protocol of anti-human IgG via its glutaraldehyde (GA) cross-linking with self-assembled 4AT on an Au electrode and the subsequent surface immunoreaction were examined. The resonant frequency (f(0)) and the motional resistance (R(1)) of the piezoelectric quartz crystal (PQC) as well as electrochemical impedance parameters were measured and discussed. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) of the ferricyanide/ferrocyanide couple were examined before and after electrode modification, the antibody adsorption and antibody-antigen reactions. We found that the amount for antibody adsorption was the greatest on the colloid Au modified surface, and that at MWCNT ranked the second, while specific bioactivity was almost identical on the four kinds of surfaces. Two parameters simultaneously obtained at the colloid Au modified surface, Deltaf(0) and DeltaC(s) (interfacial capacitance), have been used to estimate the association constant of the immunoreaction.     

Piezoelectric transmission spectroelectrochemistry with a normal piezoelectric quartz crystal as an optically-transparent electrode

Piezoelectric transmission spectroelectrochemistry (PTSEC), i.e., the combination of electrochemistry and spectroelectrochemistry (SEC) with electrochemical quartz crystal microbalance (EQCM) technique is reported by using a normal piezoelectric quartz crystal (PQC) as an optically-transparent electrode (OTE). A theoretical relationship between the PQC response and the spectroelectrochemical response is derived and used to estimate the apparent molar absorptivity of the absorbing species deposited on the OTE on the PQC surface. The complex of copper with aspartic acid is used to test this new PQC-SEC technique. Results show that the combination of three such diverse techniques provides a very useful methodology for studying electrode processes and electrode surface characteristics in situ.     

A novel dual-impedance-analysis EQCM system--investigation of bovine serum albumin adsorption on gold and platinum electrode surfaces

Both quartz crystal micro-balance (QCM) impedance and electrochemical impedance spectroscopy (EIS) methods are widely used in interface studies. This paper presents details about a new strategy for simultaneous, mutual-interference-free and accurate measurements of QCM impedance and EI, through connecting a suitable capacitance in series with the piezoelectric quartz crystal (PQC) between QCM impedance and EIS measurement instruments. Combined and individual measurements of QCM impedance and EIS during silver deposition gave results comparable with each other, demonstrating the reliability of the proposed method. Bovine serum albumin (BSA) adsorption on gold and platinum electrodes in Britton-Robinson (B-R) buffers was investigated, and the Fe(CN)6(3-)/Fe(CN)6(4-) couple was used as an electrochemical probe to characterize BSA adsorption. While the reversibility of Fe(CN)6(3-)/Fe(CN)6(4-) couple on bare Au and Pt electrodes changed very slightly with decreasing solution pH from pH approximately 7 to pH approximately 2, the standard rate constant (ks) of this couple increased abruptly with solution pH below pH approximately 4.5 at a BSA-modified Au electrode, but decreased with solution pH at a BSA-modified Pt electrode. By analyzing the QCM impedance data with a modified BVD equivalent circuit and the EI data with a modified Randle's equivalent circuit, inflexion changes at pH approximately 4.5 were all found at pH-dependent responses of the resonant frequency, the double-layer capacitance, the capacitance of the adsorbed BSA layer, the peak-absorbance values of BSA solutions at 277.5 and 224.5 nm, and so on. It was also found that a BSA adsorption layer can effectively inhibit gold corrosion during ferrocyanide oxidation in a ferrocyanide-containing BR solution. Some preliminary explanations of these findings have been given. The proposed method is highly recommended for wider applications in surface science.     

In situ monitoring of the rising of aqueous solution meniscus for a partially immersed silver electrode during electrochemical reduction of oxygen

Rising phenomena of aqueous solution meniscus were found for the silver electrode of a 5 MHz piezoelectric quartz crystal (PQC) partially immersed in Na₂SO₄, NaClO₄, HClO₄ and NaF aqueous solutions at oxygen reduction potentials, respectively. A detailed study revealed that a decrease in contact‐angle hysteresis (or a contact‐angle decrease) and a continued collection of the water product at the solid‐gas‐solution interface during oxygen reduction, rather than the electrocapillary effect and an agitation effect induced by the oscillation of PQC, are responsible for the meniscus‐rising phenomena. In addition, in situ determination of the immersed height of a partially immersed Ag electrode was studied on the basis of simultaneous measurements of the electroacoustic admittance and electrochemical impedance.     

Simultaneous impedance measurements of two one-face sealed resonating piezoelectric quartz crystals for in situ monitoring of electrochemical processes and solution properties

Through admittance measurements of two piezoelectric quartz crystals in parallel on one impedance analyzer and then non-linear fitting according to an equivalent circuit of two parallel Butterworth-Van Dyke circuits, we have simultaneously obtained accurate and precise impedance responses of two one-face sealed crystals to changes in solution density and viscosity, temperature, conductance, and/or electrode mass. A series of sucrose aqueous solutions, ferri-/ferrocyanide redox switching, hot water cooling, a series of NaClO₄ aqueous solutions, bovine serum albumin adsorption and silver electrodeposition/stripping were selected as model systems for such purposes. Galvanostatic charging/discharging reactions at positive and negative poles in a Ni-Zn battery were synchronously monitored, with some quartz crystal microbalance (QCM) insights into the second reduction process of nickel hydroxide film. In all cases, the crystal immersion angle effect was found to be negligible. The present method as a versatile one is highly recommended for informative two-electrode monitoring of two concurrent chemical or biological events, or for check and/or compensation of effects due to solution density, viscosity, temperature and/or conductance during QCM researches.     

Piezoelectric quartz crystal impedance study of the Pb2+-induced precipitation of bovine serum albumin and its dissolution with EDTA in an aqueous solution.

The piezoelectric quartz crystal impedance technique (QCI) was employed to monitor in situ the Pb2+-induced precipitation of BSA onto a gold electrode and the precipitate dissolution with EDTA in an aqueous solution. The critical precipitation concentration of Pb2+, at which the resonant frequency decreased significantly, was estimated to be 4.78 x 10(-4) mol/L. The saturated adherence of the precipitate on the electrode was observed when the concentration of Pb2+ was greater than 7.53 x 10(-2) mol/L. The frequency response was mainly caused by the mass effect of the precipitate adherence to the electrode, rather than the changes in the physico-chemical properties of the contacting liquid. An excess addition of Na2EDTA after the Pb2+-BSA dissolution led to new precipitation, probably due to the formation of an EDTA precipitate in this medium (pH approximately 3). The pH effect on the response of the resonant frequency was analyzed by using the sum of two exponential functions. A larger frequency response occurred at a pH greater than pI. These findings have been reasonably explained. Also, a decrease in the concentration of the background electrolyte increased the frequency response.     

Scanning electrochemical microscopy in combination with piezoelectric quartz crystal impedance analysis for studying the growth and electrochemistry as well as microetching of poly(o-phenylenediamine) thin films

The combination of scanning electrochemical microscopy (SECM) with piezoelectric quartz crystal impedance (PQCI) analysis was proposed as a novel multiparameter method for investigating the cyclic voltammetric growth of poly(o-phenylenediamine) (PoPD) thin films at Au electrodes in aqueous solutions of various pH values and the potentiostatic microetching (localized degradation) of these films in 0.10 mol/L aqueous H2SO4 for comparative examinations on polymer porosity and stability. Two potential-sweep ranges, -0.4 to 0.9 (I) and 0 to 0.9 (II) V versus SCE, and four solutions, acidic (A, 0.20 mol/L H2SO4 + 0.10 mol/L Na2SO4; B, 0.10 mol/L H2SO4 + 0.20 mol/L Na2SO4), neutral (C, 0.10 mol/L PBS + 0.20 mol/L Na2SO4, pH 7.2), and alkaline (D, 0.20 mol/L NaOH + 0.20 mol/L Na2SO4) aqueous solutions, were selected for PoPD growth. The pH increase for the polymerization solution increased the molar percentage of polyaniline-like chains in PoPD, as quantified from the current peaks at approximately 0.6 V versus a saturated calomel electrode (SCE) for the oxidation of -NH2 groups in as-prepared PoPD (grown from solutions C and D) during their redox switching in 0.10 mol/L aqueous H2SO4 for the first time. The unusual PQCI responses observed at negative potentials (potential range I) in the first several potential cycles during the cyclic voltammetric growth of PoPD in acidic and neutral solutions have been reasonably explained as being due to the precipitation/dissolution of the poorly soluble phenazinehydrine charge-transfer complexes developed during redox switching of oligomers for the first time, which brought about much less compact PoPD films and their higher degradability than those grown in the same solution but over potential range II. SECM, scanning electron microscopy (SEM), and piezoelectric quartz crystal (PQC) frequency were used to estimate the sizes of etched microscale spots. In addition, the x-, y-, or z-axis movement of a Pt microelectrode of 25-mum diameter near the PQC electrode was found to influence negligibly the PQCI responses in 1.0 mol/L aqueous Na2SO4 containing K4Fe(CN)6 up to 0.10 mol/L, and a new protocol of dynamically electrodepositing silver microwires via the chemical-lens method was proposed for examining the local mass-sensitivity distribution on the PQC surface.     

Electrochemical piezoelectric quartz crystal impedance study on the interaction between concanavalin A and glycogen at Au electrodes

The carbohydrate research has emerged as a "new frontier" in chemical/biological field. The binding of lectin with carbohydrate is one of the important courses of life activities. The report studies concanavalin A (Con A)-glycogen interaction on gold electrode surfaces by electrochemical piezoelectric quartz crystal impedance (EPQCI) method. The piezoelectric quartz crystal (PQC) parameters, resonant frequency shift (Deltaf(0)) and the motional resistance change (DeltaR(1)), and the electrochemical impedance (EI) parameters, electrolyte resistance change (DeltaR(s)) and the double layer capacitance change (DeltaC(s)), were measured and discussed simultaneously. Two methods were adopted for measuring the Con A-glycogen association. Based on EPQCI measurement during Con A reaction with glycogen adsorbed on Au electrode, association constant K(a) and the amount of the binding sites s calculated are 1.48 x 10(6) M(-1) and 4.09, respectively. Based on single PQC measurement of glycogen reaction with Con A assembled on Au electrode, K(a) was estimated to be 1.26 x 10(6) M(-1).     

Monitoring of mutagenic process with piezoelectric quartz crystal impedance analysis

A novel method for monitoring of mutagenic process of dimethyl sulfate to Salmonella typhimurium strain (TA100) was proposed by using piezoelectric quartz crystal impedance (PQCI) analysis technique. The time courses of responses piezoelectric impedance parameters for a quartz crystal in a culture system were simultaneously obtained and discussed. It was found that the motional resistance variation (DeltaR(m)) increases and frequency shift (Deltaf) of PQC sensor decreases correspondingly during the mutagenic process of the bacteria. These parameters could reflect the variations of viscosity and density of culture system. By fitting DeltaR(m) versus time curves toward Gompertz bacterial growth model, we obtained and discussed the bacterial growth parameters for both normal growth and mutagenic process. The experiments showed that the proposed method could provide real time and multidimensional impedance information to the monitoring of mutagenic process.     

聚邻苯二胺/镍氢氧化物修饰电极的研究

采用循环伏安法(CV)在聚邻苯二胺修饰玻碳电极表面络合Ni2+,然后将其置于NaOH溶液中CV扫描成功制备了镍氢氧化物/聚邻苯二胺/玻碳修饰电极(Ni(OH)2/PoPD/GC).通过CV探讨了聚合和负载机理,电化学交流阻抗谱(EIS)表征了电极修饰过程中界面阻抗变化,扫描电镜表征了PoPD膜负载Ni(OH)2后的形态...     

Electrodeposited sol-gel-imprinted sensing film for cytidine recognition on Au-electrode surface

A novel thin molecularly imprinted sol-gel film with specific recognition for cytidine was electrodeposited on the surface of piezoelectric quartz crystal (PQC) Au-electrode. In this method, a sufficiently negative potential was applied to the electrode surface to generate hydroxyl ions, which play the role of the catalyst for the hydrolysis and condensation of 3-(aminopropyl)trimethoxysilane (APTMS). The process of the preparation of the imprinted sol-gel film was investigated in detail by using the piezoelectric quartz crystal impedance (PQCI) technique and cyclic voltammetry. The thickness of the imprinted film was controlled easily by adjusting the applied potential and the deposited time. The binding capacity and the selectivity of the electrodeposited imprinted sol-gel film were also studied in detail by using PQCI, electrochemically impedance technique and capacitance technique. The electrodeposited imprinted sol-gel film exhibited high selectivity toward cytidine in comparison to interfering substances. The dissociation constant (K_d) in the nanomolar range indicated a strong imprinted interaction existing between the electrodeposited sol-gel-imprinted film and the template cytidine.     

多壁碳纳米管负载氢氧化铁纳米胶粒修饰玻碳电极固相微萃取及电化学检测三氯生

采用多壁碳纳米管负载氢氧化铁纳米胶粒修饰的玻碳电极对三氯生进行固相微萃取富集,其萃取过程符合一级动力学方程和Temkin吸附等温方程。循环伏安法表明三氯生在0.558 V处有一不可逆的氧化峰,pH值与氧化峰电位呈良好的线性关系,表明三氯生的氧化过程为1个电子伴随着1个质子的反应。氧化峰电流随扫速增加而线性增加,为吸附控制反应,氧化峰电流与三氯生浓度的对数在3.333×10~(-6)~3.333×10~(-4)mol/L范围内呈线性关系,检出限达3.333×10~(-6)mol/L。该方法的重现性及选择性好,已用于洗手液中三氯生的检测。以MOPAC2012软件提供的PM7半经验分子轨道方法,在设计的三氯生与氢氧化铁纳米胶粒形成的络合物分子簇模型上进行半经验分子轨道计算,热力学及前线轨道相关系数的计算结果表明:形成的三氯生络合物的ΔG0,证明形成了稳定的三氯生络合物;且三氯生络合物形成过程中发生了电子转移。     

A Study on a Partially Immersed Gold Electrode Using an Electrochemical Quartz Crystal Impedance System

Simultaneous and fast measurement of the piezoelectric quartz crystal (PQC) impedanceduring electrochemical pertUrbations, i.e., the electrochemical quartz crystal impedancesystem (EQCIS) called by us, characterizes the PQC resonance better by providingmultidimensional in sl'tu piezoelectric information than the conventional electrochemicalquartz crystal microbalance (EQCM)'-'. The PQC impedance has been analyzed basedon the Butterworth-Van Dyke (BVD) equivalent electrical circuit com…     

Preparation of carbon-aerogel polypyrrole composite for desalination by hybrid capacitive desalination method

Capacitive Deionization (CDI) is an emerging technology with great potential applications. Most researchers view it as a viable water treatment alternative to reverse osmosis. This research reports the preparation and application of a carbon aerogel polypyrrole (CA-PPy) composite for the desalination of NaCl solution by the hybrid CDI method. The carbon aerogel (CA) was prepared from a Resorcinol / Formaldehyde precursor by the sol–gel method. The aerogel obtained from the sol–gel was then pyrolysed in a tube furnace to form CA. Polypyrrole (PPy) was prepared by the Oxidative chemical polymerisation of pyrrole, ferric chloride hexahydrate (oxidant), and sodium dodecyl sulfate (dopant). A composite of CA and PPy was then prepared and used to modify carbon electrodes. The CA-PPy composite was characterised to verify its composition, morphology, thermal properties, and functional groups. The electrochemical properties of the material were determined by Cyclic voltammetry (CV) and Electrochemical impedance spectroscopy (EIS) tests. The electrochemical tests were done using a GAMRY potentiostat electrochemical workstation, a 1.0 M KCl was used as the electrolyte, and the applied potential window was (-0.2 to + 0.6) V for the CV test. The EIS test was done with the same concentration of KCl electrolyte at an applied potential of 0.22 V and at a frequency range of (0.1 – 100, 000) Hz. The optimal specific capacitance of the CA is 115F/g, and that of the composite is 360.1F/g, they were both obtained at a scan rate of 5 mV/s. The CDI desalination study of the CA-PPy composite showed a salt adsorption capacity (SAC) of 10.10 mg/g (300 mg/L NaCl solution) – 15.7 mg/g (800 mg/L NaCl solution) at 1.2 V applied voltage. The salt recovery efficiency of the electrode material in the 300 mg/L solution is 27 %, in the 500 mg/L solution, it is 20.12 %, and in the 800 mg/L solution, it is 15.41 %. The electrode material also showed good electrochemical stability after nine cycles of ion adsorption/desorption study.     

电化学石英晶体阻抗系统研究金电极上Fe(CN)_6~(3-)/Fe(CN)_6~(4-)电化学过程

电化学过程的石英晶体阻抗分析法已用于现场获取电活性聚合物粘弹性等信息［１,２］．本文联用ＨＰ４３９５Ａ阻抗／网络／频谱分析仪和ＥＧ＆ＧＭ２８３恒电位仪开发出电化学石英晶体阻抗系统（ＥｌｅｃｔｒｏｃｈｅｍｉｃａｌＱｕａｒｔｚＣｒｙｓｔａｌＩｍｐｅｄａｎ...