In situ monitoring of gold-surface adsorption and acidic denaturation of human serum albumin by an isolation-capacitance-adopted electrochemical quartz crystal impedance system

Combined measurements of piezoelectric quartz crystal impedance (PQCI) and electrochemical impedance spectrum (EIS) using a suitable isolation capacitance is reported for the first time to monitor in situ adsorption and acidic denaturation of human serum albumin (HSA) on gold electrodes in Britton-Robinson (B-R) buffers. This method provides simultaneously mutual-interference-free and accurate parameters of EIS and PQCI. Effects of surface thiol-modification, electrode-potential and solution pH on HSA adsorption were examined and discussed. Comparative experiments of HSA adsorption in a B-R buffer of pH 6.42 on bare, cysteine- and 1-dodecanethiol-modified gold electrodes revealed that HSA adsorption is more significant on a hydrophobic (1-dodecanethiol-modified) surface. Insignificant electrode-potential effect implied minor electrostatic effects on HSA adsorption. The adsorption amount of HSA at pH 3.28 was found to be notably greater than those at pH 4.84 and 6.42. To characterize HSA adsorption, electrode standard rate constants (k_s) of the Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ couple were measured before and after HSA adsorption. The k_s-pH curves on an HSA-modified Au electrode revealed that k_s increased abruptly with the decrease of solution pH below pH ∼4. Moreover, pH-dependent responses of the resonant frequency, the motional resistance, the double-layer capacitance, the capacitance of adsorbed HSA layer and the peak absorbance of HSA solutions at 278 nm all exhibited an inflexion change at pH ∼4, and these findings have been explained on the basis of acidic denaturation of HSA and electrical charges carried by HSA molecules.     

Impedance Characterization of Adsorption Process of Calmodulin on Au Substrate and its Combination with Ca~(2+)

Recently, the adsorption behavior of protein on solid substrate has attracted much attention for the reason that adsorption on a substrate is the first key step for other further electrochemical investigation1. Meanwhile the free adsorption could provide a relative well-ordered structure, with which some fundamental study could be carried out conveniently2. As we know, the electrochemical impedance spectroscopy (EIS) method has become one of the powerful techniques to detect the change of i…     

A Study on Adsorption of Electrogenerated Cystine Precipitate onto An Electrode using Electrochemical Quartz Crystal Impedance System

Insiluquartzcrystalimpedance(QCI)measurementduringelectrochemicalperturbationshasfoundwideapplicationsininvestigatingmetalandpolymerdepositionetc'-',asitprovidesmultidimensionalinsitupiezoelectricinformation.QCIanalysishasbeenbasedontheButterworth-VanDyke(BVD)equivalentelectricalcircuitcomposedofamotionalarmandastaticarminparallel.Themotionalarmcontainsthreeequivalentcircuitelementsinseries,namely,themotionalresistanceRI,themotionalinductanceL,andthemotionalcapacitanceC,,whilethestaticar…     

Electrochemical evaluation of lectin-sugar interaction on gold electrode modified with colloidal gold and polyvinyl butyral

In this work, ConA and CramoLL lectins were immobilized on gold nanoparticles (AuNp) with polyvinyl butyral (PVB), and adsorbed on the surface of gold (Au) electrodes. Electrochemical impedance spectroscopy (EIS), in the frequency range from 100mHz to 100KHz, and cyclic voltammetry (CV), from -0.2 to 0.7V, were performed on these electrodes, in phosphate buffer (PBS) solution containing 10mM K(3)[Fe(CN)(6)]/K(4)[Fe(CN)(6)] (1:1) mixture as a redox probe. EIS and CV measurements showed that redox probe reactions on the modified Au electrodes were partially blocked due to the adsorption of AuNp-ConA-PVB and AuNp-CramoLL-PVB. SEM images showed the presence of aggregates of AuNp-ConA on PVB spherules in a tridimensional structure on the surface of the Au electrode. Bovine serum albumin (BSA) was adsorbed on the AuNp-Lectin-PVB modified electrode in order to block the remaining free gold sites. Both EIS and CV techniques yielded results that confirm positive responses of the lectins to ovalbumin agglutination. These results indicate an improvement of the sensitivity for detection of sugars that can be applicable to construction of a biosensor sensitive to glycoproteins in solution.     

Electrochemical Study of Schiff Bases by Means of Self‐Assembled Monolayers

In this paper, Schiffbases were investigated using cyclic voltammetry (CV) and impedance electrochemical spectroscopy (EIS) techniques by means of self‐assembled monolayers for the first time, where a 0.1 M KCl solution and the redox couple of Fe(CN)₆^3?/Fe(CN)₆^4?were used as the electrolyte and probing‐pin, respectively. The monolayers formed by the employed Schiff base were proved to be relatively stable, and its electrochemical response in the studied system with different pH values was also de scribed clearly with CV and EIS plots. The results show that the monolayer of Schiff bases could exist in the solution with pH value from 2 to 10. In the EIS measurement in the concentration range from 10^?5 M to 5× 10^?4 M, a nearly linear relation ship between the charge transfer resistance (R_ct) and the logarithm concentration of Cu²+was observed, suggesting that Cu²+ could be titrated with the EIS method quasi‐quantitatively. The phenomenon agreed with the former report very well. Using the self‐assembled monolayers to study Schiff bases with the electrochemical method is the major contribution of our work.     

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.     

硫醇－磷脂混合双层膜的电化学性质及其与蜂毒素的相互 作用研究

报道了硫醇－磷脂混合双层膜的循环伏安和电化学交流阻抗行为研究,并用电化学方法考察了蜂毒素与其相互作用,实验中通过冷冻表面沾有磷脂溶液的硫醇单层膜制备混合双层膜,研究表明双层膜在电极表面形成致密的绝缘层,阻碍了电极表面的电子传递,在双层膜体系上引入的蜂毒素可在膜表面上形成孔洞,破坏膜的绝缘性,降低膜电阻,增加膜电容,使带负电的探针Fe(CN)6^3-的氧化还原反应速度加快。     

Hexacyanoferrate as the Electrochemical Probe for 2-Mercaptobenzothiazole Modified Gold Electrode

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硫醇在金电极上的SA单分子层膜的电化学研究

金基底上的硫醇自组装单分子层膜(Self-asembledmonolayers,SAMs)具有良好的稳定性和有序性,因此在基础研究及应用技术等领域都受到了广泛的重视^[1].通过电化学方法测定自组装膜对溶液中电活性物质的异向电子转移的阻碍作用.     

Characterization of BSA-fouling of ion-exchange membrane systems using a subtraction technique for lumped data

Electrical impedance spectroscopy (EIS) techniques were used to gain insight into BSA fouling of the Neosepta CMX and AMX ion-exchange membranes (IEMs). EIS characterizations were made at concentrations above 0.1 M KCl because the conductance of the IEMs was higher than that of bulk solutions of concentration below 0.1 M KCl. Spectra, expressed in terms of dispersions of the conductance and capacitance with frequency, provided an enhanced indication of IEM fouling during separation processes. Bulk conductance measurements of the solution alone, membrane immersed in solution and fouled membrane immersed in solution showed good agreement with general theoretical predictions. Strong dispersions in capacitance were observed below 1 kHz for each of these configurations. Differences in the dispersions arising from fouling were identified by subtracting the impedance of the solution from those of unfouled and fouled IEMs in solution. The conductance and capacitance dispersions of fouled IEMs decreased with the accumulation of the BSA fouling layer on the surface.     

Insights into the electro-oxidation of hydrazine at single-walled carbon-nanotube-modified edge-plane pyrolytic graphite electrodes electro-decorated with metal and metal oxide films

Electrochemistry of edge-plane pyrolytic graphite electrodes (EPPGEs) modified with Aldrich single-walled carbon nanotubes (SWCNTs) electro-decorated with metal (Ni, Fe and Co) and their oxides have been studied. The morphology and identity of the metallic dispersions were examined by scanning electron microscopy and energy-dispersive spectroscopy. We show that SWCNTs serve as efficient conducting carbon material for electronic communication between metal films and the underlying carbon electrode. By using cyclic voltammetry and electrochemical impedance spectroscopy (EIS) techniques, it is proved that both EPPGE-SWCNT-Ni and EPPGE-SWCNT-Fe exhibit comparable electrochemical response in buffered aqueous solution (pH 7.0) and towards electro-oxidation of hydrazine in Na₂SO₄ solution. The impedance spectra of these SWCNT-metal hybrids were complicated and follow electrical equivalent circuit model typical of adsorption-controlled charge transfer kinetics. Hydrazine impedance spectra exhibited inductive loop, characteristic of Faradaic current being governed by the occupation of an intermediate state. On the other hand, the EIS data obtained in a simple redox probe, [Fe(CN)₆]³⁻/[Fe(CN)₆]⁴⁻, showed that EPPGE-SWCNT and EPPGE-SWCNT-Ni followed electrical equivalent circuit models typical of partial charge transfer or adsorption-controlled kinetics with some resemblance to the behaviour of electrolyte–insulator–semiconductor sensors.     

Fabrication of electroactive layer-by-layer films of myoglobin with gold nanoparticles of different sizes

Alternate adsorption of oppositely charged myoglobin (Mb) and gold nanoparticles with different sizes were used to assemble {Au/Mb}n layer-by-layer films on solid surfaces by electrostatic interaction between them. The direct electrochemistry of Mb was realized in {Au/Mb}n films at pyrolytic graphite (PG) electrodes, showing a pair of well-defined, nearly reversible cyclic voltammetry (CV) peaks for the Mb heme FeIII/FeII redox couple. Quartz crystal microbalance (QCM), electrochemical impedance spectroscopy (EIS), and CV were used to monitor or confirm the growth of the films. Compared with other Mb layer-by-layer films with nonconductive nanoparticles or polyions, {Au/Mb}n films showed much improved properties, such as smaller electron-transfer resistance (Rct) measured by EIS with Fe(CN)3-/4- redox probe, higher maximum surface concentration of electroactive Mb (Gamma*max), and better electrocatalytic activity toward reduction of O2 and H2O2, mainly because of the good conductivity of Au nanoparticles. Because of the high biocompatibility of Au nanoparticles, adsorbed Mb in the films retained its near native structure and biocatalytic activity. The size effect of Au nanoparticles on the electrochemical and electrocatalytic activity of Mb in {Au/Mb}n films was investigated, demonstrating that the {Au/Mb}n films assembled with smaller-sized Au nanoparticles have smaller Rct, higher Gamma*max, and better biocatalytic reactivity than those with larger size.     

膜电阻对自组装膜修饰电极电化学行为的影响

应用循环伏安和交流阻抗技术研究了 16烷基硫醇自组装膜修饰的金电极在Fe(CN) 63 - /Fe(CN) 64 - 溶液中的电化学行为 .无“针孔”缺陷的自组装膜对溶液与基底间的界面电子转移具有强烈的阻碍作用 ,当过电位较大时 ,In(I/ η)对 η1/2 之间具有良好的线性关系 .通过对Au/SAM /Hg模拟体系的电流———电压曲线进行测定 ,得到了自组装膜膜电阻的特征 .指出由于膜电阻的存在 ,自组装膜修饰电极在Fe(CN) 63 - /Fe(CN) 64 - 溶液中的行为实质上反映了膜自身的电阻特征     

Physical adsorption of protamine for heparin assay using a quartz crystal microbalance and electrochemical impedance spectroscopy

This study attempted to determine absolute heparin concentration in phosphate buffer solution (PBS, pH 7.4) by using quartz crystal microbalance (QCM) as an affinity biosensor. Electrochemical impedance spectroscopy (EIS) was also used to investigate immobilization of protamine and heparin assay. In addition, the effectiveness of physical adsorption in immobilizing protamine was confirmed by examining the preparation conditions, including the incubation time and protamine concentration. It induced maximum decrease (ca. −100 Hz) in oscillating frequency of QCM by applying 20 mg/ml protamine and 20 min for incubation in PBS. Heparin adsorption onto protamine-modified electrode in PBS revealed an exponential-like binding curve and long duration for reaching the steady state in frequency response of QCM. Moreover, two linear calibration curves were obtained judging from the initial slope (df/dt) and the frequency change (Δf) of QCM obtained after a binding interval (600 s) for heparin concentrations from 0 to 3.0 and 7.0 U/ml, respectively. In EIS analysis, calibration curves with linear concentration range of 0-3.0 U/ml were obtained for heparin in PBS when ferrocyanide was used as an electroactive marker.     

电催化界面和反应的电化学阻抗谱研究：经典永不褪色

本文章综述了电催化领域电化学阻抗谱（EIS）的相关研究. 首先概述了从二十世纪初到现在这一专业领域的发展历史. 然后介绍了电催化阻抗理论的几个里程碑. 其中,着重介绍了目前分析电催化EIS数据的主流模型——Dolin-Ershler模型. 之后,具体讨论了铂金单晶的双电层电容,特别是围绕这一基础课题的实验和理论上的挑战. 我们质疑采用Dolin-Ershler模型获取稀溶液中双电层电容的合理性. 因为在稀溶液中,双电层效应使得双电层电容具有频散特性,因而双电层电容的低频部分在分析过程中可能被遗失了. 未来,我们期待看到新的实验去证明或反驳一个最近的理论预测,即铂电极在氧化物生成电位区域中具有非单调表面电荷关系和负双电层电容.     

溶胶凝胶法固定抗体制备黄曲霉毒素免疫传感器

利用溶胶凝胶法,将正硅酸乙酯在HCl存在下水解形成的硅溶胶和黄曲霉毒素B1抗体的混合液涂于玻碳电极表面,制备非标记型电化学阻抗免疫传感器。以[Fe(CN)6]3-/4-的磷酸盐缓冲溶液为测试底液,分别研究传感器的循环伏安和交流阻抗行为。实验表明,电极因免疫反应所形成的复合物阻碍了[Fe(CN)6]3-/4-在电极表面的扩散,其氧化还原峰电流明显减小,电子转移阻抗随黄曲霉毒素浓度增加而线性增大。当介质pH=6.5和孵育时间为20 min时,免疫前后传感器的电子转移阻抗变化值最大。在此最佳条件下,传感器电子转移阻抗对黄曲霉毒素响应的线性范围为1.0～10μg/L;检出限为0.1μg/L(S/N=3)。此方法具有高的灵敏度和稳定性,可应用于食品中黄曲霉毒素的测定。     

Investigation of Ig.G adsorption and the effect on electrochemical responses at titanium dioxide electrode

The adsorption of Immunoglobulin G on a titanium dioxide (TiO(2)) electrode surface was investigated using (125)I radiolabeling and electrochemical impedance spectroscopy (EIS). (125)I radiolabeling was used to determine the extent of protein adsorption, while EIS was used to ascertain the effect of the adsorbed protein layer on the electrode double layer capacitance and electron transfer between the TiO(2) electrode and the electrolyte. The adsorbed amounts of Ig.G agreed well with previous results and showed approximately monolayer coverage. The amount of adsorbed protein increased when a positive potential was applied to the electrode, while the application of a negative potential resulted in a decrease. Exposure to solutions of Ig.G resulted in a decrease of the double layer capacitance (C) and an increase in the charge-transfer resistance (R(2)) at the electrode solution interface. As more Ig.G adsorbed onto the electrode surface, the extent of C and R(2) variation increased. These capacitance and charge-transfer resistance variations were attributed to the formation of a proteinaceous layer on the electrode surface during exposure.     

Electrochemical behavior of tungsten-containing nanocomposite with siloxane matrix

Electrochemical properties of a thin-film nanocomposite “silicon-carbon matrix-tungsten carbide” deposited onto pyroceramics (“sitall”) substrate are studied by potentiodynamic curves and electrochemical impedance spectroscopy. Transfer coefficients in model redox system [Fe(CN)₆]^3?/4? are measured. With the decreasing of the films’ electrical resistance, their experiment behavior gradually changed from that of “poor conductor” till nearly metal-like one. In particular, the electrode differential capacitance increases, which is explained by the increase in the number of conducting metal-containing clusters in the film bulk and at the film/electrolyte solution interface. Some specific features of the complex-plane plots of impedance spectra are tentatively explained by the adsorption at the nanocomposite surface elements.     

Adsorption behavior of metal ions onto a bovine serum albumin (BSA) membrane monitored by means of an electrode-separated piezoelectric quartz crystal.

The interaction between metal ions and bovine serum albumin (BSA) was studied by using a piezoelectric quartz crystal (PQC) arranged in the electrode-separated configuration. A silanized surface of the PQC was coated with a BSA membrane via a coupling reaction with glutaraldehyde. The frequency shifts obtained from PQC coated with a BSA membrane suggested that various kinds of metal ions could be adsorbed onto the BSA membrane from aqueous solutions containing a low concentration of metal ions (2 or 10 micromol dm(-3)), only when the BSA was denatured with an alkaline solution. Anionic species of Pt(IV) and Au(III) were adsorbed onto the denatured BSA membrane from an acetic acid solution at pH 2.2, and cationic species of Cd(II), Zn(II), Co(II), Ni(II), Cu(II), and Ag(I), and cations, such as Ca2+, Ba2+, and Mg2+, were adsorbed from ammonia buffer at pH 9.5, whereas Al(III), Cr(III), Fe(III), Hg(II), and Pb(II) were hardly adsorbed. The adsorption mechanisms of these metal ions are discussed, based on the electrostatic interaction between the metal ions and the denatured BSA membrane, and complex formation between the metal ions and amino acid residues of the denatured BSA. Further, the PQC coated with a denatured BSA membrane was applied to the determination of Pt and Cd, using large frequency shifts for Pt(IV) and Cd(II).     

Preparation and characterization of polystyrene/Ag core-shell microspheres--a bio-inspired poly(dopamine) approach

In this work, we have systematically investigated the formation and characterization of Self-assembled Monolayer (SAM) films of several silanes on indium tin oxide (ITO) surfaces. Silane molecules having different domains namely substrate binding domain (siloxanes), electron transport region (aliphatic and aromatic spacer) and terminal functional groups (-SH, -CH(3) groups) are employed for the study in order to tune the electron transfer (ET) behaviour across SAM modified electrode-electrolyte interface. Structural characterization of these monolayer films is carried out using X-ray photoelectron spectroscopy (XPS) studies. Wettability (hydrophilic and hydrophobic nature) of such modified electrodes is evaluated using contact angle measurements. ET behaviour of these modified electrodes is investigated by electrochemical techniques namely cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) using K(4)Fe(II)(CN)(6)|K(3)Fe(III)(CN)(6) redox couple as a probe. Disappearance of redox peaks in the CV measurements and formation of semicircle having a higher charge transfer resistance (R(ct)) values during EIS studies suggest that the resultant monolayer films are compact, highly ordered with very low defects and posses good blocking property with less pinholes. The heterogeneous ET rate constant (k) values are determined from EIS by fitting them to an appropriate equivalent circuit model. Based on our results, we comment on tuning the ET behaviour across the interface by a proper choice of spacer region.