Reversible electrochemical switching of polyelectrolyte brush surface energy using electroactive counterions

Polyelectrolyte brushes with electroactive counterions provide an effective platform for surfaces with electrochemically switchable wetting properties. Polycationic poly(2-(methacryloyloxy)-ethyl-trimethyl-ammonium chloride) (PMETAC) brushes with ferricyanide ions ([Fe(CN)6] 3-) were used as the electrochemically addressable surface. After a negative potential of -0.5 V was applied to the [Fe(CN)6](3-)-coordinated PMETAC brushes, the [Fe(CN)6](3-) species were reduced to [Fe(CN)6](4-), and the surface became more hydrophilic. By application of alternating negative and positive potentials, PMETAC brushes were switched reversibly between the reduced state ([Fe(CN)6]4-) and oxidized state ([Fe(CN)6]3-), resulting in reversible changes in water contact angles. The time required for a complete contact angle change can be tuned from 1 to 20 s, by changing the brush thickness and the concentration of supporting electrolyte. We present an electrochemical brush transport model that includes the electrochemical reaction at the charged electrode and describes ion transport through the brush phase covering the electrode. The model quantitatively describes the response of the contact angle (hydrophilicity) to the applied voltage as a function of background ionic strength and brush thickness, supporting the proposed mechanism of ion transport through the brush and electrochemical reaction at the electrode. A typical diffusion constant for ferricyanide in a PMETAC brush of any thickness in 5 mM KCl supporting electrolyte was found to be 2 x 10(-15) m2 s(-1), 5 to 6 orders of magnitude smaller than its bulk solution value.     

Electron-transfer studies in a lyotropic columnar hexagonal liquid crystalline medium

We have studied the electron-transfer properties of some redox systems on a gold electrode in a lyotropic hexagonal columnar liquid crystalline phase (H1 phase) using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The liquid crystalline medium consists of the nonionic surfactant Triton X-100 and water. The redox reactions that have been studied are ferrocene/ferricenium, [Fe(CN)6]3-/4-, and [Ru(NH3)6]3+/2+. We have confirmed by polarizing optical microscopy that the liquid crystalline nature of the medium is maintained even after the addition of the redox species and the supporting electrolyte. The CV studies show a significant shift in the half-peak potentials of these redox reactions in the liquid crystalline medium. From the EIS studies, we have measured the diffusion coefficients and the kinetic parameters for the redox species. These results are discussed and compared with the values obtained in the conventional solvent medium. The CV and impedance studies demonstrate that the hexagonal columnar phase provides a novel controlled environment for the study of electron-transfer reactions in biological and physiological media.     

Internal surface polarity of regenerated cellulose gel depends on the species used as coagulant

We report the development of a new selective and specific electrochemical biosensor for bacterial lipolysaccharide (LPS). An electrode interface was constructed using a l-cysteine-gold nanoparticle (AuNpCys) composite to be immobilized by electrostatic interaction in the network of a poly(vinyl chloride-vinyl acetate maleic acid) (PVM) layer on a gold bare electrode. The impedimetric biosensor is fabricated by self-assembled CramoLL lectin on the PVM-AuNpCys-modified gold electrode through electrostatic interaction. CramoLL is used as the recognition interface. AFM images showed that LPS was specifically recognized on the PVM-AuNpCys-CramoLL system surface. The measurements of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) showed that the electrochemical response of a redox probe system (K(4)[Fe(CN)(6)](4-)/K(3)[Fe(CN)(6)](3-)) were blocked, due to the procedures of modified electrode with PVM-AuNpCys-CramoLL. In the majority of the experiments the lectin retained its activity as observed through its interaction with LPS from Escherichia coli, Serratia marcescens, Salmonella enterica and Klebsiella pneumoniae. The results are expressed in terms of the charge transfer resistance and current peak anodic using the EIS and CV techniques for the development of a biosensor for contamination by endotoxins. A new type of sensor for selective discrimination of LPS types with a high sensitivity has been obtained.     

Research on electrochemical properties of nonaqueous ionic liquid microemulsions

The nonaqueous ionic liquid (IL) microemulsions composed of 1-butyl-3-methylimidazolium tetrafluoroborate, Triton X-100, and toluene were prepared and the electrochemical properties of the nonaqueous IL microemulsions were investigated in this paper. It is shown that characteristics of the nonaqueous IL microemulsions such as electrical conductivity, electrochemical window, and solubility are good, which indicate that the nonaqueous IL microemulsions can be used as electrolyte for electrochemical research. The electrochemical properties of the nonaqueous IL microemulsions were researched by cyclic voltammetry (CV) and electrochemical impedance spectroscopy methods using potassium ferricyanide as electroactive probe. It was found that the reversibility was better and the peak current densities of CV were higher for the [Fe(CN)₆]³⁻/[Fe(CN)₆]⁴⁻ electrode reaction in the nonaqueous IL microemulsions than those in IL. However, the electrochemical behavior of the probe in the nonaqueous IL microemulsions with different microenvironments (oil-in-IL, IL-in-oil, and bicontinuous) was different. The electrochemical property of the probe in the oil-in-IL microemulsion was the best, which was studied in detail.     

Fabrication and Characterization of DNA/QPVP‐Os Redox‐Active Multilayer Film

Calf thymus DNA was immobilized on functionalized glassy carbon, gold and quartz substrates, respectively, by the layer‐by‐layer (LBL) assembly method with a polycation QPVP‐Os, a quaternized poly(4‐vinylpyridine) partially complexed with osmium bis(2,2′‐bipyridine) as counterions. UV‐visible absorption and surface plasmon resonance spectroscopy (SPR) showed that the resulting film was uniform with the average thickness 3.4 nm for one bilayer. Cyclic voltammetry (CV) showed that the total surface coverage of the polycations increases as each QPVP‐Os/DNA bilayer added to the electrode surface, but the surface formal potential of Os‐centered redox reaction shifts negatively, which is mainly attributed to the intercalation of redox‐active complex to DNA chain. The electron transfer kinetics of electroactive QPVP‐Os in the multilayer film was investigated by electrochemical impedance experiment for the first time. The permeability of Fe(CN) in the solution into the multilayer film depends on the number of bilayers in the film. It is worth noting that when the multilayer film is up to 4 bilayers, the CV curves of the multilayer films display the typical characteristic of a microelectrode array. The nanoporous structure of the multilayer film was further confirmed by the surface morphology analysis using atomic force microscopy (AFM).     

Electrochemical characterization of the redox couple of Fe(III)/Fe(II) mediated by grafted polymer reference electrode (GPRE)

A grafted polymer reference electrode (GPRE) (polystyrene grafted with acrylonitrile as a monomer using gamma irradiation) was fabricated as a reference electrode using cyclic voltammetry (CV). The redox process of K₃Fe(CN)₆ during CV was studied. It was found that the redox current peaks of Fe(II)/Fe(III) in 0.1 M of KCl as supporting electrolyte is given the same oxidation–reduction current as in the Ag/AgCl reference electrode, indicating a good result of GPRE and, hence, it can be used for voltammetric analysis technique. The physical properties of GPRE include good hardness, insoluble in non-aqueous electrolytes (except dimethyl formamide and chloroform), and good stability at different solvents. In addition, the sensitivity under conditions of CV is significantly dependent on the scan rate (SR) and variation in concentration. At different SRs, redox peaks of K₃Fe(CN)₆ were observed in a reversible process: Fe(II)/Fe(III). Interestingly, the redox reaction of Fe(II)/Fe(III) solution using GCE versus GPRE remains constant even after 15 cyclings. It is therefore evident that the GPRE possesses some degree of stability. Also, the new reference electrode GPRE has improved the properties of electroanalysis of CV on the working electrode GCE in reliability with the relative standard deviation.     

Redox mediation at 11-mercaptoundecanoic acid self-assembled monolayers on gold

Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and digital simulation techniques were used to investigate quantitatively the mechanism of electron transfer (ET) through densely packed and well-ordered self-assembled monolayers (SAMs) of 11-mercaptoundecanoic acid on gold, either pristine or modified by physically adsorbed glucose oxidase (GOx). In the presence of ferrocenylmethanol (FcMeOH) as a redox mediator, ET kinetics involving either solution-phase hydrophilic redox probes such as [Fe(CN)6]3-/4- or surface-immobilized GOx is greatly accelerated: [Fe(CN)6]3-/4- undergoes diffusion-controlled ET, while the enzymatic electrochemical conversion of glucose to gluconolactone is efficiently sustained by FcMeOH. Analysis of the results, also including the digital simulation of CV and EIS data, showed the prevalence of an ET mechanism according to the so-called membrane model that comprises the permeation of the redox mediator within the SAM and the intermolecular ET to the redox probe located outside the monolayer. The analysis of the catalytic current generated at the GOx/SAM electrode in the presence of glucose and FcMeOH allowed the high surface protein coverage suggested by X-ray photoelectron spectroscopy (XPS) measurements to be confirmed.     

聚电解质中阳离子对铁氰化钾还原过程影响的原位显微红外光谱电化学

采用原位显微红外光谱电化学方法研究了聚电解质中不同阳离子（Ｌｉ＋,Ｎａ＋,Ｋ＋和ＴＢＡ＋）存在下铁氰化钾的电化学还原过程．观察到支持电解质阳离子对Ｆｅ（ＣＮ）３－／４－６振动频率的影响,探讨了还原反应机理     

Preparation,Characterization, and Electrocatalytic Properties of Cobalt Oxide and Cobalt Hexacyanoferrate Hybrid Films

Polynuclear mixed‐valent films of cobalt oxide and cobalt hexacyanoferrate (CoOCoHCF) have been deposited on electrode surfaces from a solution of Co²⁺ and Fe(CN)₆^3? ions by repetitive potential cycling method. Simultaneous cyclic voltammetry and electrochemical quartz crystal microbalance measurements demonstrate the steady growth of modified film. The effect of type of monovalent cations as well as acidity of the supporting electrolyte on film growth and redox behavior of resulting film was investigated. In pure supporting electrolyte, electrochemical responses of modified electrode resemble with that of a surface immobilized redox couple. The hybrid film electrodes showed electrocatalytic activity toward oxidation of NADH, hydrazine and hydroxylamine. The feasibility of using our modified electrodes for analytical application was also explored.     

Disposable electrochemical biosensor with multiwalled carbon nanotubes-chitosan composite layer for the detection of deep DNA damage.

A novel electrochemical DNA-based biosensor for the detection of deep DNA damage was designed employing the bionanocomposite layer of multiwalled carbon nanotubes (MWNT) in chitosan (CHIT) deposited on a screen printed carbon electrode (SPCE). The biocomponent represented by double-stranded (ds) herring sperm DNA was immobilized on this composite using layer-by-layer coverage to form a robust film. Individual and complex electrode modifiers are characterized by a differential pulse voltammetry (DPV) with the DNA redox marker [Co(phen)(3)](3+), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) with [Fe(CN)(6)](3-) as a redox probe in a phosphate buffer solution (PBS). A good correlation between the CV and EIS parameters has been found, thus confirming a strong effect of MWNT on the enhancement of the electroconductivity of the electrode surface and that of CHIT on the MWNT distribution at the electrode surface. Differences between the CV and EIS signals of the electrodes without and with DNA are used to detect deep damage to DNA, advantageously using simple working procedures in the same experiment.     

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.     

钙调素膜在不同pH值溶液中的循环伏安行为

自组装膜;钙调素膜在不同pH值溶液中的循环伏安行为     

玻碳电极上六氰亚铁酸钯膜的现场FTIR光谱电化学研究

本文报道六氰亚铁酸钯膜修饰电极在ＨＣｌ,ＫＣｌ和ＮａＣｌ溶液中的现场反射ＦＴＩＲ光谱电化学研究,结果表明该修饰膜具有内外两层结构,分别为Ｐｄ２Ｆｅ（ＣＮ）６和Ｍ２ＰｄＦｅ（ＣＮ）６,其中Ｍ为支持电解质一价阳离子．在１ｍｏｌ／ＬＮａＣｌ中,内层的氧化电位Ｅｍ＝０．８７Ｖ（ｖｓ．Ａｇ／ＡｇＣｌ）,外层为０．７７Ｖ．在１ｍｏｌ／ＬＨＣｌ或ＫＣｌ中两层的氧化还原波重叠为一个大ＣＶ波峰而难以分辨,然而现场ＦＴＩＲ光谱电化学清晰地分辨出这两种结构在所有３种溶液中ＣＮ的不同振动频率,发现Ｈ＋离子是最佳的支持电解质,能使这两种结构同时发生氧化反应     

柚皮苷分子印迹传感器的制备与应用

以邻氨基酚为单体,无电化学活性的柚皮苷为模板分子,采用循环伏安法(扫速为100mV/s)在碳电极上往复扫描30次,电聚合出具有识别柚皮苷分子功能的敏感膜。以扫描电子显微镜(SEM)、X射线全反射(XRR)及电化学方法对该印迹传感器进行表征。结果表明,印迹传感器敏感膜与非印迹膜在形貌结构和电化学特性方面有明显的不同。此传感器对柚皮苷有较好的选择性,响应快(30s),在6.0×10-5～1.4×10-4mol/L范围内呈线性关系,且重现性好(RSD=1.8%,n=5);传感器对柚皮苷的检出限为1.6×10-5mol/L。     

Electrochemical studies for the electroactivity of amine-capped aniline trimer on the anticorrosion effect of as-prepared polyimide coatings

The electroactive polyimide consisting of various content of amine-capped aniline trimers (ATs) have been successfully synthesized and characterized by Fourier-Transformation infrared and UV-visible absorption spectroscopy. The electroactivity of as-prepared polyimides was tested by electrochemical cyclic voltammetry (CV) studies. It was noticed that the as-prepared electroactive polyimide with higher content of amine-capped ATs shows higher electroactivity (i.e., larger redox current) than that of non-electroactive polyimide, leading to enhance corrosion protection efficiency on cold-rolled steel (CRS) electrodes. This enhanced corrosion protection efficiency has been explained based on a series of electrochemical measurements such as corrosion potential, polarization resistance, corrosion current and electrochemical impedance spectroscopy (EIS) studies in 5 wt-% NaCl electrolyte. This significant enhancement of corrosion protection on CRS electrodes as compared to non-electroactive polyimide might probably be attributed to the redox catalytic property of as-prepared electroactive polyimide coatings inducing the formation of passive layer of metal oxide.     

一种新型氧化还原电解液电化学电容器体系

以含有Fe3+/Fe2+离子对的H2SO4溶液为电解液, 以多孔炭做电极材料, 就Fe3+/Fe2+离子对在多孔炭纳米孔隙中的电化学行为及准电容效应进行了探讨. 循环伏安测试结果表明, Fe3+/Fe2+离子对在多孔炭电极纳米孔隙中发生了可逆的电化学反应. 恒流充放电结果发现, 加入Fe3+/Fe2+使得充放曲线出现对称的充放电平台, 有效地提高了电化学电容器(EC)的电能存储容量, 其单电极比电容最高达174 mAh•g−1, 比单纯的H2SO4电解液的比电容高109 mAh•g−1, 且有着良好的循环稳定性. 根据实验现象及结果, 探讨了Fe3+/Fe2+离子对在EC电极上的充放电机理, 并提出了一种新的概念——氧化还原电解液电化学电容器.     

Electrochemical characterization of polyelectrolyte/gold nanoparticle multilayers self-assembled on gold electrodes

Polyelectrolyte/gold nanoparticle multilayers composed of poly(l-lysine) (pLys) and mercaptosuccinic acid (MSA) stabilized gold nanoparticles (Au NPs) were built up using the electrostatic layer-by-layer self-assembly technique upon a gold electrode modified with a first layer of MSA. The assemblies were characterized using UV-vis absorption spectroscopy, cyclic and square-wave voltammetry, electrochemical impedance spectroscopy, and atomic force microscopy. Charge transport through the multilayer was studied experimentally as well as theoretically by using two different redox pairs [Fe(CN)(6)](3-/4-) and [Ru(NH(3))(6)](3+/2+). This paper reports a large sensitivity to the charge of the outermost layer for the permeability of these assemblies to the probe ions. With the former redox pair, dramatic changes in the impedance response were obtained for thin multilayers each time a new layer was deposited. In the latter case, the multilayer behaves as a conductor exhibiting a strikingly lower impedance response, the electric current being enhanced as more layers are added for Au NP terminated multilayers. These results are interpreted quite satisfactorily by means of a capillary membrane model that encompasses the wide variety of behaviors observed. It is concluded that nonlinear slow diffusion through defects (pinholes) in the multilayer is the governing mechanism for the [Fe(CN)(6)](3-/4-) species, whereas electron transfer through the Au NPs is the dominant mechanism in the case of the [Ru(NH(3))(6)](3+/2+) pair.     

十二烷基磺基甜菜碱与铂电极支撑的磷脂双层膜作用的电化学研究

以铂电极支撑的磷脂双层膜(Supported Bilayer Lipid Membrane,s-BLM)作为生物膜的模型,以Fe(CN)36-和Fe(CN)64-为探针分子,利用循环伏安法(CV)和交流阻抗谱(EIS)研究两性表面活性剂十二烷基磺基甜菜碱(Dodecyl Sulfobetaine,DSB)对s-BLM相互作用。结果显示,DSB可以嵌入到s-BLM的疏水区,容易使其表面分子的排列发生变化,产生缺陷或孔洞,探针分子Fe(CN)63-和Fe(CN)64-可以通过这些微孔接近电极,产生氧化还原响应。并且作用时间、DSB的浓度以及胆固醇的存在与否对二者的相互作用有直接影响。此外作用后的双层膜在0.1mol/LKCl溶液中能够自我修复,这表明DSB与s-BLM的相互作用是可逆的。     

Investigating Electrochemical Stability and Reliability of Gold Electrode‐electrolyte Systems to Develop Bioelectronic Nose Using Insect Olfactory Receptor

This article aims to demonstrate an electrochemically stable and reliable gold electrode‐electrolyte system to develop an insect odorant receptor (Drosophila melanogaster Or35a) based bioelectronic nose. Cyclic voltammograms (CVs) and electrochemical impedance spectroscopy (EIS) of bare gold electrodes, after modification with the self‐assembled monolayer (SAM) of 6‐mercaptohexanoic acid (MHA) and after immobilization with Or35a integrated into the lipid bilayers of liposomes were conducted in the presence of four different redox probes. Potassium ferri/ferrocyanide [Fe(CN)₆]^3?/[Fe (CN)₆]^4? and hydroquinone (H₂Q) redox probes revealed variable and irreversible signals at the time scale of our measurements, with atomic force microscopy (AFM) images and x‐ray photoelectron spectroscopy (XPS) results suggesting gold surface etching due to the presence of CN^? ions in case of [Fe(CN)₆]^3?/[Fe (CN)₆]^4?. Although the hexaammineruthenium complex showed stable electrochemical behaviour at all stages of biosensor development, changes in CV and EIS readings after each surface modifications were insignificant. PBS buffer as a non‐Faradaic medium, was found to provide reliable systems for electrochemical probing of modified gold electrodes with Or35a/liposomes in aqueous media. Using this system, we have shown that this novel biosensor can detect its known odorant E2‐hexenal selectively compared to methyl salicylate down to femtomolar concentration.     

Voltammetric Characterization of Grafted Polymer Modified with ZnO Nanoparticles on Glassy Carbon Electrode

In this study, a grafted polymer (GP) with ZnO nanoparticles (GP/ZnO NPs) was attached on the surface of glassy carbon electrode (GCE), in order to produce a new modified electrode (GP/ZnO NPs-GCE). The gamma irradiation method was used to grafted polystyrene (polymer) with acrylonitrile (monomer), while slow evaporation process was used to prepare the new modified electrode. The cyclic voltammetry (CV) of K₄[Fe(CN)₆] was used to study the electrochemical properties GP/ZnO NPs-GCE. The peak separation (ΔE_pa-c) was 500 mV between the redox peaks of Fe(II)/Fe(III) in an aqueous solution of 1 M KCl and the current ratio of redox current peaks (I_pa/I_pc) was ≈ 1 for the modified electrode. This indicated that the modified electrode has s good reversibility and conductivity, wherefore; it was applied in the voltammetric filed. It was found that the modified electrode GP/ZnO NPs-GCE have a reasonable solubility and stability at various pH medium. Additionally, the sensitivity of the electrochemical analysis by cyclic voltammetric (CV) method is extensively subjected to the pH medium and the scan rate (SR). A couple of redox current peaks of K₄[Fe(CN)₆] in KCl solution was observed with a reversible process: Fe³⁺/Fe²⁺. Finally a good diffusion coefficient of electroactive species (D) for the new modified electrode was found in this study by chronoamperometry method using Cottrell equation.