Use of electrochemical techniques to characterize methamidophos and humic acid specifically adsorbed onto Pt and PtO films

Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were employed to study methamidophos (MAP) and humic acid (HM) specifically adsorbed onto Pt and PtO films in pH-7.0 universal buffer. The approach was found to be sufficiently selective for use in studies involving adsorption of species in environmental systems (e.g., soil minerals), typically evaluated by batch experiments and high performance liquid chromatography (HPLC) or gas chromatography (GC). The proposed method allowed quantification of active hydrogen adsorption sites blocked by HM, both when this compound is adsorbed alone or co-adsorbed with MAP. At higher amounts of MAP in the adsorption solution, the compound was co-adsorbed more effectively than HM (kept at constant concentration). In the case of sequential specific adsorption, the first compound adsorbed typically predominates over the second. EIS was more effective for determining the number of blocked active sites on Pt than CV, which was superior for PtO films.     

Cyclic voltammetry and impedance studies of electrodeposited polypyrrole nanoparticles doped with 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt

Electrochemical synthesis of polypyrrole (PPY), doped with 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt (AMPSNa), was carried out using chronoamperometric technique. Cyclic voltammetry measurements showed that the electroactivity of PPY films, doped with AMPSNa, increases with the film thickness. Scanning electron microscopy photographs revealed that the PPY particles are in the nano-scale range and that their size depends on the potential at which the PPY has formed. Electrochemical impedance spectroscopy (EIS), in the potential range of + 1.0 and − 1.0 V, revealed in the PPY film charge transfer domination with a semicircle at high frequencies, and anion diffusion dominance at low frequencies. EIS also showed that the charge transfer resistance of PPY film at − 1.0 V is lower than what is expected and that on increasing the thickness of the PPY films, the overall impedance decreases. The proposed equivalent circuit model, based on the double layer capacity and the Warburg impedance, was replaced by two constant-phase elements to fit the experimental work of this study. The values of the fractional exponent of the first constant phase element at approximately 0.5 indicate that the processes have a diffusion-limited nature.     

Electrochemical impedance immunosensor for the detection of cardiac biomarker Myogobin (Mb) in aqueous solution

A label-free, electrochemical impedance immunosensor based on surface modified thin flat gold wire electrode is reported for the quantitative detection of cardiac biomarker Myoglobin in aqueous solution. The protein antibody, ab-Mb, was covalently immobilized through a self assembled monolayer of 11-mercaptoundecanoic acid (MUA) and 3-mercapto propionic acid (MPA) via carbodiimide coupling reaction using N-(3-dimethylaminopropyl)-N′-ethyl carbodiimide hydrochloride (EDC) and N-Hydroxy Succinamide (NHS). The immunosensor (ab-Mb/MUA-MPA/Au) was characterized by electrochemical techniques. The electrochemical performance of the immunosensor was studied by electrochemical impedance spectroscopy. The immunosensor showed an increased electrontransfer resistance on coupling with biomarker protein antigen, ag-Mb, in the presence of a redox probe [Fe (CN)₆]^3−/4−. The modified Au electrode immunosensor exhibits an electrochemical impedance response to antigen, ag-Mb concentrations in a linear range from 10 ng to 650 ng mL⁻¹ with a lowest detection limit of 5.2 ng mL⁻¹.     

DNA biosensor by self-assembly of carbon nanotubes and DNA to detect riboflavin

The fabrication of biosensors via self-assembly of single-walled carbon nanotubes (SWNTs) and DNA on a platinum electrode was presented in this paper. The carboxylic SWNTs were assembled on an amine-modified platinum electrode surface and followed by the assembly of NH₂-DNA with the carboxyl-amine coupling. The decorated surface was characterized by Field Emission Electron Microscopy (FEG-SEM) and electrochemical experiments, which showed that the reaction of DNA–SWNTs biosensor was quasi-reversible. The mechanism of DNA and riboflavin (VB₂) was studied by cyclic voltammetry and UV–Vis spectroscopy. The fabricated SWNTs-reinforced biosensor exhibits high sensitivity and low detection limit for the tested VB₂ compared to the reported methods.     

Intramolecular synergistic effect of glutamic acid, cysteine and glycine against copper corrosion in hydrochloric acid solution

The corrosion protection of copper by glutamic acid, cysteine, glycine and their derivative (glutathione) in 0.5 M hydrochloric acid solution has been studied by the electrochemical impedance spectroscopy and cyclic voltammetry. The inhibition efficiency of the organic inhibitors on copper corrosion increases in the order: glutathione > cysteine > cysteine + glutamic acid + glycine > glutamic acid > glycine. Maximum inhibition efficiency for cysteine reaches about 92.9% at 15 mM concentration level. The glutathione can give 96.4% inhibition efficiency at a concentration of 10 mM. The molecular structure parameters were obtained by PM3 (Parametric Method 3) semi-empirical calculation. The intramolecular synergistic effect of glutamic acid, cysteine and glycine moieties in glutathione is attributed to the lower energy of the lowest unoccupied molecular orbital (E_LUMO) level and to the excess hetero-atom adsorption centers and the bigger coverage on the copper surface.     

Reactivity of Nanostructured MnO2 in Alkaline Medium Studied with a Microcavity Electrode: Effect of Oxidizing Agent

The synthesis of MnO2 powders by hydrothermal method with different oxidizing agents has been successfully achieved. The characterizations by scanning electron microscopy, energy-dispersive X-ray analyses, transmission electron microscopy, and X-ray diffraction techniques confirm the synthesis of nanostructured γ-MnO2 powders. The electrochemical reactivity of these powders in 1 mol/l KOH is investigated by cyclic voltammetry and electrochemical impedance spectroscopy (EIS) by using microcavity electrode. The results reveal that the MnO2 synthesized with Na2S2O8 shows the highest electrochemical reactivity in the test medium. This is due both to its large expanded surface area and its crystallographic variety γ-MnO2 formed in the matrix of ramsdellite, which is largely used as cathodic material for primary batteries. However, the presence of pyrolusite in the structure of γ-MnO2 synthesized with (NH4)2S2O8 decreases its electrochemical reactivity due to its narrow 1×1 size tunnel, which hinders the protons insertion.     

Protection of reinforcement steel corrosion by phenyl phosphonic acid pre-treatment PART I: Tests in solutions simulating the electrolyte in the pores of fresh concrete

The carbon steel electrodes were first treated by immersion in 0.1 M phenyl phosphonic acid (C₆H₅P(O)(OH)₂, PPA) solution during 24 or 72 h, then they were transferred into the corrosion test solution representing interstice pore electrolyte polluted by seawater: (sat. Ca(OH)₂ + 0.5 M NaCl) to evaluate the protective effectiveness of the pre-treatment. The investigation was performed essentially by polarisation curves and electrochemical impedance measurements with rotating disc electrode. Very high protective effect was observed with steel pre-treated during 72 h with stationary electrode. From polarisation and electrochemical impedance spectroscopy experiments, the protective efficiency was found to be in the 90–99% range for 72 h pre-treatment. This protective property remains effective even one month immersion. EDS analysis showed the presence of the phosphorus on the steel surface, probably due to the presence of iron-PPA complex.     

Surface plasmon resonance and impedance spectroscopy on gold electrode for biosensor application

This paper describes new-label free immunoassays for the detection of atrazine using optical Surface Plasmon Resonance (SPR) and Electrochemical Impedance Spectroscopy (EIS) by employing gold functionalised with self-assembled mixed monolayer. The mixed monolayer, formed by 16-mercaptohexadecanoic acid (MHDA) and biotinyl–PE, is used as the basic layer in the fabrication of the immunoprobe. The interfacial interaction of a biotinyl–Fab fragment K47 antibody with the mixed monolayer is based on a biotin–avidin system using the neutravidin molecule. Thus, in this study the multilayer engineering is mentored by SPR and EIS methods. In addition, the specificity and sensitivity of this self-assembled multilayer system to the presence of atrazine are investigated. The limit detection of Atrazine obtained with EIS technique is equal to 20 ng/ml and with SPR technique is equal to 50 ng/ml.     

Surface modification of indium tin oxide anodes by self-assembly monolayers: Effects on interfacial morphology and charge injection in organic light-emitting diodes

Three silane derivatives including dodecyltrichlorosilane (DDTS), phenyltriethoxysilane (PTES) and 3-aminopropyl-methyl-diethoxysilane (APMDS) were used to modify the indium tin oxide (ITO) surfaces. The effects of various terminal groups of the self-assembled monolayers (SAMs) on the growth behavior and interfacial morphologies of N,N′-di(naphthalene-1-yl)-N,N′-diphenylbenzidine (NPB) film deposited on the SAM-modified ITO were studied, as well as their effects on the performance of organic light-emitting diodes (OLED) devices. The results show that the growth behavior of NPB film over-deposited on the SAM-modified ITO is mainly determined by the wettability of the surface. The covering ability and thermal stability of NPB film on the SAM-modified ITO decrease in the order: bare ITO > ITO/PTES > ITO/APMDS > ITO/DDTS. However, the covering characteristic of NPB films on these substrates did not show direct relation to the transport of carriers across the anode/NPB interface as evaluated from the cyclic voltammogram and OLED performance. The turn-on voltages for these SMA-modified OLED devices increase in the order: ITO/PTES < ITO/DDTS ≤ bare ITO < ITO/APMDS. The enhancing effect of PTES on the hole injection is ascribed to the similar structure of PTES to NPB. On the contrary, the inhibition effect of APMDS is caused from the interaction of the lone-pair electrons of amine group to the transport carriers. Since these devices are known to be hole dominant, the luminance efficiency increase in a similar order as that for the turn-on voltage: ITO/PTES < ITO/DDTS ≤ bare ITO < ITO/APMDS.     

Synthesis and electrochemical characterization of myoglobin-antibody protein immobilized self-assembled gold nanoparticles on ITO-glass plate

We report a protein immobilized self-assembled monolayer (SAM) of gold nanoparticles (GNPs) on indium-tin-oxide (ITO) coated glass plate. The protein-antibody, Mb-Ab, was covalently immobilized over the self-assembly of GNPs through a mixed SAM of 11-mercapto undecanoic acid (MUA) and 3-mercapto propionic acid (MPA) via carbodiimide coupling reaction using N-(3-dimethylaminopropyl)-N′-ethyl carbodiimide (EDC) and N-hydroxy succinimide (NHS). The whole assembly was constructed on 0.25 cm² area of ITO-glass plate (Mb-Ab/MUA-MPA/GNPs/APTES/ITO-glass) and an impedimetric study was carried out for its application in myoglobin detection. This prototype assembly was characterized by scanning electron microscopy, atomic force microscopy and electrochemical techniques. The modified electrode showed an increased electron-transfer resistance on coupling with protein antigen, Mb-Ag, in the presence of a redox probe [Fe(CN)₆]^3−/4−. Its exhibits an electrochemical impedance response to protein myoglobin-antigen, Mb-Ag, concentration in a linear range from 0.01 μg to 1.65 μg mL⁻¹ with a lowest detection limit of 1.4 ng mL⁻¹.     

Electrosynthesis and analysis of the electrochemical properties of a composite material: Polyaniline + titanium oxide

The analysis of the electrochemical and spectroscopic properties of a composite material obtained starting from the polyaniline and TiO₂ in H₂SO₄ medium, using cyclic voltamperometry, shows three redox couples characteristic of the different oxidation and reduction states of produced polymer. The electroactivity of the composite in acid medium was better than that obtained in basic medium. The impedance spectroscopy study shows that the resistance of the film increases with the aniline concentration, but is not significantly affected by the amount of TiO₂ incorporated in polymer. The increase of pH decreases the resistance of the films and consequently increases its conductivity.     

Self-assembly of organic acid molecules on the metal oxide surface of a cupronickel alloy

Corrosion of the metal oxide surface of cupronickel (CuNi) alloys is a problem in applications such as household water pipes, industrial pipelines, and marine vessels. On other substrates, thin films have been used as barriers to corrosion. Here, the formation of self-assembled monolayers (SAMs) on the CuNi metal oxide surface has been investigated. Stable, well-ordered SAMs of octadecylphosphonic acid (ODPA) and 16-phosphonohexadecanoic acid (COOH-PA) were formed on the metal oxide surface of CuNi foils (55% Cu/45% Ni) using a solution deposition method. The ODPA modified surfaces could be used to provide a non-reactive barrier that inhibits corrosion of the CuNi metal oxide surface. Meanwhile, COOH-PA films could be used for further surface reactions such as surface initiated polymerization, in which polymer coatings are grown directly from a well-ordered film. Film-modified surfaces were characterized using diffuse reflectance infrared Fourier transform spectroscopy, contact angle analysis, and matrix assisted laser desorption ionization time of flight mass spectrometry. The ability of the films to inhibit corrosion by limiting oxidation of the CuNi surface was assessed using cyclic voltammetry.     

纳米金磁颗粒的组装法制备及其核酸分离性能

以丙烯酰胺为单体,采用原位聚合法制备了Fe3O4/聚丙烯酰胺纳米磁粒(Fe3O4/PAM);利用胺基与金的相互作用,借助自组装法在Fe3O4/PAM表面组装金胶体制备了草莓型纳米金磁颗粒(Fe3O4/PAM/Au);用TEM、VSM、UV-vis对其进行了表征,并考察了表面修饰核酸探针的金磁颗粒对核酸靶分子的分离能力。结果表明,Fe3O4/PAM/Au粒子的粒径为36～56nm,具有超顺磁性,饱和磁化强度为31.2emu/g,分散在磷酸盐缓冲液中的Fe3O4/PAM/Au完全磁分离的时间为6min。修饰核酸探针的Fe3O4/PAM/Au粒子可以借助核酸杂交作用分离核酸靶分子,分离能力为118pmol/mg。     

pH and iodide ion effect on corrosion inhibition of histidine self-assembled monolayer on copper

Self-assembled monolayer (SAM) of histidine (His) was prepared on copper surface at various pH values. The effect of KI additives on corrosion protection efficiency of His SAM was also studied. The protection abilities of these films against copper corrosion in 0.5 M HCl aqueous solution were investigated using electrochemical impedance spectroscopy and polarization techniques. The results show that the film formed on the electrode is more stable at pH = 10 than that at other pH values. When the iodide ions were added into the His self-assembly solution (pH = 10), protection efficiency was further improved. The inhibition mechanism has been discussed by quantum chemical calculations.     

Anion effects on the electrochemical regeneration of Ce(IV) in nitric acid used for etching chromium

The anion impurities such as SO4(2-), Cl(-), and Cr2O7(2-) commonly present in the spent (hazardous) Cr-etch solutions from color filter manufacturing processes may influence the solutions' regeneration by the electrooxidation of Ce(III) to Ce(IV). This study, therefore, investigated the effects of these anions on Ce(III)/Ce(IV) redox reactions at glassy carbon in HNO3. In cyclic voltammetric tests, the presence of SO4(2-) decreased the formal potential but increased the peak potential separation (Delta Ep) of Ce(III)/Ce(IV) couple, and lowered the peak current for Ce(IV) reduction whereas Cl(-) did not change the formal potential and Delta Ep, but the peaks for Cl(-) and Ce(III) oxidation partially overlapped. Cr2O7(2-) slightly lowered the peak current for Ce(III) oxidation but significantly decreased that for Ce(IV) reduction. The Tafel slope for Ce(III) oxidation was approximately 65mVdecade(-1) in the absence of anion impurities. Increasing SO4(2-), Cl(-), or Cr2O7(2-) in solution raised the Tafel slope. The Ce(III)/Ce(IV) equilibrium potential decreased with the increase of SO4(2-) or Cl(-) but was hardly influenced by Cr2O7(2-) addition. These observations from individual anion species together well explained the anions' co-effect (kinetic hindrance) on the Ce(III) oxidation in HNO3, revealing that these anions are unfavorable for the electrooxidation of Ce(III) in the spent Cr-etch solutions.     

Influence of interfaces on impedance response and breakdown of oxide-metal multilayer structures

We report on the enhancement in impedance and the break-down behavior of room temperature deposited single and multi-layer metal/oxide films of comparable thicknesses. Aluminum-alumina and chromium-chrome oxide thin film structures grown by sputtering were explored as model systems in this study. Electrochemical impedance spectroscopy measurements showed that the resistance of the structure increases with an increase in the number of metal/oxide bi-layers while the total thickness was kept constant. The resistance of the multi-layer system was over an order of magnitude higher than the single bi-layer for an equivalent total thickness for the case of thin film Al-Al₂O₃. In addition, potentiodynamic polarization measurements exhibited a consistent and reproducible improvement in the break-down potential with an increase in the number of layers. Similar results are obtained for the case of the chromium-chromium oxide bi-layer system as well. Combination of interfaces and lateral current spreading in the multi-layer structure leads to superior overall break-down resistance suggesting the concept of in-situ sacrificial layers for corrosion protection.     

Electrochemical characterization of deoxyribonucleic acid on aluminum(III)/poly(l-glutamic acid) film and its application for the detection of phosphinothricin acetyltransferase gene-specific sequence

A simple strategy of transgenic sequence-specific detection without a special amplification procedure was developed on the basis of aluminum(III)/poly(l-glutamic acid) (PLGA) film. An aluminum ion (Al(III)) thin film was assembled on the surface of PLGA via the electrostatic binding of Al(III) with carboxyl, namely Al(III)/PLGA. The immobilization of deoxyribonucleic acid (DNA) was carried out on this Al(III)/PLGA film by Al(III)-single strand DNA (ssDNA) interaction. Surface hybridization between the immobilized ssDNA and its complementary ssDNA was monitored by electrochemical impedance spectroscopy (EIS) using [Fe(CN)₆]^3−/4− as a redox probe. Under the optimal conditions, this DNA electrochemical sensor was applied to determine the specific gene sequence related to phosphinothricin acetyltransferase transgene (PAT) in the transgenic plants by label-free EIS.     

Influence of Nano-Al Concentrates on the Corrosion Resistance of Epoxy Coatings

A two-stage process was used to produce nano-composite epoxy coatings.The first step involved preparing nano-AI concentrates with high concentration and low viscosity,and the second step produced nanocomposite epoxy coatings by mixing the nano-AI concentrates and epoxy resin.Later,the coating was examined with immersion and salt spray tests.The coatings were characterized by electrochemical impedance spectroscopy(EIS),scanning electron microscopy(SEM) and X-ray photoelectron spectroscopy(XPS).The results showed that the 5%nano-AI significantly improves the corrosion resistance of the coatings.There are two effects of nano-AI on the coating.Nano-AI is corroded initially to protect the substrate from corrosion, and then the aluminum oxide and aluminum hydroxide were produced after corrosion of nano-AI,which hindered the transmission of corrosion fluid into the coatings.     

磺化酞菁钴对Ni-MH电池性能的影响

研究磺化酞菁钴作为负极添加剂时Ni-MH电池容量、放电电压、电极的循环伏安特性和循环性能,并将其与酞菁钴比较.实验数据显示,当磺化酞菁钴添加量为3%时, Ni-MH-MH电池的放电中值电压较高,以1C倍率充放电循环300次时,容量仍保持在75%以上.     

热浸55%Al-Zn-1.6%Si合金镀层在氨水中的腐蚀行为研究

利用静态浸泡试验、交流阻抗测定和金相显微分析 ,研究了常温下热浸 5 5 %Al Zn 1 .6%Si合金镀层在氨水中的腐蚀行为。结果表明 5 5 %Al Zn 1 .6%Si合金镀层耐氨水腐蚀。