Fabrication of layer-by-layer deposited multilayer films containing DNA and its interaction with methyl green

Multilayer films were fabricated by layer-by-layer electrostatic deposition techniques between poly(diallyIdimethylammonium chloride) (PDDA) and calf thymus DNA (CT DNA) on glassy carbon and quartz substrates. Electrochemical impedance spectroscopy (EIS), Fourier transform infrared (FTIR) spectroscopy and UV-vis spectroscopy demonstrated the uniform assembly of PDDA/DNA multilayer films, and X-ray photoelectron spectroscopy confirmed the elemental composition of the films. Moreover, the interaction of DNA in PDDA/DNA films with methyl green was investigated by UV-vis spectroscopy and circular dichroism (CD). (C) 2001 Elsevier Science B.V. All rights reserved.

Studies on the room temperature conductivity of PEO-LiClO4-Al2O3 composite polymer electrolyte

A composite polymer electrolyte of Polyethylene oxide (PEO)-LiClO4 containing fine Al2O3 particles was studied by using differential scanning calorimetry, infrared spectroscopy and electrochemical impedance spectroscopy. Compared with the polymer electrolyte without Al2O3 particles, the glass transition temperature and the degree of crystallinity were decreased, and the room temperature conductivity of PEO-LiClO4-Al2O3 composite polymer electrolyte was considerably enhanced. Moreover, the equivalent circuits and the effect of dc potential on impedance spectroscopy were discussed.

Formation of a self-assembled monolayer of 2-mercapto-3-n-octylthiophene on gold

Monolayer assembly of 2-mercapto-3-n-octylthiophene (MOT) having a relatively large headgroup onto gold surface from its dilute ethanolic solutions has been investigated by electrochemistry. An electrochemical capacitance measurement on the permeability of the monolayer to aqueous ions, as compared with its alkanethiol counterpart [CH3(CH2)(9)SH (DT)] with a similar molecular length, shows that the self-assembled monolayers (SAMs) of MOT can be penetrated by aqueous ions to some extent. Furthermore, organic molecular probes, such as dopamine, can sufficiently diffuse into the monolayer because a diffusion-limited current peak is observed when the dopamine oxidation reaction takes place, showing that the monolayer is loosely packed or dominated by defects. But the results of electron transfer to aqueous redox probes (including voltammetry in Fe(CN)(6)(3-/4-) solutions and electrochemical ac impedance spectrum) confirm that the monolayer can passivate the gold electrode surface effectively for its very low ratio of pinhole defects. Moreover, a heterogeneous patching process involving addition of the surfactants into the SAMs provides a mixed or hybrid membrane that has superior passivating properties. These studies show that the MOT monolayer on the electrode can provide an excellent barrier for hydrated ionic probe penetration but cannot resist the organic species penetration effectively. The unusual properties of the SAMs are attributed to the entity of the relatively large thiophene moiety between the carbon chain and the thiol group.

Formation and characterization of heteropolyacid/polycation multilayer films on gold electrode

Ultrathin multilayer films of a polybasic lanthanide heteropoly tungstate-molybdate complex and a cationic polymer of quaternized poly(4-vinylpyridine) partially complexed with osmium bis(2,2'-bipyridine) have been fabricated on a gold electrode precoated with a cysteamine self-assembled monolayer. The multilayer films have been characterized by optical spectroscopy, small-angle X-ray diffraction, and electrochemical methods (cyclic voltammetry and electrochemical impedance). Especially, the electrochemical impedance spectroscopy is developed to monitor the layer deposition processes. It provides important information such as double-layer capacitance and charge-transfer resistance. All obtained results reveal regular film growth with each layer adsorption. (C) 2001 The Electrochemical Society.

Formation of self-assembled monolayers on gold electrodes with inclusion complexes of cyclodextrins and viologens

A novel kind of electroactive self-assembled monolayer (SAM) has been successfully prepared through the following procedure: (1) formation of inclusion complexes (denoted as CD/C8VC10SH) between N-(n-octyl)-N'-(10-mercaptodecyl)-4,4'-bipyridinium dibromide (C8VC10SH) and alpha-, beta-cyclodextrin (CD) under a mild condition; (2) spontaneous formation of SAM of CD/C8VC10SH on gold electrodes at room temperature. High-resolution H-1-NMR spectrum was used to confirm the formation of CD/C8VC10SH. Cyclic voltammetry was used to characterize the redox behavior of the resulting monolayers and chronoamperometry and electrochemical impedance spectroscopy to characterize their electron transfer kinetics. It was found that the redox sites in SAM of CD/C8VC10SH are effectively diluted, with a larger electron transfer rate constant than that of SAM of C8VC10SH.

The transfer of chloride ion across an anion exchange membrane

The transfer of chloride ions into a low resistance anion exchange membrane (AEM) was investigated by cyclic voltammetry (CV) and electrochemical impedance spectra. In all cases, concentration polarization of Cl- ions is exterior to the membrane. It controls the flux and produces the limiting currents: either steady state or transient (peak type) current. In CV experiments, when the size of the holes in the membrane was much smaller than the distance between membrane holes, the Cl- anion transfer showed steady state voltammetric behavior. Each hole in the membrane can be regarded as a microelectrode and the membrane was equivalent to a microelectrode array in this condition. When the hole in the membrane was large or the distance between membrane holes was small, the CV curve of the Cl- anion transfer across the membrane showed a peak shape, which was attributed to linear diffusion. In AC impedance measurement, the impedance spectrum of the membrane system was composed of two semicircles at low DC bias, corresponding to the bulk characteristics of the membrane and the kinetic process of ion transfer, respectively. The bulk membrane resistance increases with increasing DC bias and only one semicircle was observed at higher DC bias. The parameters related to kinetic and membrane properties were discussed.

Ionic conductivity of gel electrolyte based on polydiethylene glycol dimethacrylate and its copolymer

Gel electrolytes were prepared by thermal polymerization of diethylene glycol dimethacrylate (DIEGD) or its copolymer with methoxy polyethylene glycol monomethacrylate, molecular weight 400 (PEM(400)), at a molar ratio of 3/1 in the presence of propylene carbonate (PC) and LiClO4. Conductivity was measured by impedance spectroscopy. It was found that the conductivity data follow the Arrhenius equation in the homopolymer gel system, while the VTF equation holds true in the copolymer gel system. An increase in conductivity was observed in the copolymer gel system. However, whether in the homopolymer or in the copolymer gel system, a maximum ambient temperature conductivity was found at a salt concentration near 1.50 mol/l. Further, the activation energy values calculated from Arrhenius plots for the homopolymer gel system tended to reach a minimum value with increasing salt concentration. (C) 1996 Elsevier Science Ltd

Ionic conductivity of polymer gel electrolytes based on poly(polyethylene glycol dimethacrylate)

Gel electrolytes have been prepared by thermal polymerization of poly(polyethylene glycol dimethacrylate) (P(PEGD)) in the presence of propylene carbonate (PC) and alkali metal salts, such as LiClO4, LICF(3)SO(3) and LiBF4. The conductivity was studied by means of impedance spectroscopy, and it is found that the temperature dependence of conductivities follow a Arrhenius relationship when the molar percentage of PC is higher than 75% or LiClO4 concentration is lower than 0.9 mol/l. However, when LiCF3SO3 or LiBF4 is used instead of LiClO4 as the salt, the situation is different. For LICF(3)SO(3), the Arrhenius relationship almost holds true for all the salt concentrations studied; while for LiBF4, the Arrhenius equation hardly fits for any salt concentration. The dependence of activation energy on salt concentration is also examined, both for LiClO4 and LiCF3SO3, the values of E(a) tend to reach a minimum value with increasing salt concentration. Copyright (C) 1996 Elsevier Science Ltd.

Monitoring microbial populations of sulfate-reducing bacteria using an impedimetric immunosensor based on agglutination assay

An impedimetric immunosensor was fabricated for rapid and non-labeled detection of sulfate-reducing bacteria, Desulforibrio caledoiensis (SRB) by immobilizing lectin-Concanavalin A using an agglutination assay. The immobilization of lectin was conducted using amine coupling on the surface of a gold (Au) electrode assembled with 11-Mercaptounclecanoic acid. Electrochemical impedance spectroscopy (EIS) was used to verify the stepwise assembly of the sensor system. The work conditions of the impedimetric immunosensor, such as pH of the buffer solutions and the incubation time of lectin, were optimized. Faradic impedance spectra for charge transfer for the redox probe Fe(CN)(6)(3-/4-) were measured to determine SRB concentrations. The diameter of the Nyquist diagram that is equal to the charge-transfer resistance (RI) increased with increasing SRB concentration. A linear relationship between R-ct and SRB concentration was obtained in SRB concentration range of 1.8 to 1.8 x 10(7) cfu/ml. The variation of the SRB population during the growth process was also monitored using the impedimetric immunosensor. This approach has great potential for simple, low-cost. and time-saving monitoring of microbial populations. (C) 2009 Elsevier B.V. All rights reserved.

Characteristics of anodic coatings oxidized to different voltage on AZ91D Mg alloy by micro-arc oxidization technique

With increasing applied voltage, three types of anodic coatings, passive film, micro-spark ceramic coating and spark ceramic coating were made by micro-arc oxidization (MAO) technique on AZ91D magnesium alloy in alkali-silicate solution. The structure, composition characteristics and the electrochemical properties of coatings were also studied with SEM, XRD and EIS (electrochemical impedance spectroscopy) technique, respectively. It is found that the electrochemical properties are closely related to the structure and composition characteristics of the anodic coatings. At the same time, the characteristics of the three types of anodic coatings differ significantly, among them, the micro-spark ceramic coating, prepared in the voltage range of 170similar to220V exhibits compact, homogeneous structure and highest corrosion-resistance.

2,3,5-triphenyl-2H-tetrazolium chloride and 2,4,6-tri(2-pyridyl)-s-triazine on the corrosion of mild steel in HCl

Electrochemical measurement, quantum chemical method, and scanning electron microscopy (SEM) were performed to investigate the inhibitive effect of 2,3,5-triphenyl-2H-tetrazolium chloride (TTC) and 2,4,6-tri(2-pyridyl)-s-triazine(TPT) on the corrosion of mild steel in 1mol.L-1 HCl at room temperature. Impedance spectroscopy measurement showed that the polarization resistance increased and that double layer capacitance decreased with the increase in the inhibitive concentration, and the results of potentiodynamic polarization showed that the inhibitors suppressed both cathodic and anodic processes of steel corrosion without change in the mechanism. Higher the orbital density distribution strength of the lowest unoccupied molecular orbital, higher is the molecule dipole, and lower energy gap between the energy of the highest occupied molecular orbital and the energy of the lowest unoccupied molecular orbital resulted in higher inhibitory efficiency. The results of SEM analysis showed that the metal was protected from aggressive corrosion by the addition of TTC and TPT.

Electrochemical, quantum chemical and SEM investigation of the inhibiting effect and mechanism of ciprofloxacin, norfloxacin and ofloxacin on the corrosion for mild steel in hydrochloric acid

The inhibiting effect and mechanism of 1-cyclopropyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinoline carboxylicacid(ciprofloxacin), 1-ethyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinoline carboxylic acid (norfloxacin) and (-)-(S)-9-fluoro-2,3-dihydro-3-methyl-10-(4-methyl-1-piperazinyl)-7-oxo-7 H-pyrido(1,2,3-de)-1,4-benzoxazine-6 carboxylic acid (ofloxacin) on the corrosion of mild steel in 1 mol/L HCl have been studied using electrochemical method, quantum chemical method and SEM at 303 K. The potentiodynamic results showed that these compounds suppressed both cathodic and anodic processes of mild steel corrosion in 1 mol/L HCl. The impedance spectroscopy showed that R-p values increased, and C-dl values decreased with the rising of the working concentration. Quantum chemical calculation showed that there was a positive correlation between some inhibitors structure properties and the inhibitory efficiency. The inhibitors function through adsorption followed Langmuir isotherm, and chemisorption made more contribution to the adsorption of the inhibitors on the steel surface compared with physical adsorption. SEM analysis suggested that the metal had been protected from aggressive corrosion because of the addition of the inhibitors.

The inhibition of mild steel corrosion in 1 M hydrochloric acid solutions by triazole derivative

The title compound 1-(4,5-dihydro-3-phenylpyridine-1-yl)-2-(1H-1,2,4-triazole-1-yl)ethyl ketone (DTE) was synthesized and its inhibiting action on the corrosion of mild steel in 1 M hydrochloric acid solutions was investigated by means of weight loss, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and scanning electronic microscope (SEM). Results obtained revealed that DIE performed excellently as a corrosion inhibitor for mild steel in 1 M hydrochloric acid media and its efficiency attains more than 90.9% at 1.0 x 10(-3) M at 298 K. Polarization curves indicated that the inhibitor behave mainly as mixed-type inhibitor. EIS showed that the charge transfer controls the corrosion process in the uninhibited and inhibited solutions. Adsorption of the inhibitor on the mild steel surface followed Langmuir adsorption isotherm. And the values of the free energy of adsorption Delta G(ads) indicated that the adsorption of DTE molecule was a spontaneous process and was typical of chemisorption. (c) 2008 Elsevier B.V. All rights reserved.

Experimental and theoretical investigation of the adsorption behaviour of new triazole derivatives as inhibitors for mild steel corrosion in acid media

Three triazole derivatives (4-chloro-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (CATM), 4-methoxyl-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (MATM) and 4-fluoro-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (FATM)) have been synthesized as new inhibitors for the corrosion of mild steel in acid media. The inhibition efficiencies of these inhibitors were evaluated by means of weight loss and electrochemical techniques such as electrochemical impedance spectroscopy (EIS) and polarization curves. Then the surface morphology was studied by scanning electron microscopy (SEM). The adsorption of triazole derivatives is found to obey Langmuir adsorption isotherm, and the thermodynamic parameters were determined and discussed. The relationship between molecular structure of these compounds and their inhibition efficiency has been investigated by ab initio quantum chemical calculations. The electronic properties such as the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO) energy levels, energy gap (LUMO-HOMO), dipole moment and molecular orbital densities were computed. (c) 2007 Elsevier Ltd. All rights reserved.

Some new triazole derivatives as inhibitors for mild steel corrosion in acidic medium

Two triazole derivatives, 3,4-dichloro-acetophenone-O-1'-(1',3',4'-triazolyl)-methaneoxime (4-DTM) and 2,5-dichloro-acetophenone-O-1'-(1',3',4'-triazolyl)-methaneoxime (5-DTM) were synthesized, and the inhibition effects for mild steel in 1 M HCl solutions were investigated by weight loss measurements, electrochemical tests and scanning electronic microscopy (SEM). The weight loss measurements showed that these compounds have excellent inhibiting effect at a concentration of 1.0 x 10(-3) M. The potentiodynamic polarization experiment revealed that the triazole derivatives are inhibitors of mixed-type and electrochemical impedance spectroscopy (EIS) confirmed that changes in the impedance parameters (R-ct and C-dl) are due to surface adsorption. The inhibition efficiencies obtained from weight loss measurements and electrochemical tests were in good agreement. Adsorption followed the Langmuir isotherm with negative values of the free energy of adsorption Delta G(ads)(o). The thermodynamic parameters of adsorption were determined and are discussed. Results show that both 4-DTM and 5-DTM are good inhibitors for mild steel in acid media.