A DNA electrochemical sensor with poly-l-lysine/single-walled carbon nanotubes films and its application for the highly sensitive EIS detection of PAT gene fragment and PCR amplification of NOS gene

A sensitive and novel DNA electrochemical biosensor for the detection of the transgenic plants gene fragment by electrochemical impedance spectroscopy (EIS) was presented. The well-dispersed carboxylic group-functionalized single-walled carbon nanotubes (SWNTs) were dripped onto the carbon paste electrode (CPE) surface firstly, and poly-l-lysine films (pLys) were subsequently electropolymerized by cyclic voltammetry (CV) to prepare pLys/SWNTs/CPE. The morphology of pLys/SWNTs films was examined using a field emission scanning electron microscope (SEM). The pLys/SWNTs films modified electrode exhibited very good conductivity. DNA probes were easily immobilized on the poly-l-lysine films via electrostatic adsorption. The hybridization events were monitored with electrochemical impedance spectroscopy using [Fe(CN)₆]^3−/4− as indicator. The PAT gene fragment from phosphinothricin acetyltransferase gene was detected by this DNA electrochemical sensor. The dynamic detection range of this sensor to the PAT gene fragment was from 1.0 × 10⁻¹² to 1.0 × 10⁻⁷ mol/L. A detection limit of 3.1 × 10⁻¹³ mol/L could be estimated. The PCR amplification of NOS gene from the sample of a kind of transgenic modified bean was also detected satisfactorily by EIS.     

Characterization of structure and corrosion resistivity of polyurethane/organoclay nanocomposite coatings prepared through an ultrasonication assisted process

In this study, a series of castor oil based polyurethane/organically modified montmorillonite (OMMT) clay nanocomposite coatings have been successfully prepared by effective dispersing of OMMT nano-layers in polyurethane matrix through an ultrasonication assisted process. Effectiveness of ultrasonication process in de-agglomeration of clay stacks in castor oil dispersions was evaluated by optical microscopy and sedimentation test. Structure of nanocomposite coatings was investigated by wide angle X-ray diffraction (WAXD) and Fourier-transform infrared spectroscopy (FT-IR). The anticorrosive properties of nanocomposite coatings were characterized by electrochemical impedance spectroscopy (EIS), Tafel polarization study, water absorption and pull-off adhesion tests. The experimental results showed that PU/OMMT nanocomposite coatings were superior to the neat PU in corrosion protection effects. Also, it was observed that the corrosion protection of polyurethane organoclay nanocomposite coatings is improved as the clay loading is increased up to 3 wt.%.     

Poly(glutamic acid) nanofibre modified glassy carbon electrode: Characterization by atomic force microscopy, voltammetry and electrochemical impedance

Glassy carbon electrodes (GCE) were modified with poly(glutamic acid) acid films prepared using three different procedures: glutamic acid monomer electropolymerization (MONO), evaporation of poly(glutamic acid) (PAG) and evaporation of a mixture of poly(glutamic acid)/glutaraldehyde (PAG/GLU). All three films showed good adherence to the electrode surface. The performance of the modified GCE was investigated by cyclic voltammetry and differential pulse voltammetry, and the films were characterized by atomic force microscopy (AFM) and electrochemical impedance spectroscopy (EIS). The three poly(glutamic acid) modified GCEs were tested using the electrochemical oxidation of ascorbic acid and a decrease of the overpotential and the improvement of the oxidation peak current was observed. The PAG modified electrode surfaces gave the best results. AFM morphological images showed a polymeric network film formed by well-defined nanofibres that may undergo extensive swelling in solution, allowing an easier electron transfer and higher oxidation peaks.     

Anticorrosive properties of polypyrrole films modified with zinc onto SAE 4140 steel

Polypyrrole (PPy) films modified with zinc were electrosynthesized onto SAE 4140 steel in presence of bis(2-ethylhexyl) sulfosuccinate (AOT). The Zn and PPy electrodeposition was realized by using cyclic voltammetry at different temperatures. The corrosion protection properties of the films were examined in chloride solution by open circuit measurements, linear polarization and electrochemical impedance spectroscopy (EIS). The obtained results indicate that the presence of Zn in the polymer matrix improves the anticorrosive performance of PPy films. The best anticorrosion efficiency was obtained for the coatings modified at 20 °C which provided anodic protection to the steel substrate for a long period of immersion in chloride solution. Cathodic protection was observed when the electrodeposition temperature was increased. Adherence and anticorrosive properties declined sharply for the coatings electrosynthesized at 5 °C.     

Hemocompatibility evaluation of polyurethane film with surface‐grafted poly(ethylene glycol) and carboxymethyl‐chitosan

To improve the hemocompatibility and biocompatibility of polyurethanes (PUs), PU surface was firstly modified by poly(ethylene glycol) PEG through acryloyl chloride and subsequently grafted on carboxymethyl‐chitosan (CMCS). Attenuated total reflection Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy analysis confirmed that carboxyl‐chitosan was grafted onto PUs surface. The surface properties of unmodified and modified PU films were determined and compared by water contact angle assessment. After PEG and CMCS grafting, the surface energy of the PU film was increased. Furthermore, the hemocompatibility of the modified PU films was systematically evaluated by bovine serum albumin (BSA) adsorption, the dynamic blood clotting test, the platelet adhesion test, and the hemolytic test. It appears that BSA adsorption and platelet adhesion were significantly curtailed for the modified PU films. Therefore, the obtained results showed the modified PU film has better hemocompatibility. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Plasma-polymerized coatings of trimethylsilane deposited on cold-rolled steel substrates Part 2. Effect of deposition conditions on corrosion performance

Trimethyl silane (TMS) plasma-polymerized films were deposited on cold-rolled steel (CRS) under different conditions. The films were characterized by angular-dependent X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and time-of flight secondary ion mass spectrometry (TOFSIMS). The complementary information generated by these surface techniques gave detailed information on the film composition. The corrosion performance of the plasma films was estimated by electrochemical impedance spectroscopy (EIS) and by exposure in a humidity test. All films were Si-based and their composition was a function of the deposition conditions and the plasma cleaning of substrate prior to deposition. A reducing plasma for metal surface treatment resulted in a film with the highest impedance. The plasma film surfaces were highly oxidized. The contact angle was the lowest for plasma films deposited from a mixture of TMS and oxygen and their corrosion performance was the poorest.     

N-(triphenylphosphoranylidene) aniline as a novel electrolyte additive for high voltage LiCoO2 operations in lithium ion batteries

We report N-(triphenylphosphoranylidene) aniline (TPPA) as a new electrolyte additive for high performance lithium cobalt oxide (LiCoO₂) electrodes during high voltage operations. When cycled in the voltage range of 3.0–4.4 V, graphite-LiCoO₂ full cells with 0.2 wt% TPPA exhibited 10% increased discharge capacities after 200 cycles compared to those of control cells with no such additive. The enhanced cycling performance is attributed to the additive effect toward the modified surface films on LiCoO₂ electrodes that suppress the decomposition of both solvent and salt in the electrolyte. This additive effect was characterized by electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS).     

Green metal organic coating from recycled PETs and modified natural rubber for the automobile industry

Novel elastomeric polyurethane coating precursors from renewable natural rubber and waste bottle PET were prepared for metal coating applications. The elastomeric PU was synthesized from; modified natural rubber with hydroxyl functional groups (HLNR), modified NR grafted with polysiloxane (PDMS-g-LENR) and modified PETs (P-ET-PA and P-T-PA) such as a polyol/polyacid; a commercial MDI (Millionate MR-200) as an isocyanate. The physical properties such as film-thickness, gloss, hardness, adhesion (cross-cut and scratch-adhesion), impact test, Erichsen, bending and chemical resistance of the coated film were investigated by following the industry standards for automobile coatings. The properties of the coated films were influenced by the ratio of polyol/polyacid and the polyol nature. It was found that the coated film prepared from both of modified NR presented good adhesion with the metallic substrate by absence the surface treatment. Single layer of PU elastomer film prepared from both modified PETs with HLNR35 and MDI with mole ratio of 0.1:0.3:0.75 showed good physical properties following the industry standards for automobile coatings. The presence of PDMS-g-LENR in the coatings improved the thermal stability when compared to HLNR35. Furthermore, salt spray test and electrochemical impedance spectroscopy (EIS) were used to examine the corrosion behavior of the coated steel. It could be concluded that the best anticorrosive behavior was shown by the PDMS-g-LENR and P-T-PA formulas.     

Electrochemical and corrosion studies of poly(nickel-tetraaminophthalocyanine) on carbon steel

Nickel-tetraaminophthalocyanine [TAPcNi] was electropolymerized from the complex monomeric solution, onto carbon steel substrates, yielding thin adherent films of poly[TAPcNi]. The investigation of such polymer-modified electrodes was carried out by means of cyclic voltammetry, UV-vis spectroscopy, FT-IR spectroscopy and spectroelectrochemistry. The preparation of TAPcNi modified electrode was also carried out by electropolymerization of a preformed molecular film of TAPcNi, after applying a drop of TAPcNi dimethylsulphoxide solution onto carbon steel, and allowing it to dry. The comparison of the corrosion behavior of the two types of polymer-coated electrodes was carried out by electrochemical impedance spectroscopy (EIS) in acid medium. It was found that the structure and morphology of each polymer greatly influence their redox behavior and corrosion inhibition performance for steel in hydrochloric acid. The film prepared by the drop-dry method offered a better corrosion protective efficiency while the electropolymerized film presented a more conductive behavior.     

Electro-assisted preparation of dodecyltrimethoxysilane/TiO2 composite films for corrosion protection of AA2024-T3 (aluminum alloy)

Thin films of organosilanes have been successfully used as the alternative to toxic chromate coatings for surface pretreatment of metals and alloys. To further improve their corrosion performance, in the present work nano-scaled TiO₂ particles were added to the dodecyltrimethoxysilane (DTMS) films coated onto AA2024-T3 substrates, by using either the dip-coating or the cathodically electro-assisted deposition process. The obtained composite films were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM), water contact angle measurements, Fourier transform reflection-absorption IR (FTRA-IR) and electrochemical impedance spectroscopy (EIS). The results show that these two techniques (nanoparticles incorporation and the electro-assisted deposition) both facilitate the deposition process of silane films, giving thicker deposit and higher coverage surface along with higher roughness and hydrophobicity, and thereby improve their corrosion resistance. Moreover, the corrosion performance of silane films is further improved by the combined use of nanoparticles modification and electro-assisted deposition.     

电解质对卵磷脂双分子层电化学行为的影响

实验利用自组装技术在铂电极上制备支撑的卵磷脂双层膜（s-BLM）作为生物膜的模型,利用循环伏安法（cV）和电化学阻抗谱（EIS）对由电解质KCI引起的s-BLM通透性的变化进行了研究。结果表明,KCI可与s-BLM发生较强的相互作用,导致s—BLM表面磷脂分子的有序排列受到影响,产生一些离子通道,增加了对探针分子电流响应,同时降低了s—BLM的电阻。     

Inhibition Effects of a Synthesized Novel 4-Aminoantipyrine Derivative on the Corrosion of Mild Steel in Hydrochloric Acid Solution together with Quantum Chemical Studies

1,5-Dimethyl-4-((2-methylbenzylidene)amino)-2-phenyl-1H-pyrazol-3(2H)-one (DMPO) was synthesized to be evaluated as a corrosion inhibitor. The corrosion inhibitory effects of DMPO on mild steel in 1.0 M HCl were investigated using electrochemical impedance spectroscopy (EIS), potentiodynamic polarization, open circuit potential (OCP) and electrochemical frequency modulation (EFM). The results showed that DMPO inhibited mild steel corrosion in acid solution and indicated that the inhibition efficiency increased with increasing inhibitor concentration. Changes in the impedance parameters suggested an adsorption of DMPO onto the mild steel surface, leading to the formation of protective films. The novel synthesized corrosion inhibitor was characterized using UV-Vis, FT-IR and NMR spectral analyses. Electronic properties such as highest occupied molecular orbital energy, lowest unoccupied molecular orbital energy (EHOMO and ELUMO, respectively) and dipole moment (μ) were calculated and discussed. The results showed that the corrosion inhibition efficiency increased with an increase in the EHOMO values but with a decrease in the ELUMO value.     

PLA-TiO2 nanocomposites: Thermal,morphological, structural,and humidity sensing properties

In this paper, the effect of TiO₂ ceramic nanoparticles on the thermal stability, morphology, molecular mass, structure and electrical properties of the polylactic acid-Titanium dioxide (PLA-TiO₂) composites, aimed for relative humidity (RH) sensing have been reported. PLA-TiO₂ nanocomposites films were developed through a spin coating process. The developed films were characterized by X-ray diffraction (XRD), Raman spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM) and electrochemical impedance spectroscopy analysis (EIS). To investigate the RH-dependent characteristics, the devices were prepared on pre-patterned ITO substrates. The capacitive and resistive response of the nanocomposite films were studied under RH levels ranging from 20–90%. The PLA-TiO₂ nano-sensing films, having modified surface by acetone etching, exhibited superior morphological and electrical performance when compared to PLA-TiO₂ pristine samples.     

Copper/polypyrrole multilayer coating for 7075 aluminum alloy protection

The corrosion behavior of 7075 aluminum (Al), copper modified Al (Al/Cu), polypyrrole modified Al (Al/PPy) and copper (under layer)/polypyrrole (top layer) modified Al (Al/Cu/PPy) samples were investigated in 3.5% NaCl solution. The copper plating on aluminum was carried out from acidic copper sulphate solution by electroless method. Polypyrrole (PPy) was electrochemically synthesized on Al and Al/Cu electrodes from 0.1 M pyrrole containing 0.4 M oxalic acid solution using cyclic voltammetry technique. The films synthesized were characterized by Fourier transform infrared spectroscopy (FT-IR). The thermal stability of PPy films was investigated by thermogravimetric analysis (TGA). The surface morphologies were examined by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The corrosion behavior of samples was investigated by electrochemical impedance spectroscopy (EIS) and anodic polarization curves. The data obtained showed that the synthesis of PPy on top of the Cu layer significantly enhances the corrosion resistance of Al by exhibiting a barrier effect against the attack of corrosive environment.     

Gold nanoparticle/carbon nanotube hybrids as an enhanced material for sensitive amperometric determination of tryptophan

In this work, a highly sensitive electrochemical sensor for the determination of tryptophan (Trp) was fabricate by electrodeposition of gold nanoparticles (AuNPs) onto carbon nanotube (CNT) films pre-cast on a glassy carbon electrode (GCE), forming an AuNP-CNT composite-modified GCE (AuNP-CNT/GCE). Scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were used for the surface analysis of the electrode. The results indicate that the hybrid nanomaterials induced a substantial decrease in the overpotential of the Trp oxidation reaction and exhibited a remarkable synergistic effect on the electrocatalytic activity toward the oxidation of Trp. In phosphate buffer solution (pH 7.4), the modified electrode showed excellent analytical performance for the amperometric determination of Trp. The peak currents possess a linear relationship with the concentration of Trp in the range of 30 nM to 2.5 μM, and the detection limit is 10 nM (S/N = 3). In addition, the modified electrode was used to determine Trp concentration in pharmaceutical samples with satisfactory results.     

Electrochemically polymerized 2,2-dimethyl-3,4-propylenedioxythiophene on carbon fiber for microsupercapacitor

ProDOT(Me)₂ was electrochemically polymerized onto a carbon fiber microelectrode (CFME) by cyclovoltammetry under a wide potential range (0–1.6 V) with well-defined parameters. The nano to micron scale coatings on CFMEs were characterized by cyclovoltammetry, ex situ FTIR attenuated total reflectance spectroscopy (FTIR-ATR), electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM and EDX). The existence of a capacitance behavior is shown by Nyquist, Bode phase relationship.     

Investigation of alkylamine self-assembled films on iron electrodes by SEM, FT-IR, EIS and molecular simulations

Alkylamine were used to form self-assembled films for the inhibition of the corrosion of iron in 0.5 M H₂SO₄ solution. The films were characterized by electrochemical impedance spectroscopy (EIS) and surface analysis techniques including SEM and FT-IR. EIS results indicate that the inhibition ability of these alkylamine self-assembled films depends on the immersion time and the alky chain length of the adsorbate. Both longer immersion time of the electrode in the solution and longer alky chain will result in stronger inhibition ability of the films. However, when the immersion time was increased over some critical point, the inhibition ability was almost invariable. Also when the chain length reached a certain degree such as 14 carbon atoms, the inhibition ability decreased on the contrary. The ability of the corrosion inhibition of the tetradecylamine and dodecylthiol mixed films improved remarkably comparing with the tetradecylamine or dodecylthiol single films. In addition, molecular simulation was used to discuss the adsorption mechanism and good agreement with electrochemical results was obtained.     

Electrochemical behaviour of PANi/polyurethane antifouling coating in salt water studied by electrochemical impedance spectroscopy

Electrochemical behaviour of polyaniline–polyurethane (PANi–PU) antifouling coating in 3.5 wt% NaCl is studied by electrochemical impedance spectroscopy (EIS). A thick coating (∼1 mm) of 10, 15 and 20% PANi in marine grade PU, is cast over corrosion resistant aluminium alloy 2024 and its impedance characteristics are measured by EIS and compared with neat PU. On addition of 10% PANi, the impedance of the coating drastically comes down from 10⁹ to 10⁷ Ω. 20% is the maximum processable amount of PANi for the selected PU system. The coatings are exposed to 3.5 wt% NaCl and its impedance characteristics are monitored as a function of time. Changes in the impedance characteristics of the systems were found to occur as a function of the exposure time in all cases, though their evolution with time showed marked differences with PANi content. Water sorption and break down frequency are derived from the experimental results and analysed.     

Identification of inductive behavior for polyaniline via electrochemical impedance spectroscopy

Polyaniline (PANI) film electrodeposited in HCl medium using cyclic voltammetry (CV) with an upper potential limit of 0.90 V, exhibited an inductive behavior. PANI films deposited with different conditions were subjected to various applied potentials and the impedance characteristics were recorded through electrochemical impedance spectroscopy (EIS). The impedance results clearly reveal the existence of inductive behavior to PANI. Inductive behavior was observed for PANI films deposited with conditions which favor benzoquinone/hydroquinone (BQ/HQ) formation and further evidenced by X-ray photoelectron spectroscopy (XPS). A comparative analysis of the EIS and XPS results of PANI films prepared under similar conditions with the upper potential limits of 0.75 and 0.90 V, respectively, clearly documented that the presence of BQ/HQ, the degradation product of PANI, formed during the electrochemical polymerization at the upper potential limits causes inductive behavior to PANI.     

EDTA modified glassy carbon electrode: Preparation and characterization

EDTA-phenoxyamide modified glassy carbon electrode (EDTA-GC) was prepared at a glassy carbon electrode by surface synthesis. In the first step, nitrophenyl was grafted to the glassy carbon (GC) surface via the electrochemical reduction of its tetraflouroborate diazonium salt. In the second step, nitrophenyl-modified electrode (NP-GC) was subjected to the cathodic potential scan to reduce the nitro to amine group. p-Aminophenyl modified glassy carbon electrode (AP-GC) was dipped into a EDTA solution containing 1-ethyl-3(3-(dimethlyamino)propyl)-carbodiimide (EDC) as an activating agent. Thus formed ((2-anilino-2-oxoethyl){2-[bis(carboxymethyl)amino]-ethyl}amino)acetic acid modified GC electrode was denoted as EDTA-GC and characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), ellipsometry and X-ray photoelectron spectroscopy (XPS). Complexation of the EDTA-GC surface with Pb²⁺ ions was investigated if this electrode could be used as a metal sensor.