Direct electrochemical behavior of cytochrome c on sodium dodecyl sulfate modified electrode and its application to nitric oxide biosensor

Polyacrylamide (PAM), sodium dodecyl sulfate (SDS) and cytochrome c (Cyt c) were immobilized on the surface of a glass carbon electrode (GCE), respectively, to form a Cyt c /SDS/PAM/GCE. The modified electrode was characterized with the electrochemical impedance. The direct electrochemical behaviors of Cyt c on SDS/PAM/GCE were obtained by using cyclic voltammetry. A pair of well-defined and reversible redox peaks could be observed in a 0.10 M pH 7.0 phosphate buffer solution. The anodic and cathodic peak potentials of Cyt c were at 0.051 V and − 0.003 V (vs. Ag/AgCl), respectively. The Cyt c on SDS/PAM/GCE exhibited well electrocatalytic activity to reduction of nitric oxide. The relative electrochemical parameters were obtained. The resulted electrode displayed a rapid amperometric response to the reduction of nitric oxide. The catalytic current is linear to the nitric oxide concentration in the range of 8.0 × 10^− 7 M to 9.5 × 10^− 5 M and the detection limit was 1.0 × 10^− 7 M (Signal/Noise = 3). The proposed biosensor could be used to detect quantitatively nitric oxide.     

Preparation and characterization of poly(indole-3-carboxaldehyde) film at the glassy carbon surface

Indole-3-carboxaldehyde (In3C) monomer was oxidized by electrochemical methods at the glassy carbon (GC) electrode in 0.05 M tetrabutylammonium tetrafluoroborate in acetonitrile, with the aim to prepare a modified electrode. Modification was performed using cyclic voltammetry (CV) scanning from 0.0 V to 2.0 V at a scan rate of 50 mV s^− 1 for 10 cycles in 1 mM In3C monomer solution. The modified GC surface (In3C-GC) was characterized by CV response of potassium ferricyanide and ferrocene redox probes as well as by the electrochemical impedance spectroscopy. The modified surface was analyzed by reflection-absorption infrared spectroscopy and compared with the spectrum of the monomeric In3C. Elemental composition of the surface was determined by X-ray photoelectron spectroscopy. Contact angle measurements was also performed to check the changes in hydrophobic character of the bare GC and compared to that of In3C-GC surface. Thickness of the oligomeric/polymeric film was investigated by ellipsometric measurements and a surface confined polymerization mechanism was proposed.     

Structure and electrochemical reactivity of 3-[tris(2-methoxyethoxy)silyl]-propanethiol adsorbed on silver surface

A novel stable self-assembled chemisorbed layers, providing protection of metal surface against electrooxidation capable of blocking propylene carbonate (PC) electroreduction and Li electrodeposition, were produced from 3-[tris-(2-methoxyethoxy)silyl]-propanethiol (SIS2) on silver. Reflection-absorption infrared spectroscopy (RAIRS) indicated cleavage of the S-H bond upon adsorption of SIS1 [3-(trimethoxysilyl)-propanethiol] and SIS2 species with the formation of S-Ag bonds on the metal surface. By cyclic voltammetry it was found that the primary adsorbate formed on a Ag electrode at E_ad (between − 0.2 and − 1.2 V vs. SCE) underwent reductive desorption at E < − 1.3 V vs. SCE. From the charge involved in this process, the saturation surface coverage was estimated as 4.2 10^− 10 mol cm^− 2. A compact SIS2 layer after long-time aging (hydrolysis and condensation) was electroinactive and thus non-desorbable from the electrode surface during the potential cycling. The structures of SIS2 and its complexes with Li⁺ cations on the Ag surface were calculated and visualized by the AM1d semi-empirical method.     

Electrochemical studies of cystine modified self-assembled monolayer for Escherichia coli detection

An electrochemical DNA biosensor based on cystine modified self-assembled monolayer (cys-SAM) onto gold electrode (AuE) has been fabricated for Escherichia coli (E. coli) detection. This biosensing electrode has been characterized using scanning electron microscopy (SEM), FT-IR spectroscopy, cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS). Under the optimum conditions, this DNA biosensor can be used to detect complementary target DNA concentration in the range of 1 × 10^− 6 M to 1 × 10^− 20 M within 60 s of hybridization time at 25 °C and has been found to be stable for about four months when stored at 4 °C.     

Characterization of electron irradiated GaN n-p diode

Electron-beam irradiated GaN n⁺-p diodes were characterized by deep level transient spectroscopy (DLTS) and optical responsivity measurements. The GaN n⁺-p diode structures were grown by metal organic chemical vapor deposition technique, and the electron irradiation was done by the energies of 1 MeV and 2 MeV with dose of 1 × 10¹⁶ cm^− 2. In DLTS measurement, the defect states of E_c − 0.36 eV and E_c − 0.44 eV in the electron irradiated diodes appeared newly. The optical responsivity of GaN n⁺-p diode was characterized in ultra-violet region, and then the maximum optical responsivity at 350 nm was decreased after electron-beam irradiation.     

Electropolymerization of Cu-(N,N′-bis(3-methoxysalicylidene)-2-aminobenzylamine) on platinum electrode: Application to the electrocatalytic reduction of hydrogen peroxide

The complex of copper (II) with N,N′-bis(3-methoxysalicylidene)-2-aminobenzylamine (H₂L) was synthesized and characterized by elemental analysis, magnetic susceptibility, UV–vis. and FT-IR spectroscopy. The results showed that the tetradentate ligand coordinated to the Cu(II) ion through the azomethine nitrogen and phenolic oxygen atoms. The prepared complex [CuL] was electropolymerized on platinum electrode surface in a 0.1 mol dm⁻³ solution of lithium perchlorate in acetonitrile by cyclic voltammetry between 0 and 1.6 V vs. Ag/Ag⁺. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), conductance measurements, FT-IR and SEM were used to characterize polymer film of Cu(II) complex. The reduction of hydrogen peroxide on poly[CuL] has been investigated mainly in phosphate buffer medium (pH 7.2), between 0 and −0.8 V versus Ag/Ag⁺ at a scan rate 0.1 V s⁻¹.     

Deposition and structural properties of RF magnetron-sputtered ZnO thin films on Pt/Ti/SiNx/Si substrate for FBAR device

This work investigates high-quality bottom electrode and piezoelectric film used in a thin-film bulk acoustic resonator (TFBAR) device. The titanium (Ti) seeding layer and platinum (Pt) bottom electrode were deposited on silicon substrates by DC sputtering using a dual-gun system. Zinc oxide (ZnO) was then deposited onto the Pt bottom electrode by RF magnetron sputtering. Field-emission scanning electron microscopy (SEM), atom force microscopy (AFM) and the four-point probe method showed that the Pt bottom electrode deposited on the Ti seeding layer exhibited favorable characteristics, such as a crystallite size of less than 10 nm, a surface roughness of 0.69 nm and a sheet resistance of 2.27 Ω/□. The ZnO thin film with a highly c-axis-preferred orientation (FWHM = 0.28°) and a roughness of 6.22 nm was investigated by X-ray diffraction (XRD) and AFM analysis, respectively. The bottom electrode with a low resistance and the highly crystalline ZnO thin film will contribute significantly to the favorable characteristics of the FBAR devices.     

The structure and properties of SnS thin films prepared by pulse electro-deposition

SnS films were prepared onto the ITO-coated glass substrates by pulse-form electro-deposition. The potential applied to the substrates was of pulse-form and its “on” potential, V_on was − 0.75 V (vs. SCE )and “off ” potential, V_off was varied in the range of − 0.1-0.5 V. The SnS films deposited at different V_off values were characterized by XRD, EDX, SEM and optical measurements. It shows that all the films are polycrystalline orthorhombic SnS with grain sizes of 21.54-26.93 nm and lattice dimensions of a = 0.4426-0.4431 nm, b = 1.1124-1.1134 nm and c = 0.3970-0.3973 nm, though the V_off has some influence on the surface morphology of the films and Sn/S ratio. When V_off = 0.1-0.3 V, the SnS films have the best uniformity, density and adhesion, and the Sn/S ratio is close to 1/1. The direct band gap of the films was estimated to be between 1.23 and 1.33 eV with standard deviation within ± 0.03 eV, which is close to the theoretical value. The SnS films exhibit p-type or n-type conductivity and their resistivity was measured to be 16.8-43.1 Ω cm.     

Electrochemical behavior of ascorbate oxidase immobilized on graphite electrode modified with Au-nanoparticles

Direct electrochemistry of ascorbate oxidase was observed when immobilized on graphite modified with nano-sized gold structures. Au-structures were electrodeposited onto the graphite surface by means of cyclic voltammetry, then the enzyme was chemisorbed onto their surface. The electron transfer between the enzyme active center and the modified electrode surface was probed by square wave voltammetry (SWV) and cyclic voltammetry (CV). The dependence of the current maxima on the scan rate was found linear, suggesting that the redox process is controlled by surface chemistry. Bioelectrocatalytic oxidation of the enzyme substrate l-ascorbic acid was explored by constant potential amperometry over the potential range from 200 to 350 mV (vs. Ag/AgCl, 3 M KCl) at the рНs 5.6 and 7.0. At a potential as low as 200 mV, pH 7.0 and temperature 25 °C following operational parameters were determined for the enzyme electrode: a sensitivity: 1.54 μA mM⁻¹ mm⁻² (r² = 0.99₅), linear dynamic range up to 3.3 mМ, detection limit of 1.5 μМ, response time up to 20 s.     

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.     

Cadmium-sensitive electrode based on tetracetone derivatives of p-tert-butylcalix[8]arene

The performance of a cadmium-sensitive electrode based on the tetracetone derivatives of p-tert butylcalix[8]arene was investigated. The ion-sensitivity of the calix[8]arene was examined via cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectrometry, UV/Vis spectroscopy and FT-IR spectroscopy. The sensitive membrane containing the active ionophore was cast onto the surface of a gold electrode. The electrode exhibited a linear relationship between the charge transfer resistance (R_ct) and the logarithm of the detected ion concentration. The cathodic peak at a potential of 0.56 V increased linearly as the Cd^2 + ion concentration increased. The detection limit of the device reached 10^? 7 M with high sensitivity toward cadmium.     

Study of adsorption behaviors of meso-tetrakis (4-N-Methylpyridyl) porphine p-Toluenesulfonate at indium-tin-oxide electrode/solution interface by in-situ internal reflection spectroscopy and cyclic voltammetry

In situ electrochemical-absorption spectra of meso-tetrakis (4-N-Methylpyridyl) porphine p-Toluenesulfonate (TMPyP) adsorbed on the surface of an ITO (indium-tin-oxide) electrode was observed by simultaneous measurements using cyclic voltammetry (CV) and internal reflection spectroscopy. The CV experiment was performed using ITO coated on glass as the working electrode, platinum wire as the counter electrode and silver/silver chloride (Ag/AgCl) electrode as the reference electrode. It was found that, in 1 M HCl and pH = 2 Britton-Robinson solutions, TMPyP were adsorbed on ITO as P(0)H₄²⁺ state and P(0)H₂ state, respectively. Moreover, when the potential was applied on the ITO electrode, the redox reactions of TMPyP in 1 M HCl were also different from those in pH = 2 Britton-Robinson solutions. The adsorption rate, desorption rate and equilibrium constants as well as the adsorption free energy of TMPyP were determined by fitting adsorption process between TMPyP and ITO using Langmuirian adsorption model. The effect of pH on the internal reflection spectra was also explored, in which it was shown that the increase of pH lead to the enhancement of the intensity of the internal reflection spectra and the blue shift of the peak position. With the increase of ionic strength of TMPyP solution, the intensity of the internal reflection spectra decreased.     

Correlation between resistivity and oxygen vacancy of hydrogen-doped indium tin oxide thin films

Thin films of indium tin oxide (ITO) sputter-deposited by dc-plasma containing deuterium on glass substrate without any heat treatments exhibited gradual lowering in electrical resistivity with increasing the deuterium content [D₂] in plasma gas by 1% and then demonstrated a jump in resistivity by further increase of [D₂] than 1%. X-ray photoelectron spectroscopy revealed that hydroxyl-bonded oxygen in ITO grew continuingly with [D₂]. Deuterium positioned at the interstitial site increased almost quantitatively with increasing [D₂]. Rutherford backscattering spectroscopy showed gradual reduction in the oxygen content of ITO with increasing [D₂] by 1% and then demonstrated an abrupt increase of the oxygen content with the increase of [D₂] than 1%. The films with [D₂] < 1% were oxygen deficient, but those with [D₂] > 1% were excess of oxygen. The most oxygen deficient film of [D₂] = 1% was the most conductive. Behavior in the resistivity with [D₂] looks parallel to that in the oxygen content. A lower resistivity of the films corresponded well to oxygen vacancy rather than hydrogen interstitial.     

Electrophoretic deposition of siderite thin layers: Influence of electrode potential and deposition time

Siderite thin layers have been obtained by electrophoretic deposition on an inert substrate (gold). Scanning electron microscopy image exhibits a compact and homogeneous film composed of round grains which diameter is about 1-2 µm. The influence of two parameters, namely the electrode potential and the deposition time, on its thickness and its microstructure was investigated. The thickness was shown to be slightly dependent of the electrode potential (1.2 µm for − 0.70 V and 1.7 µm for − 0.95 V after 17 h). The crystallite size, estimated by X-ray diffraction patterns, was about 5 nm, depending on both electrode potential and deposition time. Despite its high sensitivity to oxygen, X-ray photoelectron spectroscopy spectra prove that the siderite surface has been kept out from oxidation. These siderite thin layers could be used as modified electrodes for further interaction studies.     

Ion-bombardment characteristics during deposition of TiN films using a grid-assisted magnetron system with enhanced plasma potential

Energy-resolved mass spectroscopy was used to investigate differences in ion-bombardment characteristics during conventional reactive magnetron sputtering of TiN films and their deposition using a grid-assisted magnetron system with anode at a high potential (up to 350 V relative to grounded chamber walls). Narrow ion energy distributions with a maximum corresponding to the ion energy close to 100 eV were obtained for the conventional magnetron deposition on a biased substrate (V_b=−100 V) in an 80%Ar+20%N₂ gas mixture at a pressure of 0.5 Pa. On the contrary, the energy distributions of ions bombarding a grounded substrate in the grid-assisted modified magnetron system with the grid potential V_g=+100 V were broadened and extended to higher energies (up to 300 eV) under the same conditions. The change in the ion energy distributions is caused by increase in the plasma potential due to the high anode potential (approximately 320 V in this case). Simultaneously, the total ion flux to the substrate decreased 5.4 times compared with the conventional system. A combined effect of the enlarged kinetic energy of ions and their substantially reduced flux resulted in production of high-quality, densified TiN films with a smooth surface.     

X-ray photoelectron spectroscopy of oxygen-containing layers formed by a linear potential scan on stepped gold (111) films in aqueous 1 M sulphuric acid

X-ray photoelectron spectroscopy (XPS) data of oxygen-containing layers (O-layers) made on stepped gold (111) film electrodes from aqueous 1 M sulphuric acid by single linear potential scans at 0.10 V s^− 1 and 298 K are reported. The potential scan covered from the open circuit potential to anodic switching potential E_as = 2.50 V versus normal hydrogen electrode (NHE) and holding times at E_as in the range 30-300 s. The anodic charge density q_a determined from the oxidation and reduction voltammetric scan is in the range 0.20 ≤ q_a ≤ 2.5 mC cm^− 2. For the potential E = 0.5 V, in the absence of O-layers, the S 2p core level spectrum indicates the presence of sulphate/bisulphate adsorbates. For E_as > 1.3 V, the O 1s core level spectrum involves the contribution from water, OH- and O-species. These spectra are deconvoluted utilising either three or four Gaussian contributions with values of peaked binding energy and full width at half-maximum height (FWMH) in good agreement with expectations. The envelope of these XPS O 1s signals after correction for the contribution of sulphate/bisulphate adsorbates and adventitious carbon approaches the XPS signal that has been reported for the core level spectrum in the O 1s region of oxidised gold surfaces produced by laser pulses at different molecular oxygen pressures. The O/OH concentration ratio in the O-layer increases with E_as ageing time t_ag and cathodic charge density q_c. The hydrous nature of the O-layer, evaluated through the analysis of the core level spectra in the O 1s region, decreases as E_as and t_ag are increased. Results are interesting to unravel the composition and structure of electrochemically grown O-layers at the surface of the gold substrate, and the influence of the history of these O-layers on the respective XPS features.     

Synthesis of a red electrophosphorescent heteroleptic iridium complex and its application in efficient polymer light-emitting diodes

The preparation and characterization of a heteroleptic iridium complex [2-(benzo[b]thiophen-2-yl)pyridine]Ir(III)[2-(4H-1,2,4-triazol-3-yl)pyridine] [(Btp)₂Ir(PZ)] were reported (2-(benzo[b]thiophen-2-yl)pyridine = Btp; 2-(4H-1,2,4-triazol-3-yl)pyridine = PZ). Electrophosphorescence was investigated in the device structure [indium-tin-oxide (ITO)/poly(ethlenedioxythiophene) (PEDOT)/poly(vinylcarbazole)(PVK)/Poly(9,9-dioctylfluorenyl-2,7-diyl) end capped with dimethylphenyl (PFO): (Btp)₂Ir(PZ)/Ba/Al] by using this iridium complex as guest and PFO as host. The red electrophosphorescent devices showed a peak emission at approximately 604 nm and shoulder at 654 nm with the Commission International de'Eclairage (CIE) coordinates of (0.64, 0.35) and external quantum efficiency of 7.7% at a doping concentration of 8 wt.% without an electron-transporting material in the emitting layer.     

2D-network of inorganic-organic hybrid material built on Keggin type polyoxometallate and amino acid: [L-C2H6NO2]3[(PO4)Mo12O36]·5H2O

A new inorganic-organic hybrid material based on polyoxometallate, [L-C₂H₆NO₂]₃[(PO₄)Mo₁₂O₃₆]·5H₂O, has been successfully synthesized and characterized by single-crystal X-ray analysis, elemental analysis, infrared and ultraviolet spectroscopy, proton nuclear magnetic resonance and differential thermal analysis techniques. The title compound crystallizes in the monoclinic space group, P2₁/c_, with a = 12.4938 (8) Å, b = 19.9326 (12) Å, c = 17.9270 (11) Å, β = 102.129 (1)°, V = 4364.8 (5) Å³, Z = 4 and R₁(wR₂) = 0.0513, 0.0877. The most remarkable structural feature of this hybrid can be described as two-dimensional inorganic infinite plane-like (2D/∞ [(PO₄)Mo₁₂O₃₆]³⁻) which forming via weak Van der Waals interactions along the z axis. The characteristic band of the Keggin anion [(PO₄)Mo₁₂O₃₆]³⁻ appears at 210 nm in the UV spectrum. Thermal analysis indicates that the Keggin anion skeleton begins to decompose at 520 °C.     

Effect of a pulsed Nd:YAG laser irradiation on multi-walled carbon nanotubes film

Multi-walled carbon nanotubes (MWCNTs) film have been analyzed by Raman spectroscopy to clarify the effect of a pulsed Nd:YAG laser heating. The MWCNTs film surface was flashed with the fundamental harmonic (λ = 1064 nm) or the second harmonic (λ = 532 nm) of a single pulse of Nd:YAG laser in the air. The dynamics of pulsed nanosecond laser heating process was simulated by the solution of the one-dimensional heat conduction equation. At the laser fluence of 500 mJ/cm² with Nd:YAG laser (λ = 1064 nm), the surface reached the maximum temperature 1395 °C at 12 ns. Moreover, the Raman spectroscopy of MWCNTs films before and after irradiation were measured. The intensity of the two characteristic Raman shifts I_D (defect-mode) and I_G (graphite-mode) was measured by the Raman spectroscopy. The maximum surface temperature was calculated and compared with the I_G/I_D ratio of MWCNTs film. The graphitization occurred on the sample after irradiation.     

Impedimetric biosensor based on magnetic nanoparticles for electrochemical detection of dopamine

One of the difficulties which limit the use of electrochemical sensors for detection of dopamine is the interference from ascorbic acid. We have sought to address this problem through the synthesis and characterization of a suitable electrode material based on magnetic nanoparticles. The interference from the ascorbic acid was overcome by fabricating a negatively charged electrode surface using PEGylated arginine functionalized magnetic nanoparticles (PA-MNPs). The nanoparticles were characterized by various techniques viz., X-ray diffraction, FT-Infrared spectroscopy, transmission electron microscopy and vibrating sample magnetometer. The electrochemical behavior of the proposed sensor was investigated by cyclic voltammetry and the sensor showed high sensitivity and selectivity for dopamine. The response mechanism of the modified electrode is based on the interaction between the negatively charged electrode and the positively charged dopamine. Under optimized conditions, linear calibration plots were obtained for amperometric detection of dopamine (DA) over the concentration range of 1–9 mM dopamine, with a linear correlation coefficient of 0.9836, sensitivity of 121 μA/mM and a detection limit of 7.25 μM. Electrochemical impedance spectroscopy (EIS) has been used to study the interface properties of modified electrodes. The value of the polarization resistance (R_p) increases linearly with dopamine concentration in the range of 10 μM to 1 mM and the limit of detection (LOD) was calculated to be 14.1 μM. High sensitivity and selectivity, micromolar detection limit, high reproducibility, along with ease of preparation of the electrode surface make this system suitable for the determination of DA in pharmaceutical and clinical preparations.