Sensitive and selective imprinted electrochemical sensor for p-nitrophenol based on ZnO nanoparticles/carbon nanotubes doped chitosan film

A sensitive and selective molecularly imprinted electrochemical sensor for p-nitrophenol detection has been developed based on ZnO nanoparticles/multiwall carbon nanotubes (MWNTs)-chitosan (CTS) nanocomposite. This nanocomposite was dripped onto an indium tin oxide electrode and then imprinted sol-gel solution was electrodeposited onto the modified electrode to construct the proposed sensor. The morphologies and electrochemical behaviors of the imprinted sensor were characterized by scanning electron microscope, X-ray diffraction, electrochemical impedance spectroscopy, square wave voltammetry and cyclic voltammetry. The imprinted sensor displayed excellent selectivity towards the target molecule p-nitrophenol. Meanwhile, the introduced nanocomposite increased surface area and active sites for electron transfer, thus remarkably enhancing the sensitivity of the imprinted sensor. Under optimal conditions, the peak current was linear to p-nitrophenol concentration ranging from 1.0 × 10^− 8 to 2.0 × 10^− 4 mol·L^− 1 with a detection limits of 1.0 × 10^− 9 mol·L^− 1 (S/N = 3). This proposed sensor was applied to the detection of p-nitrophenol in various water samples successfully.     

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.     

Transparent nanoporous tin-oxide film electrode fabricated by anodization

A transparent nanoporous tin oxide film electrode was fabricated by anodizing a tin film on a fluorine-doped tin oxide (FTO) film electrode. The resulting anodized nanoporous tin oxide (ANPTO) film has columnar-type pore channels with around 50 nm in diameter and is optically transparent. Electrochemical measurements with Fe(CN)₆³⁻ as a redox probe clearly revealed that the ANPTO film could be used for a working electrode with a large internal surface area. Moreover, it was found that ANPTO film had a wider anodic potential window (> ca. 2.0 V) than conventional metal oxide electrodes, such as FTO and indium tin oxide film electrodes (> ca. 1.3 V). The wide anodic potential window improves applicability of a transparent metal oxide electrode for various electrochemical oxidation reactions, which are often interfered by oxygen evolution in water. These results conclude that the ANPTO film can be used as an advanced transparent nanoporous film electrode.     

Molecularly imprinted polymer for the recognition of biological warfare agent staphylococcal enterotoxin B based on Surface Plasmon Resonance

Molecularly imprinted polymers (MIPs) embody a new class of materials possessing high selectivity and affinity for the target molecules. The aim of the present work is to explore the feasibility of employing the MIP as sensing material for the detection of Staphylococcal enterotoxin B (SEB) by Surface Plasmon Resonance (SPR). In this context, the MIP film was prepared by in-situ electropolymerization of 3-aminophenylboronicacid (3-APBA) on the bare gold chip in the presence of SEB molecule. The MIP of SEB exhibited a linear response from 3.2 fM to 25.6 fM (r² = 0.99) with a detection limit of 0.05 fM. K_D (equilibrium constant) and Bmax (maximum binding capacity of analyte) were calculated by using kinetic evaluation software and found to be 24 fM and 71, respectively and change in Gibb's free energy (?G) value calculated using Vant's Hoff equation was found to be −77.54 kJ/mol. Interference study was performed with the homologs of SEB such as SEA and SEC in order to know the selectivity efficiency of SEB MIP and were found to be 23.57% and 23.43%, respectively.     

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.     

Aqueous two-phase systems: a new approach for the determination of p-aminophenol

A new method has been developed for the spectrophotometric determination of p-aminophenol (PAP) in water, paracetamol formulations and human urine samples with a recovery rate between 94.9 and 101%. This method exploits an aqueous two-phase system (ATPS) liquid-liquid extraction technique with the reaction of PAP, sodium nitroprusside and hydroxylamine hydrochloride in pH 12.0, which produces the [Fe₂(CN)₁₀]¹⁰⁻ anion complex that spontaneously concentrates in the top phase of the ATPS (K[Fe₂(CN)₁₀]¹⁰⁻=97.7). The ATPS does not require an organic solvent, which is a safer and cleaner liquid-liquid extraction technique for the determination of PAP. The linear range of detection was from 5.00 to 500 μg kg⁻¹ (R ≥ 0.9990; n = 8) with a coefficient of variation of 2.11% (n = 5). The method exhibited a detection limit of 2.40 μg kg⁻¹ and a quantification limit of 8.00 μg kg⁻¹. The ATPS method showed a recovery that ranged between 96.4 and 103% for the determination of PAP in natural water and wastewater samples, which was in excellent agreement with the results of the standard 4-aminoantipyrine method that was performed on the same samples.     

Copper underpotential deposition on TiO2 electrodes: A voltammetric and electrochemical quartz crystal nanobalance study

In this work, the electrogravimetric behavior of copper electrodeposition on TiO₂ electrodes was analyzed. Copper electrodeposition was carried out in 0.1 mol L^− 1 H₂SO₄ using several concentrations of CuSO₄. The voltammetric curve displays a redox processes. The first redox process occurs in the region of − 0.30 at 0.1 V (vs. saturated calomel electrode, SCE) and it is related to bulk Cu electrodeposition and stripping. For this cathodic process, it was observed that the mass gain increases both as the sweep rate decreases and as the concentration of copper increases. The second redox process, which occurs between − 0.1 V and 0.35 V (vs. SCE), the stripping charge (and mass) are independent of both sweep rate and CuSO₄ concentration and, finally, there is a saturation charge (and saturation mass) as the deposition time is increased. From the saturated mass, obtained using an electrochemical quartz crystal nanobalance, for this electrodeposition process (248 ng cm^− 2) a roughness factor of 1.8 was calculated for the TiO₂ film.     

Kapitza resistance and thermal conductivity of Mylar at superfluid helium temperature

The Kapitza resistance and the thermal conductivity of type A Mylar sheets in the temperature range between 1.4 and 2.1 K have been determined. Four sheets with varying thickness from 37 μm to 255 μm, have been tested in steady-state condition. For a small temperature difference (10-30 mK) and heat flux density smaller than 30 Wm⁻², the total thermal resistance of the sheet is determined as a function of sheet thickness and bath temperature. The Kapitza resistance is given by R_K = (1.28 ± 0.08)T⁻³ × 10⁻³ Km² W⁻¹, and the thermal conductivity, κ = [(8.83 ± 0.75) + (11.73 ± 0.43) × T] × 10⁻³ Wm⁻¹ K⁻¹.     

Fe(CN)6 incorporation on Poly(3,4-ethylenedioxythiophene) films: Preparation and X-ray Photoelectron Spectroscopy characterization of the modified electrodes

Poly(3,4-ethylenedioxythiophene) (PEDOTh) films were potentiodynamically deposited on platinum from tetrabutylammonium hexafluorophosphate/acetonitrile solutions. Polymers prepared with different number of cycles showed reversible redox behaviour and the X-ray Photoelectron Spectroscopy (XPS) characterization revealed the existence of zones with different conductivity and confirmed the presence of PF₆⁻. The incorporation of the metallic complex Fe(CN)₆³⁻ in the PEDOTh films was made in one step, after the electrosynthesis of a film grown with a given number of potential cycles, and by means of polymerization/incorporation sequences. XPS data confirmed the presence of the inorganic species and the highest Fe 2p_3/2 peak intensity was observed for thin films (30 cycles) when the one step incorporation has been used. The XPS results suggest a partial dissociation of the Fe-(C-N) bond of the complex in the modified electrodes.     

The low temperature thermoelectric properties of CuxTiSe2−ySy

The low temperature thermoelectric properties of TiSe₂, co-doped with Cu and S, are reported. Partial S substitution for Se changes the magnitude of the indirect bandgap, while the Cu-doping independently controls the n-type carrier concentration. The Seebeck coefficients are negative, in the range of −50 to −200 μV K⁻¹, and the resistivities are 0.1-10 mΩ cm. The thermal conductivity for the sample with the largest thermoelectric power factor was found to be relatively low, 3-4 W m⁻¹ K⁻¹, and decreases with decreasing temperature. The thermoelectric efficiencies for the best materials found in this system, typified by Cu_0.02TiSe_1.7S_0.3, were largest at 0.07 at 300 K and decreased to 0.01 at 75 K.     

High temperature thermoelectric properties of (Ca, Ce)4Mn3O10

Thermoelectric (TE) properties such as resistivity (ρ), Seebeck coefficient (S), and thermal conductivity (κ) of Ca_4−3xCe_3xMn₃O₁₀ (0<x≤0.03) polycrystalline samples were measured from room temperature to 1000 K. ρ shows an obvious decrease with the increment of Ce content. The hopping conduction mechanism is used to explain the conduction behavior of these samples. The negative S values indicate that these materials are n-type. The sample of x=0.03 has the largest power factor, 0.52×10⁻⁴ Wm⁻¹ K⁻² at 1000 K. The value of κ and the dimensionless figure of merit of this sample is 1.51 Wm⁻¹ K⁻¹ and 0.034 at 1000 K, respectively.     

Rapid synthesis of homogeneous MnO2/multi-wall carbon nanotubes nanostructure and its electrochemical capacitive behavior

A homogeneous composite of MnO₂/multi-wall carbon nanotubes (MnO₂/MWCNTs) was rapidly and efficiently synthesized by a redox reaction of MnO₄⁻ and Mn²⁺ on the MWCNTs under ultrasonic irradiation. The structure and morphology of the obtained MnO₂ and MnO₂/MWCNTs composite were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and transmission electron microscopy. Electrochemical investigation indicated that the maximum specific capacitance of the MnO₂/MWCNTs composite, measured by galvanostatic charge-discharge test, was 315 F g^− 1, compared to the pristine MnO₂ (192 F g^− 1) and MWCNTs electrode (25 F g^− 1), showing the synergistic effect of MWCNTs and MnO₂. The homogeneous hybrid nanostructure and the good conductivity of MWCNTs were considered to be responsible for its preferable electrochemical performances.     

Preparation of nanostructured thin-film interfaces applicable in biosensors

Gold nanostructured thin-film electrodes (250 nm) were formed by using radio frequency (RF) diode sputtering, bias sputtering and ion etching. Biosensors based on the deoxyribonucleic acid (DNA) film immobilized at the gold surface were prepared by double-stranded DNA (dsDNA) adsorption. The behaviour of the DNA layer was investigated by using differential pulse voltammetry (DPV) with the DNA marker Co[(phen)₃]³⁺ and cyclic voltammetry (CV) with the K₃[Fe(CN)₆] indicator and DNA-Co[(phen)₃]³⁺ dissociation rate constant (k). The best result of attachment DNA binding were obtained in case of both sputtered sample only and the sample which was etched for 10 min at 150 °C.     

Thermal stability of the Mobil Five type metallosilicate molecular sieves—An in situ high temperature X-ray diffraction study

We have carried out in situ high temperature X-ray diffraction (HTXRD) studies of silicalite-1 (S-1) and metallosilicate molecular sieves containing iron, titanium and zirconium having Mobil Five (MFI) structure (iron silicalite-1 (FeS-1), titanium silicalite-1 (TS-1) and zirconium silicalite-1 (ZrS-1), respectively) in order to study the thermal stability of these materials. Isomorphous substitution of Si⁴⁺ by metal atoms is confirmed by the expansion of unit cell volume by X-ray diffraction (XRD) and the presence of Si-O-M stretching band at ∼960 cm⁻¹ by Fourier transform infrared (FTIR) spectroscopy. Appearance of cristobalite phase is seen at 1023 and 1173 K in S-1 and FeS-1 samples. While the samples S-1 and FeS-1 decompose completely to cristobalite at 1173 and 1323 K, respectively, the other two samples are thermally stable upto 1623 K. This transformation is irreversible. Although all materials show a negative lattice thermal expansion, their lattice thermal expansion coefficients vary. The thermal expansion behavior in all samples is anisotropic with relative strength of contraction along ‘a’ axes is more than along ‘b’ and ‘c’ axes in S-1, TS-1, ZrS-1 and vice versa in FeS-1. Lattice thermal expansion coefficients (α_v) in the temperature range 298-1023 K were −6.75 × 10⁻⁶ K⁻¹ for S-1, −12.91 × 10⁻⁶ K⁻¹ for FeS-1, −16.02 × 10⁻⁶ K⁻¹ for TS-1 and −17.92 × 10⁻⁶ K⁻¹ for ZrS-1. The highest lattice thermal expansion coefficients (α_v) obtained were −11.53 × 10⁻⁶ K⁻¹ for FeS-1 in temperature range 298-1173 K, −20.86 × 10⁻⁶ K⁻¹ for TS-1 and −25.54 × 10⁻⁶ K⁻¹ for ZrS-1, respectively, in the temperature range 298-1623 K. Tetravalent cation substitution for Si⁴⁺ in the lattice leads to a high thermal stability as compared to substitution by trivalent cations.     

Synergistic Interface-Assisted Electrode–Electrolyte Coupling Toward Advanced Charge Storage

Owing to the limited charge storage capability of transitional metal oxides in aqueous electrolytes, the use of redox electrolytes (RE) represents a promising strategy to further increase the energy density of aqueous batteries or pseudocapacitors. The usual coupling of an electrode and an RE possesses weak electrode/RE interaction and weak adsorption of redox moieties on the electrode, resulting in a low capacity contribution and fast self-discharge. In this work, Fe(CN)₆⁴⁻ groups are grafted on the surface of Co₃O₄ electrode via formation of Co N bonds, creating a synergistic interface between the electrode and the RE. With such an interface, the coupled Co₃O₄–RE system exhibits greatly enhanced charge storage from both Co₃O₄ and RE, delivering a large reversible capacity of ≈1000 mC cm⁻² together with greatly reduced self-discharge. The significantly improved electrochemical activity of Co₃O₄ can be attributed to the tuned work function via charge injection from Fe(CN)₆⁴⁻, while the greatly enhanced adsorption of K₃Fe(CN)₆ molecules is achieved by the interface induced dipole–dipole interaction on the liquid side. Furthermore, this enhanced electrode–electrolyte coupling is also applicable in the NiO–RE system, demonstrating that the synergistic interface design can be a general strategy to integrate electrode and electrolyte for high-performance energy storage devices.     

Amperometric biosensor based on direct electrochemistry of hemoglobin in poly-allylamine (PAA) film

Hemoglobin (Hb) was immobilized in poly-allylamine (PAA) film onto the gold electrode by layer by layer (LBL) method. The modified electrode exhibited a pair of well-defined peaks during cyclic voltammetry, which was attributed from the direct electron transfer of heme proteins. The immobilized Hb showed an excellent electrocatalytical response to the reduction of hydrogen peroxide. The sensor exhibited a fast response and high sensitivity. Through the use of optimized conditions, the linear range for H₂O₂ detection was from 2.5 × 10^− 6 M to 5 × 10^− 4 M with detection limit of 0.2 μM. The proposed biosensor showed long-lasting stability and excellent reproducibility.     

Characterization of Er and Nd doped Strontium Barium Niobate glass ceramic as temperature sensors

Temperature sensor is a vast group of the commercially approachable optical sensors. Recently has appeared a new kind of these devices using the fluorescence intensity ratio (FIR) with a very good sensitivity. The FIR technique has been carried out in Strontium Barium Niobate (SBN) glass ceramic sample to extend the knowledge of this kind of matrix. The samples has been doped with Erbium and Neodymium ions (2.5 mol%). The thermalized level ⁴S_3/2 (²H_11/2) of Er³⁺ ions was studied in a wide temperature range from 300 K to 700 K with a maximum sensitivity of 0.0017 K⁻¹ for 600 K. In these ions the FIR technique has been applied to the transitions ²H_11/2 → ⁴I_13/2 and ⁴S_3/2 → ⁴I_13/2 at 800 nm and 850 nm, respectively. The weak overlap between these thermalized emission bands is an important factor to reduce the error in the measurements. In the Nd³⁺ doped sample, the emission bands corresponding to the ⁴F_5/2 → ⁴I_9/2 and ⁴F_3/2 → ⁴I_9/2 transitions were analyzed as a function of the temperature from 300 K to 700 K with a maximum sensitivity of 0.0015 K⁻¹ for 600 K. These results are compared with other optical devices using FIR technique.     

Ion beam mixing of Co/Fe multilayers: Magnetic and structural properties

[Co(7 nm)/Fe(7 nm)]₆ multilayers were electron-beam evaporated onto Si(100) substrates in ultrahigh vacuum and irradiated at room temperature with 200-keV Xe ions, leading to ion beam mixing within the Co/Fe multilayer, but not with the Si substrate. Irradiation-induced changes in structural and magnetic properties were characterized by means of Rutherford backscattering spectroscopy, X-ray diffraction and in-plane magneto-optical Kerr effect. Irradiation with 1 × 10¹⁶ Xe ions/cm² induced Co/Fe intermixing to a 1 : 1 atomic concentration ratio (RBS) and the formation of the Fe₅₀Co₅₀ permendur phase in the intermixed zone (XRD). For lower ion fluences, the coercivity decreased strongly, but then increased slowly for higher fluences. The angular pattern of the relative remanence showed a perfect uniaxial anisotropy. The magnetic energy density was parametrized with the expression E_s / M_s ∝ (K_u1 / M_s) sin²(φ − φ₀) + (K_u2 / M_s) sin⁴(φ − φ₀), M_s being the saturation magnetization and φ₀ the symmetry angle. The second-order term K_u2 / M_s was found to decrease strongly with increasing Xe fluence.     

In-situ monitoring of the time evolution of the effective thermal conductivity of snow

We report on a 3-month long time series of in-situ measurements of the effective thermal conductivity (k_eff) of snow at 6 heights in an Alpine snowpack in the Mont-Blanc mountain range, France, at an altitude of 2400 m. Measurements were carried out automatically every 2 days using heated-needle probes embedded in the snowpack. The experimental procedure used is presented in detail and demonstrates the applicability of single heated-needle probes for the evaluation of k_eff in snow, both for long-term measurements within the snowpack and occasional use in the field. Results based on 139 automatically collected data show k_eff values ranging between 0.04 and 0.35 W m^− 1 K^− 1, and a consistent pattern of effective thermal conductivity increase throughout the measurements campaign. The temporal rate of change of k_eff varies up to 0.01 W m⁻¹ K^− 1day^− 1, with maximum values just after snowfall.     

Influence of SnO2 addition on the thermoelectric properties of Zn1 − xSnxO (0.01 ≤ x ≤ 0.05)

The grain size and the density of the Zn_1 − xSn_xO (0 ≤ x ≤ 0.05) samples decreased with increasing SnO₂ content. The addition of a small amount of SnO₂ (x ≤ 0.01) to ZnO led to an increase in both the electrical conductivity and the absolute value of the Seebeck coefficient, resulting in a significant increase in the power factor. The thermoelectric power factor was maximized to a value of 1.25 × 10⁻³ Wm⁻¹ K⁻² at 1073 K for the Zn_0.99Sn_0.01O sample.