Hydrogen peroxide biosensor based on gold nanoparticles/thionine/gold nanoparticles/multi-walled carbon nanotubes-chitosans composite film-modified electrode

In this paper, an amperometric electrochemical biosensor for the detection of hydrogen peroxide (H₂O₂), based on gold nanoparticles (GNPs)/thionine (Thi)/GNPs/multi-walled carbon nanotubes (MWCNTs)-chitosans (Chits) composite film was developed. MWCNTs-Chits homogeneous composite was first dispersed in acetic acid solution and then the GNPs were in situ synthesized at the composite. The mixture was dripped on the glassy carbon electrode (GCE) and then the Thi was deposited by electropolymerization by Au-S or Au-N covalent bond effect and electrostatic adsorption effect as an electron transfer mediator. Finally, the mixture of GNPs and horseradish peroxidase (HRP) was assembled onto the modified electrode by covalent bond. The electrochemical behavior of the modified electrode was investigated by scanning electron microscope, cyclic voltammetry and chronoamperometry. This study introduces the in situ-synthesized GNPs on the other surface of the modified materials in H₂O₂ detection. The linear response range of the biosensor to H₂O₂ concentration was from 5 × 10⁻⁷ mol L⁻¹ to 1.5 × 10⁻³ mol L⁻¹ with a detection limit of 3.75 × 10⁻⁸ mol L⁻¹ (based on S/N = 3).     

Study of optical nonlinearity of functionalized multi-wall carbon nanotubes by using degenerate four wave mixing and Z-scan techniques

The phase conjugation geometry of degenerate four wave mixing (DFWM) technique has been employed to study the third-order optical nonlinear susceptibility (χ³) and second-order hyperpolarizability of multi-wall carbon nanotubes (MWCNTs). MWCNTs were grown by thermal chemical vapor deposition method and, subsequently functionalized with carboxylic acid group to improve their solubility in an organic solvent, ethylene glycol. The average hyperpolarizability for each carbon atom has been found to be 4.74 × 10⁻⁴⁶ m⁵/V² for the pump pulse of 8 ns at 532 nm. Decreasing the pulse width of the pump laser decreases the average value of hyperpolarizability. The absorption spectra show a monotonous increase from IR through visible and give an opportunity to estimate the imaginary part of the χ³ by the open aperture Z-scan technique.     

Heat capacities of the electron acceptor 7,7,8,8-tetracyano- quinodimethane (TCNQ) and its radical-ion salt NH4(TCNQ) showing spin-Peierls transition

Heat capacities of the electron acceptor 7,7,8,8-tetracyanoquinodimethane (TCNQ) and its radical-ion salt NH₄-TCNQ have been measured at temperatures in the 12-350 K range by adiabatic calorimetry. A λ-type heat capacity anomaly arising from a spin-Peierls (SP) transition was found at 301.3 K in NH₄-TCNQ. The enthalpy and entropy of transition are Δ_trsH=(667±7) J mol⁻¹ and Δ_trsS=(2.19±0.02) J K⁻¹ mol⁻¹, respectively. The SP transition is characterized by a cooperative coupling between the spin and the phonon systems. By assuming a uniform one-dimensional antiferromagnetic (AF) Heisenberg chains consisting of quantum spin (S=1/2) in the high-temperature phase and an alternating AF nonuniform chains in the low-temperature phase, we estimated the magnetic contribution to the entropy as Δ_trsS_mag=0.61 J K⁻¹ mol⁻¹ and the lattice contribution as Δ_trsS_lat=1.58 J K⁻¹ mol⁻¹. Although the total magnetic entropy expected for the present compound is R ln 2 (=5.76 J K⁻¹ mol⁻¹), a majority of the magnetic entropy (∼4.6 J K⁻¹ mol⁻¹) persists in the high-temperature phase as a short-range-order effect. The present thermodynamic investigation quantitatively revealed the roles played by the spin and the phonon at the SP transition. Standard thermodynamic functions of both compounds have also been determined.     

Electrochemical properties of α-Fe2O3 /MWCNTs as anode materials for lithium-ion batteries

α-Fe₂O₃/MWCNTs composites were prepared by a simple hydrothermal process. The crystalline structure and the electrochemical performance of the as-synthesized samples were investigated. Results show that as anode materials for lithium-ion batteries, the α-Fe₂O₃/MWCNTs exhibit an initial discharge capacity of 1256 ± 5 mAh g⁻¹ and a stable specific discharge capacity of 430 ± 5 mAh g⁻¹ at ambient temperature, for up to 100 cycles with no noticeable capacity fading, while the initial discharge capacity of the bare Fe₂O₃ is 992.3 mAh g⁻¹, and the discharge capacity is 146.6 mAh g⁻¹ after 100 cycles. Moreover, the α-Fe₂O₃/MWCNTs composites also exhibit excellent rate performance.     

Preparation, structure and oxide ion conductivity in Ce6−xYxMoO15−δ (x=0.1-1.4) solid solutions

The Ce_6−xY_xMoO_15−δ solid solution with fluorite-related structure have been characterized by differential thermal analysis/thermogravimetry (DTA/TG), X-ray diffraction (XRD), IR, Raman, scanning electric microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) methods. The electric conductivity of samples is investigated by Ac impedance spectroscopy. An essentially pure oxide-ion conductivity of the oxygen-deficiency was observed in pure argon, oxygen and air. The highest oxygen-ion conductivity was found in Ce_5.5Y_0.5MoO_15−δ ranging from 5.9×10⁻⁵ (S cm⁻¹) at 300 °C to 1.3×10⁻² (S cm⁻¹) at 650 °C, respectively. The oxide-ion conductivities remained stable over 80 h-long test at 800 °C. These properties suggested that significant oxide-ionic conductivity exists in these materials at moderately elevated temperatures.     

Optical emission spectroscopy investigation of sputtering discharge used for SiOxNy thin films deposition and correlation with the film composition

The r.f. discharge of sputtering silicon target using argon-oxygen-nitrogen plasma was investigated by optical emission spectroscopy. Electronic temperature (T_e) and emission line intensity were measured for different plasma parameters: pressure (from 0.3 to 0.7 Pa), power density (0.6-5.7 W cm⁻²) and gas composition. At high oxygen concentration in the plasma, both T_e and the target self-bias voltage (V_b) steeply decrease. Such behaviour traduces the target poisoning phenomenon. In order to control the deposition process, emission line intensity of different species present in the plasma were compared to the ArI (λ = 696.54 nm) line intensity and then correlated to the film composition analysed by Rutherford Backscattering Spectroscopy.     

Thermal annealing effect on the crystallization and optical dispersion of sprayed V2O5 thin films

Polycrystalline vanadium pentoxide (V₂O₅) thin films have been deposited by spray pyrolysis technique on preheated glass substrate. The influence of thermal annealing on the crystallization of V₂O₅ has been investigated. X-ray diffraction analysis (XRD) revealed that the films deposited at T_sub=350 °C were orthorhombic structures with a preferential orientation along 〈0 0 1〉 direction. Moreover, the degree of crystallinity was improved by thermal annealing. Optical properties of these samples were studied by spectrophotometer in the wavelength range 300-2500 nm. Some of the important optical absorptions such as optical dispersion energies E_o and E_d, dielectric constant ε, ratio between number of charge carriers and effective mass N/m^*, wavelength of single oscillator λ₀, plasma frequency ω_p, single resonant frequency ω₀ and the average of oscillator strength S_o, have been evaluated. In the annealing process, the dielectric properties have weak dependencies of film thickness and annealing time. Furthermore, a value of carrier concentration was obtained of 3.02×10²⁵ m⁻³ for the as-deposited film and slight changes with annealing time.     

MgB2 fabrication by diffusion-controlled three layered (B-Mg-B) technique

MgB₂ was successfully fabricated through diffusion-controlled three-layered (B-Mg-B) technique under high pressure. Due to melting temperature of Mg, the material was pre-heat treated at 600 °C between 1 and 48 h. Optimum pre-heat treatment condition was found to be 600 °C for 48 h. Then, the compacted material was grinded and pelletized under pressure of 2 ton. The pellets were heat treated at 600-900 °C for 1-48 h. Optimum heat treatment condition was determined to be 800 °C for 1 h for formation of almost pure MgB₂. Diffusion coefficient was determined with Fick's law and EDX data. Diffusion coefficient value for B in Mg matrix and Mg in B matrix was determined to be 1.66×10⁻⁷ and 3.14×10⁻⁸ cm²/sn, respectively. Best T_c value (39.4 K) was obtained for material heat treated at 800 °C for 1 h. A symmetric hysteresis was obtained for the best MgB₂ material and magnetization decreased with increase in the temperature and the applied magnetic field.     

Propagation regimes of intense circularly polarized laser beam in magnetoactive plasma

This paper presents an analytical and numerical investigation of an intense circularly polarized wave propagating along the static magnetic field parallel to oscillating magnetic field in magnetoactive plasma. In the relativistic regime such a magnetic field is created by pulse itself. The authors have studied different regimes of propagation with relativistic electron mass effect for magnetized plasma. An appropriate expression for dielectric tensor in relativistic magnetoactive plasma has been evaluated under paraxial theory. Two modes of propagation as extraordinary and ordinary exist; because of the relativistic effect, ultra-strong magnetic fields are generated which significantly influence the propagation of laser beam in plasma. The nature of propagation is characterized through the critical-divider curves in the normalized beam width with power plane For given values of normalized density (ω_p/ω) and magnetic field (ω_c/ω) the regions are namely steady divergence (SD), oscillatory divergence (OD) and self-focusing (SF). Numerical computations are performed for typical parameters of relativistic laser-plasma interaction: magnetic field B = 10-100 MG; intensity I = 10¹⁶ to 10²⁰ W/cm²; laser frequency ω = 1.1 × 10¹⁵ s⁻¹; cyclotron frequency ω_c = 1.7 × 10¹³ s⁻¹; electron density n_e = 2.18 × 10²⁰ cm⁻³. From the calculations, we confirm that a circularly polarized wave can propagate in different regimes for both the modes, and explicitly indicating enhancement in wave propagation, beam focusing/self-guiding and penetration of E-mode in presence of magnetic field.     

Heat capacity of paramagnetic nickelocene: Comparison with diamagnetic ferrocene

Nickelocene [bis(η⁵-cyclopentadienyl)nickel: Ni(C₅H₅)₂, electron spin S=1, the ground state configuration ³A_2g] is paramagnetic and belongs to a typical molecule-based magnet. Heat capacities of nickelocene have been measured at temperatures in the 3−320 K range by adiabatic calorimetry. By comparing with those of diamagnetic ferrocene crystal, a small heat capacity peak centered at around 15 K and a sluggish hump centered at around 135 K were successfully separated. The low-temperature peak at 15 K caused by the spin is well reproduced by the Schottky anomaly due to the uniaxial zero-field splitting of the spin S=1 with the uniaxial zero-field splitting parameter D/k=45 K (k: the Boltzmann constant). The magnetic entropy 9.7 J K⁻¹ mol⁻¹ is substantially the same as the contribution from the spin-manifold R ln 3=9.13 J K⁻¹ mol⁻¹ (R: the gas constant). The sluggish hump centered at around 135 K arises from rotational disordering of the cyclopentadienyl rings of nickelocene molecule. The enthalpy and entropy gains due to this anomaly are 890 J mol⁻¹ and 6.9 J K⁻¹ mol⁻¹, respectively. As the hump spreads over a wide temperature region, separation of the hump from the observed heat capacity curve involves a little bit ambiguity. Therefore, these values should be regarded as being reasonable but tentative. The present entropy gain is comparable with 5.5 J K⁻¹ mol⁻¹ for the sharp phase transition at 163.9 K of ferrocene crystal. This fact implies that although the disordering of the rings likewise takes place in both nickelocene and ferrocene, it proceeds gradually in nickelocene and by way of a cooperative phase transition in ferrocene. A reason for this originates in loose molecular packing in nickelocene crystal. Molar heat capacity and the standard molar entropy of nickelocene are larger than those of ferrocene beyond the mass effect over the whole temperature region investigated. This fact provides with definite evidences for the loose molecular packing in nickelocene crystal.     

Selective MOCVD of titanium oxide and zirconium oxide thin films using single molecular precursors on Si(1 0 0) substrates

Titanium oxide (TiO₂) and zirconium oxide (ZrO₂) thin films have been deposited on modified Si(1 0 0) substrates selectively by metal-organic chemical vapor deposition (MOCVD) method using new single molecular precursor of [M(OⁱPr)₂(tbaoac)₂] (M=Ti, Zr; tbaoac=tertiarybutyl-acetoacetate). For changing the characteristic of the Si(1 0 0) surface, micro-contact printing (μCP) method was adapted to make self-assembled monolayers (SAMs) using an octadecyltrichlorosilane (OTS) organic molecule which has -CH₃ terminal group. The single molecular precursors were prepared using metal (Ti, Zr) isopropoxide and tert-butylacetoacetate (tbaoacH) by modifying standard synthetic procedures. Selective depositions of TiO₂ and ZrO₂ were achieved in a home-built horizontal MOCVD reactor in the temperature range of 300-500 °C and deposition pressure of 1×10⁻³-3×10⁻² Torr. N₂ gas (5 sccm) was used as a carrier gas during film depositions. TiO₂ and ZrO₂ thin films were able to deposit on the hydrophilic area selectively. The difference in surface characteristics (hydrophobic/hydrophilic) between the OTS SAMs area and the SiO₂ or Si-OH layer on the Si(1 0 0) substrate led to the site-selectivity of oxide thin film growth.     

Synthesis, characterization and cytotoxicity of surface amino-functionalized water-dispersible multi-walled carbon nanotubes

Surface functionalization of multi-walled carbon nanotubes (MWCNTs), with amino groups via chemical modification of carboxyl groups introduced on the nanotube surface, using O-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium hexafluorophosphate (N-HATU) and N,N-diisopropylethylamine (DIEA) is reported. The N-HATU coupling agent provides faster reaction rate and the reaction occurs at lower temperature compared to amidation and acylation-amidation chemistry. The amines, 1,6-hexanediamine (HDA), diethylenetriamine (DETA), triethylenetetramine (TETA) and 1,4-phenylenediamine (PDA) were used. The resulting materials were characterized with different techniques such as FTIR, XRD, elemental analysis, TGA, TEM, UV-vis spectroscopy and cyclic voltammetry. MWCNTs functionalized with PDA posses the best dispersibility and electron transfer properties in comparison to the others amines. Functionalized MWCNTs, at the concentrations between 1 and 50 μg ml⁻¹, were not cytotoxic for the fibroblast L929 cell line. However, the concentrations of MWCNTs higher of 10 μg ml⁻¹ reduced cell growth and this effect correlated positively with the degree of their uptake by L929 cells.     

Study of S ion-assisted sulfurization of n-GaAs (1 0 0) surface

The chemical structure and site location of sulfur atoms on n-GaAs (1 0 0) surface treated by bombardment of S⁺ ions over their energy range from 10 to 100 eV have been studied by X-ray photoelectron spectroscopy and low energy electron diffraction. The formation of Ga-S and As-S species on the S⁺ ion bombarded n-GaAs surface is observed. An apparent donor doping effect is observed for the n-GaAs by the 100 eV S⁺ ion bombardment. It is found that the S⁺ ions with higher energy are more effective in the formation of Ga-S species, which assists the n-GaAs (1 0 0) surface in reconstruction into an ordered (1 × 1) structure upon subsequent annealing. The treatment is further extended to repair Ar⁺ ion damaged n-GaAs (1 0 0) surface. It is found that after a n-GaAs (1 0 0) sample is damaged by 150 eV Ar⁺ ion bombardment, and followed by 50 eV S⁺ ion treatment and subsequent annealing process, finally an (1 × 1) ordering GaAs (1 0 0) surface with low surface states is obtained.     

The Raman spectroscopic studies of aligned MWCNTs treated under high pressure and high temperature

The study of the aligned multiwalled carbon nanotubes (MWCNTs) for interlinking bonding under high pressures and temperatures have been conducted in the diamond anvil cell. The MWCNT samples were analyzed using the Raman spectroscopy, when treated under the combinations of pressure and temperature ranges of 2-20 GPa and 25-500 °C. The analyses show the formation of interlinking bonding at a pressure above 2.5 GPa when treated under the temperature 500 °C, based on the significant change of the relative intensity between D- and G-bands in the Raman spectra. Comparisons of the data obtained before and after the high pressure and high temperature treatments are reported. The result indicates that the aligned MWCNTs may be easier to form the interlinking bonding compared to randomly oriented MWCNTs.     

Oxygen plasma functionalization of poly(p-phenilene sulphide)

Surface effects during plasma activation of poly(p-phenilene sulphide)—PPS have been studied. Samples that were exposed to weakly ionized highly dissociated oxygen plasma created an inductively coupled radiofrequency discharge with the power of 100 W. The electron density and temperature were measured with a double Langmuir probe and were 4 × 10¹⁵ m⁻³ and 3 eV, respectively, while the neutral atom density was measured with a fiber optics catalytic probe and was 4 × 10²¹ m⁻³. The surface tension was determined by measuring the contact angle of deionized water, while the appearance of surface functional groups was detected by XPS. The surface tension of untreated PPS was 7 × 10⁻³ N/m or/and increased to 7 × 10⁻² N/m in few seconds of plasma treatment. It remained fairly constant for longer plasma treatments. The XPS survey spectrum showed little oxygen on untreated samples, but its concentration increased to about 20 at.% in few seconds. Detailed high resolution XPS C 1s peak showed that the carbon was left fairly stable during plasma treatment. The main functional groups formed were rather sulphate in sulphite groups, as determined from high resolution S 2p peak. Namely, a strong transition from sulphide to sulphate state of sulfur was observed. The spontaneous deactivation of the polymer surface was measured as well. The deactivation was fairly logarithmic with the characteristic decay time of several hours.     

Impedance study of polymethyl methacrylate composites/multi-walled carbon nanotubes (PMMA/MWCNTs)

The dielectric behavior of polymethyl methacrylate/multi-walled carbon nanocomposites (PMMA/MWCNTs) was investigated using impedance spectroscopy technique. The composites were prepared using melt mixing with MWCNTs loading ranging from 0.01 to 10 wt%. The experimental results showed that the measured impedance reflects the insulating behavior of the host material (PMMA) with no appreciable effects of the filler less than 8.5 wt%. However, for the sample containing 10 wt%, the calculated value of dc conductivity increases with increasing temperature from 2.0×10⁻⁶ (Ω m)⁻¹ to attain a value of 4.8×10⁻⁶ (Ω m)⁻¹ at 110 °C. The percolation threshold derived from the dielectric data was estimated to be higher than 8.5 wt% and lower than 10 wt%. A temperature dependent electrical relaxation phenomenon was only observed in the sample containing 10 wt% of MWCNTs. The frequency dependence of the ac conductivity data followed a power law.     

Sliding tribological properties of untreated and PIII-treated PETP

Poly(ethylene terephthalate) (PETP) was treated by plasma immersion ion implantation (PIII or PI³) in nitrogen. The surface changes were characterised by XPS and water contact-angle measurements. Sliding tribological properties of untreated and nitrogen PIII-treated PETP against conventional low carbon structural steel S235 were studied under dry and water-lubricated conditions by a pin-on-disc tribometer.XPS results suggested the evolution of surface composition and bonding towards those of amorphous hydrogenated carbon-nitride. Water contact-angle decreased implying increased surface wettability. At a very low Pv factor (0.0075 MPa m s⁻¹) for the nitrogen PIII-treated PETP the dry friction coefficient was smaller than, while the lubricated friction coefficient was similar to, the corresponding value of the untreated variant. At higher Pv factors (near 0.1 MPa m s⁻¹), however, both the dry and lubricated friction coefficients were higher for the treated sample than for the untreated variant, suggesting an increased adhesion component of friction for the nitrogen PIII-treated PETP in this region.     

Crystallization studies on AgI-Ag2O-MoO3 superionic system synthesized by melt quenching and mechanical milling

Crystallization in the melt-quenched (MQ) and mechanically milled (MM) superionic systems has been thoroughly investigated using differential scanning calorimetry, X-ray diffraction and electrical conductivity measurements. It is observed that the two systems obey different crystallization processes. The conventionally melt-quenched samples exhibit only one crystallization peak near 112 °C, whereas, the mechanochemically synthesized samples show two well-separated crystallization peaks at T_cl∼75-97 °C and T_c2∼132±2 °C. The higher value of electrical conductivity in the mechanochemically synthesized samples (∼10⁻² Ω⁻¹ cm⁻¹ at 300 K) than the melt-quenched samples is attributed to the higher value of disorder (entropy) in the former.     

Novel chemical synthetic route and characterization of zinc selenide thin films

Zinc selenide (ZnSe) thin film have been deposited using chemical bath method on non-conducting glass substrate in a tartarate bath containing zinc sulfate, ammonia, hydrazine hydrate, sodium selenosulfate in an aqueous alkaline medium at 333 K. The deposition parameter of the ZnSe thin film is interpreted in the present investigation. The films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), optical absorption, electrical measurements, atomic absorption spectroscopy (AAS). The ZnSe thin layers grown with polycrystalline zinc blende system along with some amorphous phase present in ZnSe film. The direct optical band gap ‘E_g’ for the film was found to be 2.81 eV and electrical conductivity in the order of 10⁻⁸(Ω cm)⁻¹ with n-type conduction mechanism.     

Submillimeter-wave spectroscopy of HCO in the excited vibrational states

The pure rotational transitions of HCO⁺ in excited vibrational states located below 5000 cm⁻¹ over the ground state have been investigated with a high-sensitivity frequency/magnetic field double modulation submillimeter-wave spectrometer in the frequency range of 280-810 GHz. The ions were generated in an extended negative glow discharge through a gas mixture of a few millitorrs of H₂ and CO and 12 mTorr of Ar buffer gas. Throughout the experiments, the cell was maintained at liquid nitrogen temperature. In the present study, we have determined accurate molecular constants for the excited vibrational states. Our analysis suggests that there may be a higher order Coriolis interaction between the (0 3 1) and (1 2 0) states. In previous investigations, the Stark effect caused by the electric field present in the discharge plasma was cited as a reason for non-observations of low-J lines in the (02²0) and for the systematic shifts observed for low-J lines in the (01¹0), (02²0), (03¹0), and (04²0) states of HCO⁺ as well as DCO⁺. In the present investigation, some low-J lines in the (02²0) and (04²0) states have been observed in emission. Furthermore, J = 8-7, J = 9-8 lines in (03^1e1) were detected in emission. This finding indicates that missing low-J lines for the Δ sublevel obtained in the past is not due to the Stark effect but due to small population differences in those levels.