The electrochemical properties of thermophilic cytochrome P450 CYP119A2 at extremely high temperatures in poly(ethylene oxide)

The electrochemical measurements were carried out by using thermophilic cytochrome P450 CYP119A2 (P450st) modified with poly(ethylene oxide) (PEO) in PEO₂₀₀ as an electrochemical solvent. The PEO modified P450st gave clear reduction–oxidation peaks by cyclic voltammetry in oxygen-free PEO₂₀₀ up to 120 °C. The midpoint potential measured for the P450st was −120 mV vs. [Fe(CN)₆]⁴⁻/[Fe(CN)₆]³⁻ at 120 °C. The peak separation, ΔE, was 16 mV at 100 mV/s. The estimated electron transfer rate of PEO-P450st at 120 °C was 35.1 s⁻¹. The faster electron transfer reaction was achieved at higher temperatures. The electrochemical reduction of dioxygen was observed at 115 °C with the PEO-modified P450st system.     

Cathodoluminescence study of defects in thermal treatment of zinc titanate thin films deposited by a cosputtering process

The effects of thermal treatment of polycrystalline ZnO–TiO₂ systems on their luminescence emission and phase properties were investigated using ex situ cathodoluminescence and backscattering electron microscopy. The main features of the spectrum are a blue band at 2.75 eV for the phase of TiO and a complex visible band at 2.18 eV for the phase of ZnO, whose peak intensity depends on the annealing temperature. The spectrum intensity is dominated by the ZnO phase when annealing temperature was 720°C, which is attributed to abnormal grain growth. Competition is observed between the broad band peaked at 2.18 eV and visible band peaked at 2.75 eV as the annealing temperature changed (820°C‐920°C). The cathodoluminescence density is gradually governed by the TiO₂ phase, and the emission in polychromatic and monochromatic imaging is stronger equally at 920°C. The nucleation of the TiO₂ and ZnO grains is present in the backscattering electron images as well.     

Structural and electronic properties of HfO2 films on Si through H2O2 wet oxidation with improved thermal stability

The thermal stability and material properties of HfO₂ thin films on Si substrates with and without H₂O₂ wet chemical oxidation were investigated. The HfO₂ samples were deposited through plasma-enhanced atomic layer deposition and subjected to thermal annealing. They were then examined using X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, reflection electron energy loss spectroscopy, and conductive atomic force microscopy. For the Si substrate without H₂O₂ wet chemical oxidation, a native oxide (~1.8 nm) was formed on the substrate before HfO₂ deposition. After the annealing process at 600°C, the band gap (E_g) of the HfO₂ films increased from 6.0 to 6.2 eV due to the diffusion of Si into HfO₂. Furthermore, the conduction and valence band offsets (ΔE_c and ΔE_v, respectively) between HfO₂ and Si changed from 1.02 to 1.42 and 3.86 to 3.66 eV, respectively. After the H₂O₂ wet oxidation of the Si substrate, a 1.5-nm chemical oxide was formed instead of a native oxide. The band offset and E_g values of HfO₂ were similar before and after 600°C annealing (ΔE_v = 3.86 eV, ΔE_c = 1.02 eV, and E_g = 6.0 eV), implying the high thermal stability of the HfO₂ films. Accordingly, wet oxidation not only prevents diffusion from chemical oxide but also markedly improves the oxide leakage current, which is useful for developing highly efficient and thermally stable HfO₂ gate oxides in Si-based integrated circuit devices.     

Catalytic transformation of silicon tetraisocyanate Si(NCO)4 to a polymeric silylcarbodiimide

A new way for the preparation of inorganic polymeric carbodiimide‐based networks is presented which resembles the transformation of molecular isocyanates using 1‐phenyl‐3‐methyl‐2‐phospholene‐1‐oxide as a catalyst. The respective reaction sequence, well established in preparative organic chemistry, has been applied for the synthesis of carbodiimide‐based SiNC(O) materials. Starting from Si(NCO)₄ (silicon tetraisocyanate), a transformation to an insoluble extended inorganic array was achieved in boiling dodecan (T = 216 °C). Analysis of the polymer using X‐ray diffraction, FT‐IR, density measurement, matrix‐assisted laser desorption/ionization time of flight and TGA revealed that this highly moisture‐sensitive amorphous network consists of oligomers of high molar mass and exhibits a high density of around 1.5 g cm^?3, which corresponds quite well to the calculated density of crystalline Si(NCN)₂ reported in the literature. Degradation of this 'SiNC(O) phase' with the release of N₂ and (CN)₂ finally provided SiC as the only crystalline product. No indication of the formation of crystalline Si₃N₄ or intermediate crystalline 'SiC₂N₄', silicon carbodiimide (= Si(NCN)₂), was noticed. Copyright © 2013 John Wiley & Sons, Ltd.     

Modifying transparent electrode with conjugated organic semiconductor hole transport material as interface for enhancing performance of organic solar cell

Indium tin oxide (ITO) is used as a substrate was covered with 4-[4-(4-methoxy-N-naphthalen-2-ylanilino) phenyl] benzoic acid (MNA) as a self-assembled monolayer (SAM). Poly(3-hexylthiophene) (P3HT) and 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6) C₆₁ (PCBM) were mixed and used as a donor–acceptor in organic solar cell (OSC). The MNA (SAM) layer is used as an interface instead of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT: PSS) for hole injection. The HOMO-LUMO energy level of MNA-SAM molecule and the electronic charge distribution were calculated theoretically using Chemissian software. The HOMO-LUMO energy level of the MNA is calculated as E_HOMO = ?5.10 eV and E_LUMO = ?1.60 eV. The OSC modified with MNA showed an efficient performance in the absence of PEDOT: PSS as hole transport layer. The annealing of the ITO/SAM/P3HT: PCBM films at different temperatures are also investigated to study the effect of reducing defects. The interface structures of the organic semiconductor layer on ITO were characterized by Atomic Force Microcopy (AFM). In addition, Kelvin Probe Microscopy (KPM) is used to understand how the annealing changes the surface potential energy of the ITO/SAM substrate. Using the KPM method, which measures the surface potential energy of the films, the energy bands of the ITO were increased to maximum 5.09 eV. The ITO/SAM/P3HT: PCBM film's surface potential was determined to be 0.18 eV after being annealed at 80 °C. The surface potential of the modified films was discovered to be 0.33 V and 0.39 V when the annealing temperature was raised from 80 °C to 120 °C and 160 °C. The maximum device efficiency was demonstrated by the ITO/SAM/P3HT: PCBM film after an hour of annealing at 160 °C.     

Dielectric and magnetic properties of multiferroic BiFeO3 ceramics sintered with the powders prepared by hydrothermal method

BiFeO₃ ceramics were sintered in the temperature range of 700–900 °C by using the pure BiFeO₃ powders hydrothermally synthesized at 250 °C. The low reaction temperature and low sintering temperature prevent the element volatilization and phase decomposition. The ceramics sintered at 800 and 850 °C exhibit much dense microstructure with clear grains and grain boundaries. They also show high dielectric constant, dielectric dispersion and low loss tangent. At room temperature, the dielectric behaviors of BiFeO₃ ceramics are mainly attributed to the transition of localized charge carriers and the microstructure of grains and grain boundaries. The temperature dependence of dielectric constant and loss tangent confirms that the localized charge carriers are a main contribution to the dielectric permittivity. Activation energy E_α of relaxation process for the BiFeO₃ ceramic sintered at 850 °C is 0.397 eV. The obtained BiFeO₃ ceramics show magnetic responses, which are relative to the grain size.     

Synthesis,structure, physical properties,and electronic structure of KGaSe2

The ternary gallium selenide KGaSe₂ has been synthesized by solid-state reactions and good quality crystal has been obtained. KGaSe₂ crystallizes in the monoclinic space group C2/c with cell dimensions of a = 10.878(2) Å, b = 10.872(2) Å, c = 15.380(3) Å, and β = 100.18(3)°. In the structure, adamantane like [Ga₄Se₁₀]⁸⁻ units are connected by common corners forming two-dimensional [GaSe₂]⁻ layers which are separated by K⁺ cations. KGaSe₂ exhibits congruent-melting behavior at around 965 °C. It is transparent in the range of 0.47–20.0 μm and has a band gap of 2.60(2) eV. From a band structure calculation, KGaSe₂ is a direct-gap semiconductor. The band gap is mainly determined by the [GaSe₂]⁻ layer.     

Structural and optical properties of ZnO thin films by the spin coating Sol-Gel method

ZnO thin films were deposited onto glass subsrates by a Sol-gel spin coating method. The structural and optical properties of ZnO thin films were investigated. The molar ratios of the zinc acetate dihydrate to Monoethanolamine were maintained 1:1. The as-grown film was sintered 250 °C for 10 min, then annealed in air at 500 °C for 30 min. The XRD results indicate that ZnO films were strongly oriented to the c-axis of the hexagonal nature. Absorption measurements were carried out as a function of temperature with 10 K steps in the range 10–320 K. The band gap energy was measured 3.275 and 3.267 eV for 0.5 and 1.0 molarity (M) ZnO thin films at 300 K. The steepness parameters were observed between 10 and 320 K and their extrapolations converged at (E₀, α₀) = 3.65 eV, 172,819 cm⁻¹ and 3.70 eV, 653,436 cm⁻¹ for 0.5 and 1.0 M ZnO thin films, respectively.     

Effect of sol temperature on the structure,morphology, optical and photoluminescence properties of nanocrystalline zirconia thin films

Transparent nanocrystalline zirconia thin films were prepared by sol–gel dip coating technique using Zirconium oxychloride octahydrate as source material on quartz substrates, keeping the sol at room temperature (SET I) and 60 °C (SET II). X-ray diffraction (XRD) pattern shows the formation of mixed phase [tetragonal (T) + monoclinic (M)] in SET I and a pure tetragonal phase in SET II ZrO₂ thin films annealed at 400 °C. Phase transformation from tetragonal to monoclinic was achieved in SET II film annealed at 500 °C. Atomic force microscopy analysis reveals lower rms roughness and skewness in SET II film annealed at 500 °C indicating better optical quality. The transmittance spectra gives a higher average transmittance >85% (UV–VIS region) in SET II films. Optical spectra indicate that the ZrO₂ films contain direct—band transitions. The sub- band in the monoclinic ZrO₂ films introduced interstitial O⁻defect states above the top of the valance band. The energy bandgap increased (5.57–5.74 eV) in SET I films and decreased (5.74–5.62 eV) in SET II films, with annealing temperature. This is associated with the variations in grain sizes. Photoluminescence (PL) spectra give intense band at 384 and 396 nm in SET I and SET II films, respectively. A twofold increase in the PL intensity is observed in SET II film. The “Red” shift of SET I films and “Blue” shift of SET II films with annealing temperature, originates from the change of stress of the film due to lattice distortions.     

Enhanced electrical conductivity in Ce0.79Gd0.20Co0.01O2−δ for low temperature solid oxide fuel cell applications

Very high electrical conductivity of ～0.021 S/cm at 600 °C is obtained in Ce_0.79Gd_0.20Co_0.01O_2?δ. Corresponding activation energy of conduction ～0.43 eV measured in the temperature range of 400–700 °C is found to be notably low. Improved electrical properties with 99% of the theoretical density as obtained for these specimens, prepared using powder of average particle size ～20 nm and subsequent sintering at 1100 °C, is considered to be a significant step to reduce the processing temperature. The measured electrical potential of ～1 V indicates the suitability of its use as an electrolyte in electrochemical devices.     

Synthesis and photovoltaic property of polymer semiconductor with phthalimide derivative as a promising electron withdrawing material

Donor–acceptor type (DA-type) polymeric photovoltaic material with a dicarboxylic imide-substituted benzene (phthalimide) derivative as electron-withdrawing units, poly[4,4′-didodecyl-2,2′-bithiophene-co-5,5′-(3,6-bis(thieno-2-yl)-N-octyl-phthalimide] (PDBTTPT), was synthesized by a Stille coupling reaction. It had an optical band gap of 1.96 V and a relatively low HOMO energy level of ?5.34 eV in spite of it being a thiophene-based polymer. Photovoltaic devices with PDBTTPT/PC₇₁BM active layers were fabricated under a variety of conditions for optimizing device performance. PDBTTPT exhibited the best power conversion efficiency (PCE) of 1.5% in the device where 80 wt.% of the PC₇₁BM was contained in the active layer (PDBTTPT:PC₇₁BM = 1:4, w/w) and which was pre-annealed at 120 °C for 10 min. In addition, a device which was pre-annealed at 140 °C for 10 min and a device which was post-annealed at 120 °C for 10 min showed analogous PCE values of 1.5% as well, although small differences were exhibited between various parameters, such as V_OC, J_SC, and FF.     

The influence of precursor temperature on strontium sulphide doped silver for optoelectronic application

This research aims at the study of strontium sulphide doped silver using 0.1 mol of strontium chloride hexahydrate (SrCl2.6H2O), Thioacetamide (C₂H₅NS), and 0.01 mol of silver nitrate (AgNO3) as the cationic, anionic, and dopant concentrations via electrochemical deposition technique. The film had a strong peak at (111) and (211) which corresponds to 2theta values of 26.69° and 51.77° for undoped SrS and doped SrS respectively, and a flawless crystalline peak with a cubic phase that is indexed at orientations (111), (112), (200), and (211). SrS/Ag of deposited different precursor temperatures (room, 35, 40, and 45)^o correspond to 2theta values of 26.69°, 33.79°, 37.60°, and 51.77° respectively. The crystal lattice is shown by the rise in peak intensity with higher 2theta degree values; the appearance of an unindexed peak is caused by the substrate utilized for the deposition. Clove-like material with precipitate is visible in the SrS material's micrograph; the big nano grain on the surface of the substrate exhibits photon absorption but lacks any signs of pinholes. At the introduction of dopant and heating the precursor at 35 °C, 40 °C, and 45 °C there is a drastic change in the micrograph of the films, for the films at 35 °C the nanoparticle clave together with a melted wax with a sharp large white precipitate which is very visible on the surface of the film and the material deposited at 40 °C and 45 °C there is no visible precipitate on the film which show that as the precursor temperature increases it eliminate lattice strain and improve the photovoltaic properties of the deposited material. The energy band gap of strontium sulphide (SrS) and strontium sulphide doped silver (SrS/Ag) at different precursor temperatures of 35 °C, 40 °C, 45 °C is 1.50–2.35 eV.     

Nonstoichiometry,point defects and magnetic properties in Sr2FeMoO6−δ double perovskites

The phase stability, nonstoichiometry and point defect chemistry of polycrystalline Sr₂FeMoO_6?δ (SFMO) was studied by thermogravimety at 1000, 1100, and 1200 °C. Single-phase SFMO exists between ?10.2≤log pO₂≤?13.7 at 1200 °C. At lower oxygen partial pressure a mass loss signals reductive decomposition. At higher pO₂ a mass gain indicates oxidative decomposition into SrMoO₄ and SrFeO_3?x. The nonstoichiometry δ at 1000, 1100, and 1200 °C was determined as function of pO₂. SFMO is almost stoichiometric at the upper phase boundary (e.g. δ=0.006 at 1200 °C and log pO₂=?10.2) and becomes more defective with decreasing oxygen partial pressure (e.g. δ=0.085 at 1200 °C and log pO₂=?13.5). Oxygen vacancies are shown to represent majority defects. From the temperature dependence of the oxygen vacancy concentration the defect formation enthalpy was estimated (ΔH_OV=253±8 kJ/mol). Samples of different nonstoichiometry δ were prepared by quenching from 1200 °C at various pO₂. An increase of the unit cell volume with increasing defect concentration δ was found. The saturation magnetization is reduced with increasing nonstoichiometry δ. This demonstrates that in addition to Fe/Mo site disorder, oxygen nonstoichiometry is another source of reduced magnetization values.     

Effect of Co60 γ-irradiation on the optical properties of thin films from the system GeSe3–Sb2Se3–ZnSe

Optical transmittance in the range from 200 nm to 1100 nm is measured for fresh and γ-irradiated thermally evaporated chalcogenide films of GeSe₃, Sb₂Se₃, ZnSe, (GeSe₃)₈₀(Sb₂Se₃)₂₀ and (GeSe₃)₇₀(Sb₂Se₃)₁₀(ZnSe)₂₀. The effect of ZnSe incorporation with both GeSe₃, Sb₂Se₃ results in amorphous γ-radiation sensitive (GeSe₃)₇₀(Sb₂Se₃)₁₀(ZnSe)₂₀ composition as obtained from the estimated optical parameters. Optical energy gap, E_g, for (GeSe₃)₇₀(Sb₂Se₃)₁₀(ZnSe)₂₀ film shows a noticeable decrease from 1.81 eV at 0 kGy to 1.52 eV at 690 kGy and conversely the corresponding band tail width, E_e, increases from 0.123 eV at 0 kGy to 0.138 eV at 690 kGy. By contrast, the estimated values of E_g and E_e for (GeSe₃)₈₀(Sb₂Se₃)₂₀ compositions, show no change with different γ-irradiation doses in the same range. The obtained results could be explained in terms of the band edge shift into the energy gap due to either the formation of localized states at the edges or weakening in the composition cohesive energy as reformation of new weaker bonds appear.     

Preparation,crystal structure,and spectroscopic,chemical, and electrochemical properties of (2E,4E)-1,4-di(3-guaiazulenyl)-1,3-butadiene compared with those of (E)-1,2-di(3-guaiazulenyl)ethylene

Wittig reaction of (E)-3-(3-guaiazulenyl)propenal (11) with (3-guaiazulenylmethyl)triphenylphosphonium bromide (9) in ethanol containing NaOEt at 25 °C for 24 h under argon gives the title new (2E,4E)-1,3-butadiene derivative 4, in 33% isolated yield, which upon treatment with hexafluorophosphoric acid (i.e., 65% HPF₆ aqueous solution) in tetrahydrofuran (=THF) at 25 °C for 1 h under aerobic conditions affords a new air (two-electron) oxidation product (E)-ethylene-1,2-bis(3-guaiazulenylmethylium) bis(hexafluorophosphate) (14), quantitatively, and further, zinc-reduction of 14 in trifluoroacetic acid (=CF₃COOH) at 0 °C for 1 h under argon reverts 4, quantitatively. Along with the above interesting results, our discovered another preparation method, spectroscopic properties, crystal structure, and electrochemical behavior of 4, which serves as a strong two-electron donor and acceptor, compared with those of the previously reported (E)-1,2-di(3-guaiazulenyl)ethylene (3) are documented in detail.     

Reactions of the HO2 radical with OH,H, Fe2+ and Cu2+ at elevated temperatures

The temperature dependence of the rate constant for the reactions of HO₂ with OH, H, Fe²⁺ and Cu²⁺ has been determined using pulse radiolysis technique. The following rate constants, k (dm³ mol⁻¹ s⁻¹) at 20°C and activation energies, E_a (kJ mol⁻¹) have been found. The reaction with OH was studied in the temperature range 20–296°C (k=7.0×10⁹, E_a=7.4) and the reaction with H in the temperature range 5–149°C (k=8.5×10⁹, E_a=17.5). The reaction with Fe²⁺ was studied in the temperature range 16–118°C (k=7.9×10⁵, E_a=36.8) and the reaction with Cu²⁺ in the temperature range 17–211°C (k=1.1×10⁸, E_a=14.9).     

Bioelectrocatalytic formate oxidation and carbon dioxide reduction at high current density and low overpotential with tungsten-containing formate dehydrogenase and mediators

We show a great possibility of mediated enzymatic bioelectrocatalysis in the formate oxidation and the carbon dioxide (CO₂) reduction at high current densities and low overpotentials. Tungsten-containing formate dehydrogenase (FoDH1) from Methylobacterium extorquens AM1 was used as a catalyst and immobilized on a Ketjen Black-modified electrode. For the formate oxidation, a high limiting current density (j_lim) of ca. 24 mA cm^− 2 was realized with a half wave potential (E_1/2) of only 0.12 V more positive than the formal potential of the formate/CO₂ couple (E°′_CO2) at 30 °C in the presence of methyl viologen (MV^2 +) as a mediator, and j_lim reached ca. 145 mA cm^− 2 at 60 °C. Even when a viologen-functionalized polymer was co-immobilized with FoDH1 on the porous electrode, j_lim of ca. 30 mA cm^− 2 was attained at 60 °C with E_1/2 = E°′_CO2 + 0.13 V. On the other hand, the CO₂ reduction was also realized with j_lim ≈ 15 mA cm^− 2 and E_1/2 = E°′_CO2 − 0.04 V at pH 6.6 and 60 °C in the presence of MV^2 +.     

Electrical transport properties of Zn doped ZnO

Electrical resistivity and Hall effect measurements at 77–373°K are presented for Zn doped ZnO crystals. The crystals have been doped systematically at 600–1100°C in controlled pressures of Zn. The concentration of electrons at room temperature is in the range n_RT = 2.5 × 10¹⁶, to 3.6 × 10¹⁸, cm^?3. The donor level E_D and the concentrations of donors N^D and acceptors N_A have been calculated from a best fit to the experimental relationships log n versus $\text{1}\text{T}$ and log μ_H versus log T. At dilute concentrations of donors, two donor levels have been observed, E_D^I = 0.043–0.045 eV and a deeper level E^II_D greater than 0.165 eV. The ZnO was found to behave as a metal at N_D ～ 6 × 10¹⁸, cm^?3.At least two different donors have to be assumed in order to explain the experimental results. It is suggested that interstitial Zn is the electrical active donor at higher doping levels. The nature of the other donor is not clear. Neither 1s¹ H-type nor 1s² He-type donors seem to explain all the observations consistently.     

Low temperature sintering study of nanosized Mn–Zn ferrites synthesized by sol–gel auto combustion process

The objective of present research was to sinter nanosized Mn–Zn ferrites (MZF) at low temperature (≤1,000 °C) by avoiding the formation of nonmagnetic phase (hematite). For this purpose, MZF powder was synthesized by sol–gel auto combustion process at 220 °C and further calcined at 450 °C. In calcined powder, single phase (spinel) was confirmed by X-ray diffraction analysis. Pellets were pressed, having 43% of the theoretical density and showing 47 emu gm⁻¹ saturation magnetization (M _s). Various combinations of heating rate, dwelling time and gaseous environment were employed to meet optimum sintering conditions at low temperature (≤1,000 °C). It was observed that sintering under air or N₂ alone had failed to prevent the formation of nonmagnetic (hematite) phase. However, hematite phase can be suppressed by retaining the green compacts at 1,000 °C for 180 min in air then further kept for 120 min in nitrogen. Under these conditions, spinel phase (comprising of nano crystallites), 90% of theoretical density and 102 emu gm⁻¹ of saturation magnetization has been achieved.