Microwave enhanced synthesis of N-propargyl derivatives of imidazole: A green approach for the preparation of fungicidal compounds

N-Propargyl imidazole has been synthesized by Knoevenagel condensation of benzaldehyde with propargyl bromide, assisted by microwave irradiation. Two alkaline-promoted clays (Li⁺- and Cs⁺-exchanged saponites) have been used as catalysts. The influence of several factors, such as irradiation power, irradiation time and alkaline promoter has been studied. The catalysts were characterized by XRD and chemical analysis. The basicity enhancement is directly connected to the presence of alkaline metal promoters in the saponite structure. In addition, a significant increase in the conversion values has been found when the reaction is activated by microwave irradiation, as compared with thermal activation. The yield to the N-propargyl imidazole shows a maximum for the Cs⁺-saponite at 750 W in only 5 min of microwave irradiation. This green and solvent-free procedure can be extended to the preparation of other N-substituted heterocycles, which could serve as precursors in the primary route to pharmaceutical compounds of interest.     

Synthesis and thermal stability of Zn3N2 powder

This paper reports that Zn₃N₂ powder of high quality has been synthesized by a nitridation reaction of Zn powder with NH₃ gas (flow rate 500 ml/min) at the nitridation temperature of 600 °C for 120 min. X-ray diffraction indicates that Zn₃N₂ is cubic in structure with the lattice constant being a=9.788 Å. X-ray photoelectron spectroscopy shows the differences of chemical bonding states between Zn₃N₂ and ZnO, and confirms the formation of N-Zn bonds. Thermal gravimetric analysis and differential thermal analysis are employed to investigate the thermal decomposition behavior of Zn₃N₂ powder. It is found that Zn₃N₂ is unstable when exposed to open air above 500 °C.     

Characterization of HfOxNy gate dielectrics using a hafnium oxide as target

Hafnium oxynitride (HfO_xN_y) gate dielectric has been deposited on Si (1 0 0) by means of radio frequency (rf) reactive sputtering using directly a HfO₂ target in N₂/Ar ambient. The thermal stability and microstructural characteristics for the HfO_xN_y films have been investigated. XPS results confirmed that nitrogen was successfully incorporated into the HfO₂ films. XRD analyses showed that the HfO_xN_y films remain amorphous after 800 °C annealing in N₂ ambient. Meanwhile the HfO_xN_y films can also effectively suppress oxygen diffusion during high temperature annealing and prevent interface layer from forming between HfO_xN_y films and Si substrates. AFM measurements demonstrated that surface roughness of the HfO_xN_y films increase slightly as compared to those pure HfO₂ films after post deposition annealing. By virtue of building reasonable model structure, the optical properties of the HfO_xN_y films have been discussed in detail.     

Nitrogen-doped carbon nanotubes with tunable structure and high yield produced by ultrasonic spray pyrolysis

Nitrogen-doped carbon nanotubes (CN_x) were prepared by ultrasonic spray pyrolysis from mixtures of imidazole and acetonitrile. Imidazole, as an additive, was used to control the structure and nitrogen doping in CN_x by adjusting its concentration in the mixtures. Scanning electron microscopy observation showed that the addition of imidazole increased the nanotube growth rate and yield, while decreased the nanotube diameter. Transmission electron microscopy study indicated that the addition of imidazole promoted the formation of a dense bamboo-like structure in CN_x. X-ray photoelectron spectroscopy analysis demonstrated that the nitrogen content varied from 3.2 to 5.2 at.% in CN_x obtained with different imidazole concentrations. Raman spectra study showed that the intensity ratio of D to G bands gradually increased, while that of 2D to G bands decreased, due to increasing imidazole concentration. The yield of CN_x made from mixtures of imidazole and acetonitrile can reach 192 mg in 24 min, which is 15 times that of CN_x prepared from only acetonitrile. The aligned CN_x, with controlled nitrogen doping, tunable structure and high yield, may find applications in developing non-noble catalysts and novel catalyst supports for fuel cells.     

Auger electron spectroscopy of Au/NiOx contacts on p-GaN annealed in N2 and O2 + N2 ambients

We have designed a promising contact scheme to p-GaN. Au/NiO_x layers with a low concentration of O in NiO_x are deposited on p-GaN by reactive dc magnetron sputtering and annealed in N₂ and in a mixture of O₂ + N₂ to produce low resistivity ohmic contacts. Annealing has been studied of NiO_x layers with various contents of oxygen upon the electrical properties of Au/NiO_x/p-GaN. It has been found that the Au/NiO_x/p-GaN structure with a low content of oxygen in NiO_x layer provides a low resistivity ohmic contact even after subsequent annealing in N₂ or O₂ + N₂ ambient at 500 °C for 2 min.Auger depth profiles and transmission electron microscopy (TEM) micrographs reveal that while annealing in O₂ + N₂ ambient results in reconstruction of the initial deposited Au/NiO_x/p-GaN contact structure into a Au/p-NiO/p-GaN structure, annealing in N₂ brings about reconstruction into Au/p-NiO/p-GaN and Ni/p-NiO/p-GaN structures. Hence, in both cases, after annealing in N₂ as well as in O₂ + N₂ ambient, the ohmic properties of the contacts are determined by creation of a thin oxide layer (p-NiO) on the metal/p-GaN interface. Higher contact resistivities in the samples annealed in O₂ + N₂ ambient are most likely caused by a smaller effective area of the contact due to creation of voids.     

Ultrasound assisted the preparation of 1-(4-nitrophenyl) imidazole under a new multi-site phase-transfer catalyst – Kinetic study

In this work, the nitroarylation of imidazole catalyzed by a new novel dual-site phase-transfer catalyst was carried out in an alkaline solution/imidazole in chlorobenzene two-phase medium with ultrasonic irradiation (40 kHz, 300 W). This new synthesized phase-transfer catalyst, N¹,N⁶-diethyl-N¹,N¹,N⁶,N⁶-tetraisopropylhexane-1,6-diaminium dichloride (MPTC), which possesses two-site activity, was obtained from the reaction of 1,6-dichlorohexane and N-ethyl-N-isopropylpropane-2-amine. The reaction of imidazole and alkali was carried out at the interface to generate sodium imidazole anion which can further react with MPTC form quaternary ammonium imidazole anion along with ultrasonic irradiation (40 kHz, 300 W). This ion-pair further react with 1-chloro-4-nitrobenzene which is present in the organic phase to produce 1-(4-nitropheny) imidazole. The reaction follows a pseudo first-order rate law. Kinetics of the reactions such as effect of the catalysts, ultrasonic effect, agitation speed, temperature, alkaline concentration, amount of 4-nitrochlorobenzene and the solvent effect on the reaction rate were investigated in detail. Peculiar phenomenon for the dependence of the reaction rate on the amount of MPTC and ultrasonication are explained satisfactorily.     

Experimental investigation of the CMN matrix element in the band anticrossing model for GaAsN and GaInAsN layers

The temperature dependence of bandgap energy of GaAs_0.98N_0.02 and Ga_0.95In_0.05As_0.98N_0.02 compounds has been analysed in order to determine the C_MN matrix element of the band anticrossing model. We have found that the element equals 2.48 and 2.60 eV for GaAs_0.98N_0.02 and Ga_0.95In_0.05As_0.98N_0.02 layers, respectively. When the same value has been assumed for annealed layers, an increase in the energy of the resonant nitrogen level E_N has been obtained. Two possible mechanisms leading to the increase in this energy are discussed in this work.     

Density functional theory study of Ir atom deposited on γ-Al2O3 (001) surface

Iridium adsorption on γ-Al₂O₃ (001) surface has been studied using the ab initio calculation method and the electronic structures of the bare and the Ir adsorbed γ-Al₂O₃ (001) surfaces have been analyzed. By modeling different adsorption sites, one can conclude that the energetically most favorable sites for the Ir are the top sites of the O atoms at the γ-Al₂O₃ (001) surface terminated with octahedral Al. Charge redistribution around the Ir atom adsorbed on the surface improves the activity of the Ir atom as a catalyst.     

Investigation of SiO2/Si3N4 films prepared on sapphire by r.f. magnetron reactive sputtering

Sapphire is a desired material for infrared-transmitting windows and domes because of its excellent optical and mechanical properties. However, its thermal shock resistance is limited by loss of compressive strength along the c-axis of the crystal with increasing temperature. In this paper, double layer films of SiO₂/Si₃N₄ were prepared on sapphire (α-Al₂O₃) by radio frequency magnetron reactive sputtering in order to increase both transmission and high temperature mechanical performance of infrared windows of sapphire. Composition and structure of each layer of the films were analyzed by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), respectively. Surface morphology and roughness of coated and uncoated sapphire have been measured using a talysurf. Flexural strengths of sapphire sample uncoated and coated with SiO₂/Si₃N₄ have been studied by 3-point bending tests at different temperatures. The results show that SiO₂/Si₃N₄ films can improve the surface morphology and reduce the surface roughness of sapphire substrate. In addition, the designed SiO₂/Si₃N₄ films can increase the transmission of sapphire in mid-wave infrared and strengthen sapphire at high temperatures. Results for 3-point bending tests indicated that the SiO₂/Si₃N₄ films increased the flexural strength of c-axis sapphire by a factor of about 1.4 at 800 °C.     

Preparation of nitrogen-doped titanium dioxide with visible-light photocatalytic activity using a facile hydrothermal method

Nitrogen-doped TiO₂ (N-TiO₂) nanoparticles have been successfully prepared via a direct and simple hydrothermal reaction of a commercial Degussa P25 with triethanol amine as solvent and nitrogen source. As-prepared N-TiO₂ was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet-visible light (UV-vis) absorption spectra, electron probe microanalysis (EPMA) and X-ray photoelectron spectroscopy (XPS) techniques. The results confirm that hydrothermal reaction is an effective way to incorporate nitrogen into the TiO₂ lattice, especially nitrogen substitute for titanium. The nitrogen concentration in TiO₂ can be as high as 21% (molar ratio), which is described as Ti_1−yO_2−xN_x+y (in this paper, x=0.36, y=0.27, i.e., Ti_0.73O_1.64N_0.63). The chemical statuses of N have been assigned to N-Ti-O and O-N-O in the TiO₂ lattice as identified by XPS. Photocatalytic degradation of methyl orange has been carried out in both UV-vis (simulated solar light) and the visible region (λ>400 nm). N-TiO₂ exhibits higher activity than the Degussa P25 TiO₂ photocatalyst, particularly under visible-light irradiation. This study has developed a promising and practical pathway to new nitrogen-doped photocatalysts.     

2-Propanol photodegradation over nitrogen-doped NaNbO3 powders under visible-light irradiation

Nitrogen-doped perovskite-type materials, yellowish NaNbO_3−xN_x powders, had been developed as visible-light-sensitive photocatalysts for decomposition of gaseous 2-propanol. The NaNbO_3−xN_x samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible (UV-vis) light diffuse reflectance spectroscopy, Brunauer-Emmett-Teller (BET) measurement, and scanning electron microscopy (SEM). The UV-vis spectra confirmed that the spectral response of the NaNbO₃ powders could be tuned to visible-light region by nitrogen doping technique. The photocatalytic activities of NaNbO_3−xN_x samples were evaluated by decomposing gaseous 2-propanol into acetone and CO₂ under visible-light irradiation (400 nm<λ<520 nm). The NaNbO_3−xN_x sample annealed at 833 K showed the highest visible-light photocatalytic activity among all the nitrogen-doped samples. The relationship between nitrogen doping amount and photocatalytic activity of NaNbO_3−xN_x samples was also investigated and discussed.     

Thermal and quantum fluctuations induced additional gap in single-particle spectrum of d-p model

The possibility of thermal and quantum fluctuations induced attractive interaction leading to a pairing gap Δ_tq in the single-particle spectrum of d-p model in the limit of a large N of fermion flavor is investigated analytically. This is an anomalous pairing gap in addition to the one with d-wave symmetry originating from partially screened, inter-site coulomb interaction. The motivation was to search for a hierarchy of multiple many-body interaction scales in high-T_c superconductor as suggested by recent experimental findings. The pairing gap anisotropy stems from more than one source, namely, nearest neighbor hoppings and the p-d hybridization, but not the coupling of the effective interaction. The temperature at which Δ_tq vanishes may be driven to zero by using a tuning parameter to have access to quantum criticality (QC) only when N?1. For the physical case N=2, the usual coherent quasi-particle feature surfaces in the spectral weight everywhere in the momentum below the pairing gap Δ_tq. Thus it appears that the reduction in spin degeneracy has the effect of masking quantum criticality.     

Compositional analysis of ferroelectric films coated with carbon layer using laser-induced plasmas spectroscopy

An experimental investigation of the effect of different thickness of carbon layer coated on ferroelectric films on the atomic emission intensity using laser-induced plasmas spectroscopy technique with charge-coupled device (CCD) experimental system has been conducted. The experimental results show that the intensity of the spectra emitted with the carbon layer thickness of 15 μm is much higher than that of pure ferroelectric films. By using this best experimental condition, the atomic concentration ratios of ferroelectric films are evaluated by rationing the integrated intensities of selected spectral emission lines of the plasma produced from the films. And the experimental results show that N_La/N_Co and N_Sr/N_Co atomic concentration ratios are almost in agreement with the corresponding values obtained by traditional compositional analysis techniques of inductively coupled plasma (ICP).     

Structural, optical properties and band gap alignments of ZrOxNy thin films on Si (1 0 0) by radio frequency sputtering at different deposition temperatures

ZrO_xN_y thin films have been prepared by radio frequency magnetron sputtering at various substrate temperatures. The effect of substrate temperature on structural, optical properties and energy-band alignments of as-deposited ZrO_xN_y thin films are investigated. Atomic force microscopy results indicate the decreased root-mean-square (rms) values with substrate temperature. Fourier transform infrared spectroscopy spectra indicate that an interfacial layer has been formed between Si substrate and ZrO_xN_y thin films during deposition. X-ray photoelectron spectroscopy and spectroscopy ellipsometry (SE) results indicate the increased nitrogen incorporation in ZrO_xN_y thin films and therefore, the decreased optical band gap (E_g) values as a result of the increased valence-band maximum and lowered conduction-band minimum.     

Physical properties of the delafossite LaCuO2

High-quality LaCuO₂, elaborated by solid-state reaction in sealed tube, crystallizes in the delafossite structure. The thermal analysis under reducing atmosphere (H₂/N₂: 1/9) revealed a stoichiometric composition LaCuO_2.00. The oxide is a direct band-gap semiconductor with a forbidden band of 2.77 eV. The magnetic susceptibility follows a Curie-Weiss law from which a Cu²⁺ concentration of 1% has been determined. The oxygen insertion in the layered crystal lattice induces p-type conductivity. The electrical conduction occurs predominantly by small polaron hopping between mixed valences Cu^+/2+ with an activation energy of 0.28 eV and a hole mobility (μ_300 K=3.5×10⁻⁷ cm² V⁻¹ s⁻¹), thermally activated. Most holes are trapped in surface-polaron states upon gap excitation. The photoelectrochemical study, reported for the first time, confirms the p-type conduction. The flat band potential (V_fb=0.15 V_SCE) and the hole density (N_A=5.8×10¹⁷ cm⁻³) were determined, respectively, by extrapolating the curve C⁻² versus the potential to their intersection with C⁻²=0 and from the slope of the linear part in the Mott-Schottky plot. The valence band is made up of Cu-3d orbital, positioned at 4.9 eV below vacuum. An energy band diagram has been established predicting the possibility of the oxide to be used as hydrogen photocathode.     

A facile one-pot solvothermal route to tubular forms of luminescent polymeric networks [(C3N3)2(NH)3]n

A facile one-pot solvothermal route has been developed for the synthesis of tubular luminescent polymeric networks [(C₃N₃)₂(NH)₃]_n, structurally related to the proposed g-C₃N₄. XRD patterns showed a characteristic 002 basal plane diffractions, indicating an interlayer d spacing of 3.23 Å. XPS spectra show that the C1s and N1s have a symmetric peak and an asymmetric peak at 288.10 and 399.00 eV, respectively. The bulk composition C₆N_8.9H_4.5 determined by elemental analysis is comparable to the calculated value C₆N₉H₃ for this proposed polymer. FTIR spectra indicated the presence of s-triazine ring, which was further supported by the luminescent and UV-vis absorption characteristics probably depending on π→π^* electronic transition. The tubular structure has been studied by TEM, SAED, and HREM.     

Thermal, mechanical, and electronic properties of glycine-sodium nitrate crystal

Glycine-sodium nitrate, C₂H₅N₂NaO₅ (GSN), crystals were grown from aqueous solutions by slow cooling with a temperature lowering rate of 1 °C/day in the range of 40-22 °C. These crystals were analyzed by differential thermal and thermogravimetric analysis (DTA-TGA) and mechanical hardness tester in order to obtain their thermal and mechanical properties. Mechanical characterization was done by studying the variation of microhardness with applied load. The dielectric properties of GSN were calculated by using the CASTEP code within the framework of the generalized gradient approximation (GGA). For better understanding of the optical properties of GSN, the second derivative of ε₂(E) was evaluated. DTA-TGA analysis showed that the material has a thermal stability up to 198 °C. The microhardness test was carried out for several faces of GSN crystals, and the tests revealed a load dependence to hardness. Analysis of the second derivative of ε₂(E) allowed to obtain better resolution of the electronic transitions involving the energy bands. Besides, a theoretical representation of the orbitals’ energy diagram was obtained. A discussion about the relation of structure-properties and molecular character of GSN is presented here.     

2D array design based on Fermat spiral for ultrasound imaging

The main challenge faced by 3D ultrasonic imaging with 2D array transducers is the large number of elements required to achieve an acceptable level of quality in the images. Therefore, the optimisation of the array layout, in order to reduce the number of active elements in the aperture, has been a research topic in the last years. Nowadays, array technology has made viable the production of 2D arrays with larger flexibility on elements size, shape and position, allowing to study other configurations different to the classical matrix organisation, such as circular, archimedes spiral or polygonal layout between others.In this work, the problem of designing an imaging system array with large apertures and a very limited number of active elements (N_e=128 and N_e=256) using the Fermat spiral layout has been studied. As summary, a general discussion about the most interesting cases is presented.     

Adsorption model determination of N2O/Ag(1 1 0) by theoretical studies of near-edge X-ray absorption fine structure

The nitrogen 1s near-edge X-ray absorption fine structure (NEXAFS) spectra of the N₂O adsorbed on Ag(1 1 0) have been studied by the multiple-scattering cluster (MSC) and self-consistent field (SCF) DV-Xα methods. Two adsorption models, in which the N₂O molecule attached to the Ag substrate through the central nitrogen (N_C) atom and the terminal nitrogen (N_T) atom, respectively, have been checked up thoroughly. The MSC calculation and the R-factor analysis show that the N₂O molecule is attached to the Ag substrate through the terminal nitrogen atom with the adsorption height h = 3.4 ± 0.1 Å. In the overlayer the N₂O molecules arrange themselves into a tilted chain due to the interaction between the cations and the anions in the molecules. The physical cause of the resonances in the NEXAFS spectra mentioned above has been discussed by the DV-Xα method, which confirms the MSC calculations.     

The influence of hydrogen on the growth of gallium catalyzed silicon oxide nanowires

In this paper, we report that amorphous silicon oxide nanowires can be grown in a large quantity by chemical vapor deposition with molten gallium as the catalyst in a flow of mixture of SiH₄, H₂ and N₂ at 600 °C. Meanwhile, when we grow these nanowires under the same conditions but without H₂, octopus-like silicon oxide nanostructures are obtained. The reasons and mechanisms for the growth of these nanowires and nanostructures are discussed. Blue light emission is observed from SiO_x nanowires, which can be attributed to defect centers of high oxygen deficiency. These SiO_x nanowires may find applications in nanodevices and reinforcing composites.