Studies on the electrochemiluminescent behavior of luminol on indium tin oxide (ITO) glass

The electrochemiluminescence (ECL) of luminol on indium tin oxide (ITO) glass was high even under a low potential around 0.4-0.5 V, which was quite different from other electrodes such as platinum. ITO nanoparticles were synthesized and used in the research on ITO glass in the ECL process. A static interaction between ITO and luminol is confirmed from UV-vis and fluorescence spectra. Then the ECL enhancement can be supposed to originate from the adsorption of luminol on ITO, which facilitated luminol’s oxidization to the excited state, giving out ECL. On the other hand, ITO can catalyze the generation of reactive oxygen species (ROSs), similar to some other nanomaterials, which also favored the ECL enhancement of luminol.     

Phase equilibria and excess properties for binary systems in reactive distillation processes Part I. Methyl acetate synthesis

Isothermal vapor–liquid equilibrium (VLE) and excess enthalpy (H^E) data were measured for binary systems required for the design of reactive distillation processes for the methyl acetate production. The isothermal P–x data were measured with the help of a computer-operated static apparatus. A commercial isothermal flow calorimeter was used for the determination of the heats of mixing. Temperature-dependent interaction parameters for the UNIQUAC model were fitted simultaneously to the experimental data from this work and other authors.     

The role of oxygen and hydrogen partial pressures on structural and optical properties of ITO films deposited by reactive rf-magnetron sputtering

Sn doped In₂O₃ films are deposited by rf-magnetron sputtering at 300 °C under Ar, Ar + O₂ and Ar + H₂ gas ambients. For the film prepared under argon ambient, electrical resistivity 6.5 × 10⁻⁴ Ω cm and 95% optical transmission in the visible region have been achieved optimizing the power and chamber pressure during the film deposition. X-ray diffraction spectra of the ITO film reveal (2 2 2) and (4 0 0) crystallographic planes of In₂O₃. With the introduction of 1.33% oxygen in argon, (2 2 2) peak of In₂O₃ decreases and resistivity increases for the deposited film. With further increase of oxygen in the sputtering gas mixture crystallinity in the film deteriorates and both the peaks disappeared. On the other hand, when 1.33% hydrogen is mixed with argon, the resistivity of the deposited film decreases to 5.5 × 10⁻⁴ Ω cm and the crystallinity remains almost unchanged. In case of reactive sputtering, the deposition rate is lower compared to that in case of non-reactive sputtering. HRTEM and first Fourier patterns show the highly crystalline structure of the samples deposited under Ar and Ar + H₂ ambients. Crystallinity of the film becomes lower with the introduction of oxygen in argon but refractive index increases from 1.86 to 1.9. The surface morphology of the ITO films have been studied by high resolution scanning electron microscopy.     

Numerical solutions of a model for the propagation of a surface-catalysed flame in a tube

Numerical simulations of a surface-catalysed flame in a tubeare performed, corresponding to an experiment where a premixedfuel is fed into a tube whose inner surface is coated with acatalyst. In these experiments, subsequent to ignition, a reactionwave can be seen as a red-hot region which propagates back alongthe tube towards the inlet, and is due to low temperature combustionoccurring only on the inner surface of the tube where the catalystis present. The solutions of a mathematical model for this behaviourshow that initial-value problems do indeed result in such steadilypropagating waves. The numerically obtained wave speeds andsteady solution are compared to a previous large Damköhlernumber (D_a) asymptotic analysis using a simple reaction ratemodel, and agreement is very good even for moderately largevalues of D_a. However, for such Damköhler numbers, thewave speeds are found to be much larger than observed experimentally.Indeed, the simulations show that O(1) values of D_a are requiredto obtain the lower experimental wave speeds. Nevertheless,the wave speeds as a function of flow rate through the tubedo not agree well with the preliminary experimental resultsfor any choice of the parameters. A more realistic, Arrheniusreaction rate model is then considered. The Arrhenius modelpredicts a rapid change in temperature at the wave front, inmuch better agreement with the experiments than for the simplerreaction model.     

Spectral methods for compressible reactive flows

High order simulations are necessary in order to capture fine details in resolving supersonic reactive flows. However, high Mach number compressible flows feature sharp gradients and discontinuities, which present a challenge to successful simulations using high order methods. Spectral methods have proven a powerful tool in simulation of incompressible turbulent flows, and recent advances allow the application of spectral methods to compressible reactive flows. We review the recent advances in the theory and application of spectral methods which allow stable computations of discontinuous phenomena, and the recovery of high order information via postprocessing, and present applications of high Mach number reactive flows. To cite this article: D. Gottlieb, S. Gottlieb, C. R. Mecanique 333 (2005).     

Simulation numérique des détonations à double structure cellulaireNumerical simulation of detonations with double cellular structure

We present the results of numerical two-dimensional simulations of detonation cellular structures under non-monotonous heat release provided by a chemical reaction comprising two successive exothermic steps. The influence of the rate of the second step of chemical reaction on the detonation cellular structure has been investigated. Our simulations are the first that reproduce a cellular structure composed of two clearly distinct sets of cells with different characteristic sizes where fine cells completely fill up larger ones, as has been observed experimentally. To cite this article: V. Guilly et al., C. R. Mecanique 334 (2006).     

碳四液化气在离子浸渍改性纳米HZSM-5沸石上的转化反应研究

在小型常压固定床反应器中研究了不同离子浸渍改性对纳米ZSM-5固体酸催化剂上丁烷和丁烯转化的影响.结果表明,混和碳四中异丁烷比正丁烷易转化,丁烯异构体的转化与其在原料中的含量有关.在贫烯烃原料中,丁烯倾向于生成.在富丁烯原料中,丁烯倾向于转化.但在两种情况下,产物中各丁烯含量大体上按异丁烯、顺反-丁烯-2和丁烯-1顺序递减.采用锌离子改性时异丁烷转化率提高、正丁烷转化率降低.锌离子改性有利于芳烃选择性,但是副产物甲烷和乙烷的产率也较高;铁离子改性对丁烷和丁烯的转化影响不大,但能减少甲烷和乙烷的生成,并提高芳烃选择性;与锌改性相比,锌钠双离子改性降低了异丁烷、正丁烷和丁烯-1的转化率,减少了芳烃产率,但能明显促进丙烯和丁烯的生成.上述结果为碳四液化气综合利用提供了有益信息.     

High Tg nematic thermosets: Synthesis, characterization and thermo-mechanical properties

In this paper the synthesis and characterization of a new family reactive nematic oligomers based on 4-hydroxybenzoic acid (4-HBA) will be presented. We modified the backbone using para- and meta-substituted aromatic monomers such as terephthalic acid (TA), isophthalic acid (IA), hydroquinone (HQ), resorcinol (RS), 4,4′-bisphenol (BP) and 3-hydroxybenzoic acid (3-HBA). All oligomers, with a target M_n of 5000 and 9000 g mol⁻¹, were end-capped with reactive phenylethynyl functionalities and synthesized using standard melt condensation techniques. Curing of the phenylethynyl reactive functionalities proceeds through chain extension and crosslinking, depending upon the temperature and time and can be carried out between 310 and 400 °C. Fully cured nematic thermosets could be obtained with glass-transition temperatures previously not accessible (T_g > 400 °C). The cured polymers exhibit excellent tensile properties, i.e. tensile strength (83 MPa) and elongation at break (9%). This approach allows us to prepare all-aromatic polymers with a combination of useful properties such as ease of processing, high T_g’s, and excellent mechanical properties.     

Evaluation of chemiluminescence reagents for selective detection of reactive oxygen species

In order to evaluate the chemiluminescence (CL) reagents for selective detection of reactive oxygen species (ROS), we comprehensively measured the CL responses of 20 CL reagents (three luminol derivatives, two imidazopyrazinone derivatives, eight lophine derivatives, six acridinium ester derivatives and lucigenin) against six types of ROS (superoxide anion: O₂⁻, hydroxyl radical: OH, hydrogen peroxide: H₂O₂, hypochlorite anion: ClO⁻, singlet oxygen: ¹O₂, and nitric oxide: NO). As a result of the screening, it was found that nine CL reagents selectively detected O₂⁻ while one CL reagent selectively detected OH. However, no CL reagent had selectivity on the detection of H₂O₂, ClO⁻, ¹O₂ and NO. Our screening results could help to select the most suitable CL reagent for selective determination of different ROS.As an application study, 4-methoxyphenyl-10-methylacridinium-9-carboxylate (MMAC), one of the acridinium ester derivatives, showed high selectivity on the detection of O₂⁻, and thus was applied to the assay of superoxide dismutase (SOD) activity. The dynamic range and detection limit of the developed CL assay were 0.1-10 and 0.06 U mL⁻¹, respectively. Significant correlation (r = 0.997) was observed between the results by the CL assay using MMAC and the spectrophotometric assay using 2-(4-iodophenyl)-3-(4-nitrophenyl)-5-(2,4-disulfophenyl)-2H-tetrazolium monosodium salt.