Nanosized cationic and anionic manganese porphyrins as mesoporous catalysts for the oxidation of olefins: Nano versus bulk aggregates

In this study, catalytic activity of bulk and nano‐sized meso‐tetrakis(4‐sulfonatophenyl)porphyrinatomanganese(III) acetate, MnTPPS₄(OAc), (ammonium salt) and meso‐tetrakis(3‐methylpyridyl)porphyrinatomanganese(III) acetate, MnT(3‐MePy)P(OAc) (tosylate salt) for the oxidation of olefins with tetra‐n‐butylammonium Oxone has been studied and compared with that of the bulk counterparts. The nanoparticles were prepared by mixing solvent techniques using water, (triethyleneglycol) monomethyl ether and dimethylsulfoxide or acetonitrile. The formation of nano‐sized catalysts was confirmed by UV‐Vis spectroscopy, DLS and AFM. Nitrogen porosimetry measurements indicated the homogeneous pore size distribution in the bulk and nano‐sized manganese porphyrins. In spite of the high oxidizability of Oxone, the heterogenized manganese porphyrins showed a significantly higher oxidative stability relative to their homogeneous counterparts within a reaction time of 6 h. The increase in the catalytic activity induced by the formation of nano‐sized catalysts was more pronounced in the case of MnT(3‐MePy)P(OAc). MnT(3‐MePy)P(OAc) may be recovered and reused for at least 4 times without any significant decrease in the catalyst efficiency. In the case of MnTPPS₄(OAc) a large decrease in the catalytic activity was observed after the first use of the catalyst. The latter was attributed to higher degrees of catalyst degradation in the case of MnTPPS₄(OAc).     

Sensitive Quantification of Fe(III) in Food Samples at Screen Printed Carbon Electrode Modified with Graphene and Piroxicam by Catalytic Adsorptive Voltammetry

A new disposable sensitive voltammetric sensor for the determination of Fe(III) based on a graphene (G) and piroxicam (Pir) modified screen printed carbon electrode (Pir/G/SPCE) has been developed. The developed method is based on accumulation of Fe(III) on the surface of the prepared sensor strip, formation a complex with Pir and subsequent reduction the adsorbed chelated Fe(III) at ?0.03 V (vs. Ag/AgCl) coupled with the catalytic enhancement of bromate. Characterizations of the modified electrode surface were performed by field emission scanning electron microscopy (FE‐SEM), energy dispersive X‐ray spectroscopy (EDX) and electrochemical impedance spectroscopy (EIS). Electrochemical behavior of the modified SPCEs was investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Under the optimum conditions, the catalytic voltammetric method exhibited linear calibration plot in the concentration ranges of 1–100 ng mL^?1 and 100–3500 ng mL^?1 Fe(III) with a limit of detection of 0.3 ng mL^?1. The sensor strip displayed good reproducibility with 1.7 % relative standard deviation (RSD%). The developed method was successfully applied for the determination of iron in food samples such as vegetables, fruit, and cereal.     

Seed priming with cold plasma improved seedling performance,secondary metabolism,and expression of deacetylvindoline O-acetyltransferase gene in Catharanthus roseus

The plasma-primed seeds of Catharanthus roseus were cultured in a hormone-free culture medium under sterile conditions. Plasma of 30 or 60 s improved root length (mean = 41.4%) and biomass (mean = 47%), whereas plasma of 90 s delayed plant growth. The plasma treatments enhanced concentrations of photosynthetic pigments and soluble phenols. Plasma of 90 s increased the proline level. With a similar trend, plasma priming induced activities of phenylalanine ammonia-lyase, catalase (about twofold) and peroxidase (31%) enzymes. Plasma also upregulated the expressions of deacetylvindoline O-acetyltransferase gene by an average of 7.8 times. Similarly, the plasma-treated seedlings contained higher concentrations of alkaloids (mean = 72%). Here, molecular evidence is provided on the plasma-associated modifications in secondary metabolism.     

Radiative transfer in fine structures of solar prominences

In the first part we used Ambartsumains method of addition of layers to show that various problems of radiative transfer in a plane-parallel inhomogeneous atmosphere may be reduced to the solution of the cauchy problems for linear differential equations. The idea of the approach is that we start with the determining of the reflection and transmission coefficients of an atmosphere by solving the initial-value problem for a set of linear differential equations of the first order. After that the internal radiation field is found immediately without solving any new equation.There are some solar prominence fine structures which are not observable. Thus, we need to use theoretical methods to study their geometric and physical properties. It is believed that observed intensities and their fluctuations are related to such fine structures in the line of sight. Regarding the fact that the spectrum line corresponding to the transition will not be sharp and will have a spread in frequency that can be described by absorption profiles. So, the second part of the present study is an attempt to determine the intensity fluctuations in the frequency-dependent case with different absorption profiles such as Doppler, Voigt and Lorentz profiles. It became evident that the intensity fluctuations vary with absorption profile and optical depth variations in the line of sight. It should be noted that the present study focuses on the LTE absorbing atmosphere.     

Facile fabrication of Zn/Zn5(OH)8Cl2·H2O flower-like nanostructure on the surface of Zn coated with poly (N-methyl pyrrole)

Zn/Zn₅(OH)₈Cl₂·H₂O flower-like nanostructures was electrodeposited on the coated Zn with poly (N-methyl pyrrole) in 0.1 M Zn (NO₃)₂ and 0.1 M KCl solution. The morphology and the structure of the Zn/Zn₅(OH)₈Cl₂·H₂O were characterized by Field Emission Scanning Electron Microscopy (FESEM), Fourier transform infrared (FT-IR) spectroscopy and X-ray diffraction analysis (XRD). The FT-IR results showed special peaks at 908 and 728 cm⁻¹ related to Zn₅(OH)₈Cl₂·H₂O. The FESEM results indicated that Zn/Zn₅(OH)₈Cl₂·H₂O consists of a flower-like nanostructure and these flower-shaped structures contain many shaped nanopetals with the thickness of 27.8 nm. The XRD result confirmed that the major phase of electrodeposited product in 0.1 M KCl as supporting electrolyte was Zn₅(OH)₈Cl₂·H₂O. The ability of PMPy to create a thin film and the existence of several pores in its matrix act as a mold for the growth of Zn/Zn₅(OH)₈Cl₂·H₂O flower-like nanostructure. The trapping of Cl⁻ and OH⁻ within pores can be considered as the reason for the formation of flowerlike Zn/Zn₅(OH)₈Cl₂·H₂O nanostructures in 0.1 M KCl.     

Solving nonlinear parabolic PDEs via extended hybrid BDF methods

The details of new methods based on backward differentiation formulas (BDF) for the MOL solution of one-dimensional nonlinear time dependent PDEs are presented. In these extended hybrid BDF methods, we say EHBDF, one additional stage point (or off-step point) together with one step point have been used in the first derivative of the solution. All presented methods, of order p, p = 2,3,..., 12, are A(α)-stable whereas they have wide stability regions comparing with those of some known methods such as BDF, extended BDF (EBDF) and modified EBDF (MEBDF) methods.     

A new model for automatic normalization of multitemporal satellite images using Artificial Neural Network and mathematical methods

Relative Radiometric Normalization is often required in remote sensing image analyses particularly in the land cover change detection process. Normalization process minimizes the radiometric differences between two images caused by inequalities in the acquisition conditions rather than changes in surface reflectance. A wide range of RRN methods have been developed to adjust linear models. This paper proposes an automated Relative Radiometric Normalization (RRN) method to adjust a non-linear model based on an Artificial Neural Network (ANN) and unchanged pixels. The proposed method includes the following stages: (1) automatic detection of unchanged pixels based on a new idea that uses CVA (Change Vector Análysis) method, PCA (Principal Component Analysis) transformation and K-means clustering technique, (2) evaluation of different architectures of perceptron neural networks to find the best architecture for this specific task and (3) use of the aforementioned network for normalizing the subject image. The method has been implemented on two images taken by the TM sensor. Experimental results confirm the effectiveness of the presented technique in the automatic detection of unchanged pixels and minimizing imaging condition effects (i.e., atmosphere and other effective parameters).     

New class of hybrid BDF methods for the computation of numerical solutions of IVPs

A new class of hybrid BDF-like methods is presented for solving systems of ordinary differential equations (ODEs) by using the second derivative of the solution in the stage equation of class 2 + 1hybrid BDF-like methods to improve the order and stability regions of these methods. An off-step point, together with two step points, has been used in the first derivative of the solution, and the stability domains of the new methods have been obtained by showing that these methods are A-stable for order p, p =?3,4,5,6,7and A(α)-stable for order p, 8 ≤ p ≤?14. The numerical results are also given for four test problems by using variable and fixed step-size implementations.     

Insight into Heterogeneity Effects in Methane Hydrate Dissociation via Pore-Scale Modeling

A large number (1253) of high-quality streaming potential coefficient (\(C_\mathrm{sp})\) measurements have been carried out on Berea, Boise, Fontainebleau, and Lochaline sandstones (the latter two including both detrital and authigenic overgrowth forms), as a function of pore fluid salinity (\(C_\mathrm{f})\) and rock microstructure. All samples were saturated with fully equilibrated aqueous solutions of NaCl (10\(^{-5}\) and 4.5 mol/dm\(^{3})\) upon which accurate measurements of their electrical conductivity and pH were taken. These \(C_\mathrm{sp}\) measurements represent about a fivefold increase in streaming potential data available in the literature, are consistent with the pre-existing 266 measurements, and have lower experimental uncertainties. The \(C_\mathrm{sp}\) measurements follow a pH-sensitive power law behaviour with respect to \(C_\mathrm{f}\) at medium salinities (\(C_\mathrm{sp} =-\,1.44\times 10^{-9} C_\mathrm{f}^{-\,1.127} \), units: V/Pa and mol/dm\(^{3})\) and show the effect of rock microstructure on the low salinity \(C_\mathrm{sp}\) clearly, producing a smaller decrease in \(C_\mathrm{sp}\) per decade reduction in \(C_\mathrm{f}\) for samples with (i) lower porosity, (ii) larger cementation exponents, (iii) smaller grain sizes (and hence pore and pore throat sizes), and (iv) larger surface conduction. The \(C_\mathrm{sp}\) measurements include 313 made at \(C_\mathrm{f} > 1\) mol/dm\(^{3}\), which confirm the limiting high salinity \(C_\mathrm{sp}\) behaviour noted by Vinogradov et al., which has been ascribed to the attainment of maximum charge density in the electrical double layer occurring when the Debye length approximates to the size of the hydrated metal ion. The zeta potential (\(\zeta \)) was calculated from each \(C_\mathrm{sp}\) measurement. It was found that \(\zeta \) is highly sensitive to pH but not sensitive to rock microstructure. It exhibits a pH-dependent logarithmic behaviour with respect to \(C_\mathrm{f}\) at low to medium salinities (\(\zeta =0.01133 \log _{10} \left( {C_\mathrm{f} } \right) +0.003505\), units: V and mol/dm\(^{3})\) and a limiting zeta potential (zeta potential offset) at high salinities of \({\zeta }_\mathrm{o} = -\,17.36\pm 5.11\) mV in the pH range 6–8, which is also pH dependent. The sensitivity of both \(C_\mathrm{sp}\) and \(\zeta \) to pH and of \(C_\mathrm{sp}\) to rock microstructure indicates that \(C_\mathrm{sp}\) and \(\zeta \) measurements can only be interpreted together with accurate and equilibrated measurements of pore fluid conductivity and pH and supporting microstructural and surface conduction measurements for each sample.