n-Butane Isomerization Over SO4 =/NiO/Al2O3/ZrO2 Catalysts. Effect of the Reaction Pressure and Metal Loading

The effect of alumina and nickel in sulfated ZrO₂ as a catalyst for n-butane isomerization was investigated. Samples were synthesized by supporting nickel sulfated zirconia on boehmite and then calcining the material. The crystalline structure of ZrO₂ was studied by X-ray powder diffraction and refined by the Rietveld method. Surface areas were determined by N₂ adsorption and BET analysis, while the acid properties were studied by NH₃ adsorption. The chemical reaction was carried out in a fixed-bed microreactor at 338 K under atmospheric (78 kPa) or 245 kPa total pressure. Results showed that either nickel or alumina improved the catalytic activity, but a synergic effect was observed when both components assisted. The catalytic activity was related to the relative content of tetragonal zirconia and acid site density. Alumina stabilized tetragonal zirconia increased the acid site density and presumably led to a better dispersion of nickel oxide. The catalytic activity could be related to both oxidation and acid sites produced by nickel. A bimolecular reaction mechanism helps explain the observed trends. The increase in the reaction rate would be explained by the increase in the rate of the initial step of dehydrogenation either caused by a better dispersion of nickel or higher operating pressure.     

Chemical analysis of ozonized theobroma fat

Ozonized theobroma fat is used as raw material in the manufacture of pessaries and cosmetic creams. Ozonization of theobroma fat with water was carried out at different applied ozone dosages, and the resultant PV, acid value, iodine value, total hydroperoxide content, and FA content were determined. PV and total hydroperoxide content showed a notable increase with applied ozone dosage up to 35.7 mg/g. Acid value varied slightly from 4.1 to 9.9 mg KOH/g, and the iodine value fell to zero. PV and total hydroperoxide content increased slightly with a higher applied ozone dosage. The comparison of total hydroperoxide measurement using ferrous oxidation in xylenol orange assay and traditional iodometric assay for PV determination showed a significant linear correlation. Small amounts of oleic acid were found in ozonized theobroma fat samples with iodine value equaling zero, which demonstrated that iodine value determination is an inexact assay. During ozonization of theobroma fat, an increase in acid value of 18.9-fold with respect to the initial value was observed owing to decomposition of peroxide.     

Surface properties of fluorinated hybrid coatings

A commercial perfluoropolyether containing alkoxysilane functionalities was employed to prepare organic–inorganic hybrid coatings by using the sol‐gel process in the presence of tetraethoxysilane. Contact angle analysis revealed a strong hydrophobic and oleophobic character of the coatings almost independently from the molecular weight of the starting fluorinated oligomer. Surface tension values were in the range of 14–16 mN/m, suggesting a preferential segregation of fluorinated segments onto the surface of the coating. Atomic force microscopy showed the presence very smooth surfaces permitting to neglect the contribution of the surface roughness to wettability. Friction coefficient values were markedly lower with respect to the value of uncoated glass substrate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1483–1488, 2006     

On the Gröbner basis triangularization of constraint equations in natural coordinates

Efficient dynamic simulation code is essential in many situations (including hardware-in-the-loop and model-predictive control applications), and highly beneficial in others (such as design optimization, sensitivity analysis, parameter identification, and controller tuning tasks). When the number of modeling coordinates n exceeds the degrees-of-freedom of the system f, as is often the case when closed kinematic chains are present, the governing dynamic equations consist of n second-order ordinary differential equations (ODEs) coupled with m=n?f algebraic constraint equations. This set of n+m index-3 differential-algebraic equations can be difficult to solve in an efficient yet accurate manner. Embedding (or generalized coordinate partitioning) can be used to obtain f ODEs (one for each independent acceleration), which are generally more amenable to numerical integration; however, the dependent positions are typically computed from the independent positions at each time step. Newton–Raphson iteration is often used for solving the position-level kinematics, but only provides solutions to within a specified tolerance, and can require several iterations to converge. In this work, Gröbner bases are used to obtain recursively solvable symbolic solutions for the dependent positions, which can then be evaluated to within machine precision using a fixed number of arithmetic operations. Natural coordinates are particularly attractive in this context, since the resulting constraint equations are maximally quadratic polynomials and are, therefore, easily triangularized. The proposed approach is suitable for use in an automated formulation procedure and, as demonstrated by three examples, is capable of generating highly efficient simulation code with minimal additional effort required at the formulation stage.     

Kinetic modeling of pentachlorophenol adsorption from aqueous solution on activated carbon fibers

The adsorption equilibrium data of pentachlorophenol (PCP) onto activated carbon fiber (ACF) in felt form were obtained in a batch adsorber at T = 25 °C and pH 12 and the Langmuir isotherm fitted reasonably well with the experimental data. The rate of adsorption of PCP on ACF was investigated in this work and the experimental concentration decay data were obtained in a differential column batch adsorber. The overall rate of adsorption of PCP was interpreted by a diffusional model that takes into account the external mass transport and intrafiber diffusion. The experimental concentration decay can be described quite well with the diffusional model if the overall rate of adsorption is mainly controlled by intrafiber diffusion and the external mass transport is not important to the overall rate of adsorption. Moreover, intrafiber diffusion was significantly affected by restricted diffusion since the molecular diameter of the PCP was closed to 55% of the average pore diameter. The effect of restricted diffusion was estimated using correlations reported in the literature. The molecules of PCP adsorbed on the surface of the pore also hindered the diffusion of PCP molecules inside the pores.     

Random Copolymers with 2,2′-Dioxy-1,1′-biphenyl-phosphazene and Chiral 2,2′-dioxy-1,1′-binaphthylphosphazene Units Functionalized in the 6,6′-Positions with PPh<Subscript>2</Subscript> Groups as Precursors for Ru(arene) Catalysts

The chiral phosphazene copolymers {[NP(O₂C₁₂H₈)]_0.9[NP(O₂C₂₀H₁₂)]_0.1} (1) and {[NP(O₂C₁₂H₈)]_0.9[NP(O₂C₂₀H₁₀Br₂)]_0.1} _n (2) [(O₂C₁₂H₈) = 2,2′-dioxy-1,1′-biphenyl; (O₂C₂₀H₁₂) = R-2,2′-dioxy-1,1′-binaphthyl and (O₂C₂₀H₁₀Br₂) = R-6,6′-dibromo-2,2′-dioxy-1,1′-binaphthyl] were prepared by sequential substitution from [NPCl₂] _n and the corresponding dihydroxy-biphenyl or binaphthyl reagents in the presence of Cs₂CO₃ and K₂CO₃. The reaction of (2) with ^tBuLi in THF, followed by addition of PPh₂Cl and a treatment with SiHCl₃/PPh₃ to eliminate any oxidized OC₆H₄P(O)Ph₂ groups, gave the phosphine containing copolymer {[NP(O₂C₁₂H₈)]_0.9[NP(O₂C₂₀H₁₀[PPh₂]₂)]_0.1} _n (3), that was used as a chiral ligand to support [Ru(p-cymene)Cl] complexes. The resulting catalyst was active for hydrogen transfer from isopropyl alcohol to acetophenone but the placement of the Ru centers in the 6,6′-positions of the binaphthoxyphosphazene units induced no enantioselectivity. Dedicated to Professor Christopher Allen.     

Iron, folic acid and vitamin B12 deficiencies related to anemia in adolescents from a region with a high incidence of congenital malformations in Venezuela

Since in recent years for certain age groups, the main cause of anemia is not iron deficiency, we intended to study the effect of iron, folic acid and vitamin B12 deficiencies on anemia prevalence in adolescents from Venezuela. One hundred adolescents aged between 12 and 19 years participated in the study. Each subject was interviewed about antecedents and habits and a physical examination and a 24-hour food recall questionnaire were performed. From a blood sample, hemoglobin and hematocrit concentrations were determined and serum was separated for quantification of ferritin, folic acid and vitamin B12 concentrations. Prevalence of anemia was 78% and for iron, folic acid and vitamin B12 deficiencies were 34.66, 90.9 and 18.18%, respectively. From anemic cases, 35.89% presented iron deficiency, while 91.02% presented folic acid deficiency. Only 19.23% of adolescents with anemia presented also vitamin B12 deficiency, but all the cases with vitamin B12 deficiency, were anemic. Simultaneous iron and folic acid deficiencies affected 30.76% of anemic cases. The high prevalence of deficiencies found in this work could be explained by insufficient intake and inadequate food habits. The prevalence of anemia was associated to folic acid deficiency rather than to iron deficiency, due to the high prevalence of folic acid deficiency. The high prevalence of nutritional deficiencies found in this work, especially regarding folic acid deficiency, require immediate interventions.     

A color image watermarking framework for copyright protection of stereo images based on binocular just noticeable difference and LU decomposition

Multimedia Tools and Applications - The copyright protection of three-dimensional (3D) content is a matter of interest in artistic and creative works due to the rights of the holder for the...     

Development and implementation of a hybrid scale up model for a batch high shear wet granulation operation

The high shear wet granulation (HSWG) operation consists of several rate processes influenced by the raw material properties, process operational parameters, and equipment design. Their combined effect determines the granule attributes. In literature, these rate processes have been modeled using different dimensionless numbers and their correlations. Each of these dimensionless numbers represent only certain rate processes. Since many of these rate processes occur at the same time, it is necessary to simultaneously model them to account for all the important degrees of freedom. Most of the HSWG scale up approaches in literature calculate scale up conditions based on a single rate process or operating parameter of interest that can lead to sub-optimal process design. We present the development of a hybrid HSWG scale up model accounting simultaneously for all the rate processes. The approach was successfully implemented to scale up the HSWG operation across laboratory, pilot, and commercial scales.     

Biofilm Responses to Flow Regulation by Dams in Mediterranean Rivers

Dams regulate downstream hydrology and modify water quality, which in turn can impinge on the biota, especially in rivers naturally subject to large hydrological variability, such as those under Mediterranean climate. The effect of dams on biofilms was analysed in three tributaries (Cinca, Siurana and Montsant) of the Ebro River (NE Spain). We hypothesized that flow regulation would lead to lower spatial variability of biofilms on the streambed and to a decrease in their metabolic rate per unit biomass, especially during low flow periods. Biofilm characteristics were studied in five transects evenly spaced along river reaches upstream (control) and downstream (impact) of dams in each river, along with riverbed granulometry, hydraulics and water chemistry. Chlorophyll‐a, respiratory activity, photosynthetic capacity and efficiency, and extracellular enzymatic activities (β‐d ‐glucosidase, alkaline phosphatase and leucine‐amino‐peptidase) of epilithic biofilms were measured in different seasons. Spatial variability of chemical and biological variables was reduced downstream of the dams. Chlorophyll‐a concentration, photosynthetic efficiency and respiration capacity were higher in impact than in control reaches, but generally, low inorganic phosphorus concentrations resulted in comparable phosphatase activities downstream and upstream of dams. On the other hand, β‐d ‐glucosidase and leucine‐amino‐peptidase activities were higher at impact reaches. Biofilms were thicker and metabolically more active at the impact reaches, with higher ability to transform dissolved organic matter. Overall, results from this study provide evidence that dams can largely affect the structure and activity of river biofilms, with foreseeable important consequences for river ecosystem functioning. Copyright © 2014 John Wiley & Sons, Ltd.