Spatio-temporal modeling of perimetric test data

This work describes the application of a spatio-temporal modeling to the study of glaucoma, a very serious ocular illness. The aim of this modeling is to solve various significant medical problems, namely the forecasting of future observations, the classification of observations as normal or defective, and the simulation of new longitudinal data sets. In order to ascertain whether a patient suffers from glaucoma, a perimetry is performed. The output of a perimetry is called a visual field and consists of a map with 52 numerical values plotted on a regular grid. In this work, a data set of healthy patients' visual fields is used. The work begins with an exploratory spatial data analysis. A semi-parametric approach is used to model the mean, and the variogram is fitted using a Matérn function. Once the spatial structure has been analysed, the spatial mean is subtracted from all the observations in the data set and the spatio-temporal correlation of the residuals is explored. All this information is used to build a space-time model, the parameters of which are estimated by maximum likelihood. Different methods are used to check the goodness of fit.     

Zeolite‐catalyzed isomerization of oleic acid to branched‐chain isomers

Branched‐chain (bc) saturated fatty acids (SFA) have potential as oleochemical intermediates since they have better oxidative stability than linear unsaturated fatty acids (UFA) and have better low‐temperature properties than linear SFA. Previous studies in converting UFA to bc‐FA using clay catalysts have resulted in only modest yields and conversions. Recent reports, however, have suggested that certain zeolites can be effective catalysts for converting UFA to bc‐FA in higher yields and conversions. In this work, we examined the scope and potential of the zeolite‐catalyzed synthesis of bc‐FA starting from readily available monounsaturated linear FA. Our results show that common UFA such as oleic acid can be converted to bc‐isomers using modified Ferrierite zeolite catalysts with high conversions (98%) and high selectivity (85%) and that the zeolite catalysts are reusable for at least three cycles. The positions of branching (methyl) on the FA chain were determined from the GC‐MS spectra of the picolinyl esters of the bc‐FA.     

Cure kinetics of a diglycidyl ether of bisphenol a epoxy network (n = 0) with isophorone diamine

The study of the cure reaction of a diglycidyl ether of bisphenol A epoxy network with isophorone diamine is interesting for evaluating the industrial behavior of this material. The total enthalpy of reaction, the glass‐transition temperature, and the partial enthalpies at different curing temperatures have been determined with differential scanning calorimetry in dynamic and isothermal modes. With these experimental data, the degree of conversion and the reaction rate have been obtained. A kinetic model introduces the mechanisms occurring during an epoxy chemical cure reaction. A modification of the kinetic model accounting for the influence of the diffusion of the reactive groups at high conversions is used. A thermodynamic study has allowed the calculation of the enthalpy, entropy, and Gibbs free energy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Morphological and Thermal Properties of ABS/Montmorillonite Nanocomposites Using ABS with Different AN Contents

Acrylonitrile‐butadiene‐styrene (ABS)/clay nanocomposites have been prepared using two types of ABS with different AN contents and a chemically modified clay, Cloisite 20A. The composites were prepared by melt mixing in a twin‐screw extruder. Their morphological properties were characterized by XRD and TEM. The thermal stability of the polymer nanocomposites was studied using TGA and flammability tests. The results were analyzed in terms of the effect of the clay content and the type of ABS used on the clay dispersion and the thermal stability of the nanocomposites. Experimental results confirmed that better dispersion and intercalation and/or exfoliation can be obtained when using an ABS with a higher AN content. The study using TGA and flammability tests showed that the nanodispersed layers of silicate enhanced the thermal stability of the ABS matrix, and that an ABS with higher AN content was more effective in providing fire retardancy. This suggests that when using higher AN contents, more polar groups are present within the polymer matrix, allowing a more homogeneous dispersion and intercalation of the chain polymers into the organomodified montmorillonite clay (MMT), and even some exfoliation of the nanoclay.

     

Comparative study of the physical aging of the epoxy systems BADGE n = 0/m‐XDA and BADGE n = 0/m‐XDA/PEI

The physical aging of the epoxy network consisting of a diglycidyl ether of bisphenol A, m‐xylylenediamine, and polyetherimide was studied by differential scanning calorimetry. The glass transition temperature and the variation of the specific heat capacities have been calculated using the method, based on the intersection of both enthalpy–temperature lines for glassy and liquid states. The apparent activation energy (E_H) was calculated using a single method that involved separate temperature and excess enthalpy dependency. All calorimetric data were compared with those obtained for the epoxy network without thermoplastic. thermoplastic. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3931–3935, 2006     

Modèles Hydrodynamiques pour la Séparation des Courants dans un Décanteur Pilote

Despite of its general use in industry, particle sedimentation is still a not well understood unit operation. Hydrodynamics is complex in essence, mainly because the possible volumes are depending on the operating conditions, which in turn has consequences on the stability of the equipment in unsteady state conditions.     

Modelling Industrial Wastewater Ozonation In Bubble Contactors. 1. Rate Coefficient Determination

A study of the ozonation of distillery and tomato wastewaters was carried out in a small bubble contactor in order to obtain kinetic data for scaling-up. Thus, several parameters, such as chemical oxygen demand (COD), 254 nm absorbance (A₂₅₄) and organic carbon content (OC), were followed during ozonation at different experimental conditions.

For distillery wastewaters all parameters investigated have the highest decreases during the first minutes of ozonation, A₂₅₄ showing the highest disappearance rates. Thus, during the first fifteen minutes of ozonation an important decrease of the 254 nm absorbance (? 75%) was observed. At further reaction times values of all parameters studied decrease slowly, eventually reaching a plateau value. During approximately the first two hours of reaction, dissolved ozone was never found, which suggested that fast or moderate gas-liquid reactions took place in the wastewaters.     

Modified Indigo Method For Gaseous And Aqueous Ozone Analyses

The indigo method developed by Bader and Hoigné for aqueous ozone analysis was modified to allow for both gaseous and aqueous ozone determination. Gas or water samples were extracted with a gas-tight syringe containing a known volume of indigo reagent. The modified procedure provided a more consistent basis for gaseous and aqueous ozone determination allowing for more accurate ozone mass balance calculations. Direct gaseous ozone UV absorbance with molar absorptivity of 3,000 M^?1cm^?1 at 258 nm was used as primary standard to determine the molar absorptivity of the indigo reagent. The molar absorptivity of indigo reagent, assuming a 1:1 stoichiometric ratio for the reaction between indigo and ozone, was determined to be 23,150 ± 80 M^?1cm^?1, or approximately 16 percent higher than that of 20,000 M^?1cm^?1 suggested by Bader and Hoigné. An independently calibrated membrane-electrode ozone monitor showed good correlation with indigo method results using the molar absorptivity value determined in this study. The apparent molar absorptivity of aqueous ozone at the wavelength of 258 nm measured by the modified indigo method increased from 2,400 to 3,600 M^?1cm^?1 in the investigated ozone concentration range of 0.4 to 11.0 mg/L. This variation might have been caused by the inherent interference of unidentified ozone byproducts, which presence was supported with scanning spectra in the wavelength range of 200 to 300 nm.     

Protective effect of estrogens and catecholestrogens against peroxidative membrane damagein vitro

The antioxidant effects of natural estrogens (estrone E₁; 17β-estradiol), synthetic estrogens (17α-ethynylestradiol, EE₂; mestranol, MES; diethylstilbestrol, DES) and catechle-strogens (2-hydroxyestradiol; 4-hydroxyestradiol 4-OHE₂) on lipid peroxidation induced by different means in rat liver microsomes were investigated. The extent of lipid peroxidation was determined by measuring thiobarbituric acid reactive substances. Prooxidants included Fe³⁺/ADP/reduced NADPH, Fe²⁺/ascorbate,tert-butyl hydroperoxide (t-BOOH) and 2,2′-azobis (2-amidinopropane) (AAPH). Estrogens and catecholestrogens decreased lipid peroxidation in all four systems tested. In the iron/ascorbate model it was shown that (i)-OHE₂ and DES had analogous patterns of inhibition, irrespective of the presence of NADPH or the functional integrity of the microsómes, and (ii) the antioxidant activities of E₁, EE₂ and MES were dependent on the assay conditions with the activity being markedley higher when estrogen metabolism was favored. When peroxidation was initiated by the peroxyl radical generator AAPH, the inhibitory effects observed were least pronounced. Our data also showed that, in each of the systems, all inhibitors displayed the same order of inhibitory potency with DES and catecholestrogens being the most potent antioxidants under all experimental conditions used. The present results confirm earlier findings and point toward a link between estrogen metabolism and estrogen antioxidant activity. The data also indicate that estrogens and catecholestrogens interact with the peroxidative process at different levels with their interactions with iron or the metal-derived species being the most important modes of inhibition.     

Analysis of lipoxygenase kinetics by high-performance liquid chromatography with a polymer column

Soybean lipoxygenase (LOX; EC 1.12.11.12) catalyzes the oxygenation of polyunsaturated fatty acids, acylglycerols and phosphoglycerols, producing a regio-and enantiospecific hydroperoxide product. The goal of this work was to measure the relative rate of LOX-catalyzed oxidation of mixtures of lipids containing linoleate, using high-performance liquid chromatography (HPLC) and a light-scattering detector (LSD). Previous literature sugested that reversed-phase HPLC with silicabased columns could be used for the separation of individual fatty acids, acylglycerols, phosphoglycerides and their oxidation products. However, these columns produced ineffective separations of phosphoglycerides unless choline chloride and a strong base, such as KOH, are present in the mobile phase. Such modifiers precluded the use of the LSD. It was found that a reversed-phase column based upon an organic polymer support, rather than on silica, was able to separate these mixtures with a ternary solvent gradient of methanol/water/acetonitrile without the need for the addition of modifiers. The oxidation time course of a mixture of linoleic acid, trilinolein and 1-linoleoyl-2-stearoyl-sn-glycero-3-phosphocholine was followed using the developed HPLC method. The results showed that trilinolein and phosphatidylcholine reacted at one-tenth the rate of linoleic acid. The diacylglycerol, 1,3-dilinolein, was oxidized at a rate that was approximately 40% that of linoleic acid, with the formation of mono-and dihydroperoxides as well as other unidentified products.