Autoxidation of saturated fatty acids. II. The determination of the site of hydroperoxide groups in autoxidizing methyl palmitate

The monohydroperoxides of methyl palmitate oxidized at 150C were concentrated, purified, and reduced to yield a mixture of isomers of monohydroxy palmitate. No evidence of unsaturation in these molecules could be obtained, and no direct method for the resolution or identification of the individual isomers was found. Nuclear magnetic resonance (NMR) spectroscopy of the reduced esters suggested that the hydroxy groups were not located at either end of the chain of the fatty ester. To establish the location of the initial oxidative attack on saturated esters, the reduced esters of oxidized methyl palmitate were chemically cleaved at the location of the hydroxy group by means of chromium trioxide oxidation and by the Beckmann transformation. The resulting mono- and dibasic fatty acids were methylated and analyzed by gas chromatography. This analysis indicated that the oxidation of methyl palmitate did not occur selectively at one location along the ester. Although all carbon atoms can apparently be oxidized, preferential oxidation was observed toward the center of the molecule.     

Flood hazard maps in the European context

The implementation of the EU Floods Directive by water authorities across Europe has generated a lack of consistency in the present situation, especially regarding the scales adopted, the hydrological scenarios and the elements represented on flood hazard and risk maps. From the EU-funded project HYTECH, this article presents a general overview of Floods Directive implementation in eight European countries, highlighting the differences between them, with particular attention to flood hazard maps. For the implementation cycle that started at the beginning of 2016, a minimization of such differences is necessary in order to manage flood risk in a better and more integrated way.     

Biodesulfurization of dibenzothiophene sulfone by Arthrobacter sp. and studies with oxidized Illinois No. 6 coal

A bacterium identified as Arthrobacter sp. was grown on dibenzothiophene (DBT) sulfone as a sole source of sulfur, producing sulfite and sulfate. Sulfur in DBT sulfone (1.0 mM) was nearly quantitatively converted to sulfate by the organism. The organism could also use DBT sulfone as a sole source of carbon and energy. There was evidence for transient accumulation of benzoic acid in the culture medium after growth of the cells slowed. The DBT sulfoxide analogue 9-fluorenone was converted by resting cells to a product identified as 1,10-dihydroxy-1,10-dihydrofluoren-9-one, suggesting that DBT sulfone may be metabolized via an angular hydroxylation resulting in carbon- sulfur bond cleavage. This strain of Arthrobacter showed no ability to desulfurize oxidized Illinois No. 6 coal.     

Surface properties of commercial polymer films following various gas plasma treatments

Surface properties of a number of commercial thermoplastic polymer films were investigated before and after brief exposures to RF induced, low temperature gas plasmas. Water wettability and adhesion of vapor deposited aluminum to thin films (8–12 micron) of polyethylene, polypropylene, polyester, polysulfone, polycarbonate, and polyvinylidene fluoride films were studied before and after treatments with oxygen, 96% CF₄/4% O₂, and helium plasmas. Treatment with oxygen plasmas showed the greatest change in water wettability for polyvinylidene fluoride and polypropylene films, while treatment with 96% CF₄/4% O₂ showed dramatic changes in wettability of polycarbonate, polysulfone, and polystyrene. Excellent adhesion of aluminium was found for polymers that had been previously exposed to gas plasmas.     

Statistical Analysis of the Intergranular Film Thickness in Silicon Nitride Ceramics

Silicon nitride materials typically reveal thin amorphous intergranular films along grain boundaries, with only the exception of special boundaries. It is known that such grainboundary films strongly affect the high-temperature properties of the bulk material. High-resolution electron microscopy (HREM) was used to study these amorphous films in different Si₃N₄ ceramics. The observed film thicknesses at grain boundaries in these materials varied between 5and 15 Å. It was shown that the grain-boundary film thickness strongly depends on film chemistry. Careful inspections of film-thickness measurements across grain boundaries in a given material suggest that the film widths vary on the order of 1 Å. Therefore, a quantitative evaluation should allow for the determination of the standard deviation of the film thickness. The amorphous film widths along grain boundaries in four materials were measured over the entire length (up to 1 μm) of the grain boundary between two triple points. Forty to fifty data points were evaluated for each boundary, giving a Gaussian-like distribution of the film thickness around a median value, which corresponded well with the film width measured from single HREM micrographs. The accuracy achieved by the statistical method was better than ± 1 Å.     

PHASE-SPACE DIFFUSION EQUATIONS FOR SINGLE BROWNIAN PARTICLE MOTION NEAR SURFACES

In numerous physical processes involving the motion of micron and submicron sized particles near surfaces, such as the filtration of hydrosols and aerosols, the particle motion is the net result of the combined effects of fluid convection, external forces, particle inertia, Brownian particle motion, and particle-surface fluid dynamic interactions. The most general method of describing particle motion under the combined action of these effects is through the so-called Fokker-Planck equation. In the absence of particle-surface fluid dynamic interactions, the Fokker-Planck equation is well-known, and it has been applied in a general way to problems involving the adsorption or deposition of Brownian particles onto surfaces through a solution technique known as the Brownian dynamics simulation method.

In this study, the Fokker-Planck equation for Brownian particle motion near surfaces is generalized to include particle-surface fluid dynamic interactions. The Fokker-Planck equation is shown to follow from the Liouville equation for the Brownian particle and n-fluid molecules present in the system, thus, establishing a firm theoretical foundation for the Fokker-Planck equation and the various other phase-space diffusion equations that follow from it.

Based on diagonalization of the Fokker-Planck equation, its short-time behavior is also derived here which enables a generalization of the Brownian dynamics method for the study of particle motion near surfaces including fluid dynamic interactions. Additionally, a perturbation solution of the Fokker-Planck equation under the conditions of small, but finite particle Stokes number is also derived. These solutions are shown to agree with previously given representations of the Smoluchowski or convective-diffusion equation for Brownian particle motion near surfaces, as well as with inertial corrections to the Smoluchowski equation available in the literature. This latter equation is also generalized here to include particle-surface fluid dynamic interactions.     

Control policies for an industrial acetylene hydrogenation reactor

This paper addresses the problem of finding optimal operational policies for an acetylene reactor for day to day operation. A lumped parameter model based on four main reactions is developed and used to examine the effects of the reactor manipulated variables on key reaction parameters. An optimal and a sub-optimal operational policy which minimize the ethylene loss over time are formulated and the solution techniques are presented. The results indicate that the reactor model is in good agreement with industrial plant data. The performance of the optimal control policy is very similar to the performance of the sub-optimal control policy. However, the sub-optimal formulation, while retaining the dominant features of the optimal response, reduces the computational requirements. Finally, some issues concerning the real-time implementation of an advanced acetylene reactor control scheme are presented. These include the estimation of the optimum regeneration cycle, a recursive model update algorithm, the process optimizer and their overall coordination. A preliminary analysis of the benefits associated with the advanced control scheme suggests a considerable reduction in the yearly ethylene loss.     

Mass determination of the fatty acids released from tannin-stimulated rabbit alveolar macrophages

Previous studies with macrophages that had been prelabeled with [¹⁴C]arachidonic acid (20∶4) have shown that condensed tannin is a potent agonist for the release of arachidonic acid. However, it has not been demonstrated that the percentage release of [¹⁴C]20∶4 accurately reflects the metabolic activity of the endogenous 20∶4 pool. In order to measure the 20∶4 mass release relative to the total cellular 20∶4 pool, the free fatty acids of freshly isolated alveolar macrophages were derivatized with a fluorescent reagent, and then separated and quantified by high-performance liquid chromatography. The amounts of esterified fatty acids were measured by gas chromatography of the methyl esters. Free fatty acid levels were compared to those of the total esterified plus unesterified fatty acids to determine the actual percentage released of each fatty acid. Tannin-stimulated release of 20∶4 mass reflected that previously reported for the release of [¹⁴C]20∶4 label but at a slower rate and at a much lower percentage indicating that [¹⁴C]20∶4 had been incorporated into part of a more reactive pool. The specificity of the fatty acid release induced by tannin and β-1,3-glucan, a known agonist for 20∶4 release, was also examined. Both agonists promoted an increase in the levels of free 20∶4 and of other fatty acids. A comparison of the absolute increases of each of the fatty acids indicated that tannin caused a preferential increase in the mass of free 20∶4, whereas β-1,3-glucan evoked a selective increase in the mass of 16∶0. Deceased.     

An analysis of thermal warpage in injection molded flat parts due to unbalanced cooling

To illustrate the potential effect of unbalanced cooling on warpage of flat parts, a simplified two-part analysis is presented. First a computational model for amorphous polymers cooling in an injection molding cavity is presented. The simulation is a finite difference solution of the one-dimensional, transient heat conduction equation with constant material properties. Plastic and mold temperature profiles are calculated through the cooling cycle and the transients from cycle to cycle are included. Temperatures are predicted for both sides of the mold allowing asymmetrical cooling to be analyzed. The model is verified analytically and is in agreement with published data. Secondly, a simplified method of predicting the thermal warpage of a fiat part from calculated temperature profiles is discussed and illustrated. The relative effects on calculated part warpage of asymmetric mold geometry and cooling fluid temperature are predicted with this analysis method. The sensitivity of warpage to these design factors is illustrated for an example part.