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.     

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.     

Activated gas plasma surface treatment of polymers for adhesive bonding

Polyethylene, polypropylene, poly(vinyl fluoride) (Tedlar), polystyrene, nylon 6, poly(ethylene terephthalate) (Mylar), polycarbonate, cellulose acetate butyrate, and a poly(oxymethylene) copolymer were treated with activated helium and with activated oxygen. Mechanical strengths of adhesive-bonded specimens prepared from treated and from untreated coupons were compared. Polyethylene (PE) and polypropylene (PP) showed the greatest increases in bond strength. Oxygen and helium were both effective with polyethylene, but polypropylene showed no improvement when treated with activated helium. The results with excited helium parallel the effects of ionizing radiation on these two polymers, as does the appearance of unsaturation bands in the infrared (965 cm^?1 in PE, and 887 and 910 cm^?1 in PP). Active nitrogen produced excellent bond strength with polyethylene but not with polypropylene. Of the remaining polymers examined, Tedlar, polystyrene, and nylon 6 showed the greatest improvement in bondability after treatment, and Mylar showed moderate improvement. Polycarbonate, cellulose acetate butyrate, and the poly(oxymethylene) copolymer gave approximately two-fold increases in lap-shear bond strength. In several cases, significant differences in response to time of treatment and type of excited gas were found.     

NN-based Prediction Interval for Nonlinear Processes Controller

Neural networks (NNs) are extensively used in modelling, optimization, and control of nonlinear plants. NN-based inverse type point prediction models are commonly used for nonlinear process control. However, prediction errors (root mean square error (RMSE), mean absolute percentage error (MAPE) etc.) significantly increase in the presence of disturbances and uncertainties. In contrast to point forecast, prediction interval (PI)-based forecast bears extra information such as the prediction accuracy. The PI provides tighter upper and lower bounds with considering uncertainties due to the model mismatch and time dependent or time independent noises for a given confidence level. The use of PIs in the NN controller (NNC) as additional inputs can improve the controller performance. In the present work, the PIs are utilized in control applications, in particular PIs are integrated in the NN internal model-based control framework. A PI-based model that developed using lower upper bound estimation method (LUBE) is used as an online estimator of PIs for the proposed PI-based controller (PIC). PIs along with other inputs for a traditional NN are used to train the PIC to predict the control signal. The proposed controller is tested for two case studies. These include, a chemical reactor, which is a continuous stirred tank reactor (case 1) and a numerical nonlinear plant model (case 2). Simulation results reveal that the tracking performance of the proposed controller is superior to the traditional NNC in terms of setpoint tracking and disturbance rejections. More precisely, 36% and 15% improvements can be achieved using the proposed PIC over the NNC in terms of IAE for case 1 and case 2, respectively for setpoint tracking with step changes.

     

Creating geometrically robust designs for highly sensitive problems using topology optimization

Resonance and wave-propagation problems are known to be highly sensitive towards parameter variations. This paper discusses topology optimization formulations for creating designs that perform robustly under spatial variations for acoustic cavity problems. For several structural problems, robust topology optimization methods have already proven their worth. However, it is shown that direct application of such methods is not suitable for the acoustic problem under consideration. A new double filter approach is suggested which makes robust optimization for spatial variations possible. Its effect and limitations are discussed. In addition, a known explicit penalization approach is considered for comparison. For near-uniform spatial variations it is shown that highly robust designs can be obtained using the double filter approach. It is finally demonstrated that taking non-uniform variations into account further improves the robustness of the designs.     

EDITORIAL

The process undertaken by an information seeker, in order to form relevance decisions regarding documents, is defined as “Document Triage.” To better facilitate users’ needs in their triage activities, interactive interfaces have begun to evolve within on-line academic repositories. In order to complement current work on interface design and interaction, and produce custom guidelines to inform the creation of triage interfaces, we examine how interfaces that alter the document presentation and structure affect information seekers’ visual and navigational attention. We present a set of heuristics for both creating and evaluating such interfaces.     

Interval or moments: which carry more information?

In many practical situations, we do not have enough observations to uniquely determine the corresponding probability distribution, we only have enough observations to estimate two parameters of this distribution. In such cases, the traditional statistical approach is to estimate the mean and the standard deviation. Alternatively, we can estimate the two bounds that form the range of the corresponding variable and thus, generate an interval. Which of these two approaches should we select? A natural idea is to select the most informative approach, i.e., an approach in which we need the smallest amount of additional information (in Shannon’s sense) to obtain the full information about the situation. In this paper, we follow this idea and come up with the following conclusion: in practical situations in which a 95 % confidence level is sufficient, interval bounds are more informative; however, in situations in which we need higher confidence, the moments approach is more informative.     

Taking science education beyond schooling

Abstract

The shape and content of science education has always been articulated from the scientist's perspective. Recently, an increasing number of science educators have recognized the serious limitations of this perspective and have proposed to define scientific literacy from societal or citizenship perspectives. In this article, I argue that these alternatives will remain as limited as their predecessors unless the very structures of schooling are called into question. Furthermore, I argue that alternatives cannot be designed at the drawing board by theoreticians, but have to be grounded in praxis, thereby providing concrete trajectories along which science education can actually change.