Low-Field Nuclear Magnetic Resonance Time Domain Characterization of Polyunsaturated Fatty Acid–Rich Linseed and Fish Oil Emulsions during Thermal Air Oxidation

Linseed contains high levels of polyunsaturated fatty acids (PUFA), such as α-linolenic acid (> 50% ALA-18:3), that are naturally protected against thermal oxidation by their encapsulation within linseed oil bodies (OB) by multiple components including antioxidant proteins and mucilage emulsifying agents. Linseed OB emulsions (LSE) can be produced by grinding linseed seeds, adding water, adjusting pH, and sonication. This is a process that can encapsulate externally added PUFA to minimize their thermal oxidation, as it does for the intrinsic ALA PUFA. Fish oil (FO) encapsulation into this LSE platform to form linseed fish oil emulsions (LSFE) offers the possibility of a nutritive delivery system of the biologically essential FO PUFA eicosapentaenoic acid and docosahexaenoic acid. In this study, ¹H low-field nuclear magnetic resonance (LF-NMR) is used to characterize LSE's and LSFE's chemical and structural properties as well as their stability and changes under thermal oxidation (55 °C for 96 hours). ¹H LF-NMR data processing was developed to generate one-dimensional (1D) T₁ (spin–lattice), 1D T₂ (spin–spin), and 2D (T₁ vs. T₂) relaxation time spectra that can characterize OB emulsions and monitor their time domain fingerprints (spectrum peaks) of chemical and structural changes during the oxidation process. The ¹H LF-NMR analysis were further supported and correlated with conventional peroxide value test, self-diffusion, droplet size distribution, zeta potential estimation of surface stability, and gas chromatography–mass spectrometry analysis of fatty acid profile changes under thermal oxidation conditions. The 1D and 2D LF-NMR relaxation spectra showed that the LSE and LSFE did not suffer intense oxidation process, due to PUFA assembly in OB oxidative protection. These results were further confirmed by the supportive analytical methodologies. The results of this study demonstrate the efficacy of ¹H LF-NMR methodology to monitor PUFA's rich oil and emulsion thermal oxidation.     

A study of the impact of the willingness-to-learn of CAD novice users on their competence development

The notion that ‘attitude drives behavior’ manifests itself in a variety of ways in educational and occupational settings. As applied to CAD competence development, industrial training of novice CAD users on their way to becoming competent CAD users consume a lot of corporate resources. This paper is the third paper in the line of research that attempts to answer the question having to do with what it takes to make a competent CAD user. Specifically, we examine the CAD-specific factors revolving around the trainees’ willingness-to-learn CAD.These factors are analyzed in two stages. At the start of the training, trainees’ initial attitude towards CAD is established by means of a short questionnaire. Afterwards, throughout the training, trainees’ behavior (online and offline practice) is gauged and, in turn, a relation is established to illustrate how this practice leads to the development of CAD-specific skills. For this purpose, another short questionnaire was utilized. Strong correlations were established relating the trainees’ CAD-specific behavior with the CAD-specific outcomes of learning CAD syntax.Furthermore, and in order to assess the quality of the trainees’ learning of CAD, overall competence was monitored throughout the study via performance measures that describe the time it took the trainees to build test models (speed), which reflects upon the ability to learn the syntax of the CAD tool (declarative knowledge). The sophistication of the models is also used as another measure. Correlating the trainees’ character attributes with these assessed measures, it was found that the stronger is the trainees’ will to learn CAD, the stronger is the likelihood to learn faster. Perhaps more importantly, trainees with initial favorable attitude toward CAD were shown to develop increasingly positive behavior that manifested through additional practice and other forms of visible effort.     

Analyzing CAD competence with univariate and multivariate learning curve models

Understanding how learning occurs, and what improves or impedes the learning process is of importance to academicians and practitioners; however, empirical research on validating learning curves is sparse. This paper contributes to this line of research by collecting and analyzing CAD (computer-aided design) procedural and cognitive performance data for novice trainees during 16-weeks of training. The declarative performance is measured by time, and the procedural performance by the number of features used to construct a design part. These data were analyzed using declarative or procedural performance separately as predictors (univariate), or a combination of declarative or procedural predictors (multivariate). Furthermore, a method to separate the declarative and procedural components from learning curve data is suggested.     

The influence of low- and high-linear energy transfers on some physical properties of poly(methyl-methacrylate) samples

Clear poly(methyl-methacrylate)—PMMA—dosimeter is widely used in food irradiations. Positron annihilation lifetime spectroscopy (PALS) is one of the unique tools used for studying free-volumes and open-volume type defects in solid media. The Vicker's microhardness measurements offer a simple and nondestructive tool for investigating the mechanical behavior of polymer materials. PALS as well as microhardness measurements were carried out for PMMA samples, irradiated with low- and high-linear energy transfers (LET). The low-LET irradiations were provided at lethal doses of gamma radiations for vegetative bacteria. Such irradiations showed a chain scission in the PMMA samples. High-LET irradiations showed behavior different from the low-LET ones. The observed behavior depends on the alpha particle fluence. The microhardness testing was carried out for virgin and irradiated PMMA samples at high-LET. A negative correlation was found between PALS measurements and microhardness results. The optical characteristics and structural studies for the virgin and irradiated PMMA samples were in agreement with the PALS and microhardness measurements. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Alkyl Tail Segments Mobility as a Marker for Omega-3 Polyunsaturated Fatty Acid-Rich Linseed Oil Oxidative Aging

Omega-3 polyunsaturated fatty acid (PUFA)-rich linseed oil (LSO) is an important component in biological systems, foods, and many other industrial products. In recent years, LSO has attracted increased attention in the field of functional foods, which has highlighted its facile susceptibility to aging by autoxidation. Common colorimetric and a long list of spectral methodologies have been used to follow after and predict LSO shelf life's quality, especially in regards to aging by autoxidation. These standard methodologies are nevertheless limited, because of the complexity of the LSO's chemical and physical changes. The goal of the present study is to develop a sensorial ¹H LF-NMR energy relaxation time application based on monitoring primary chemical and structural changes occurring with time and temperature during oxidative thermal stress for better and rapid evaluation of LSO's aging process. Using ¹H low-field NMR, the different T₂ times of energy relaxations due to spin–spin coupling, and proton motion/mobility of LSO molecular segments were monitored. As previously reported, we characterized the chemical and structural changes in all phases of the autoxidation aging process. Starting from the initiation phase (abstraction of hydrogen radical, fatty acid chain rearrangement, and oxygen uptake yielding hydroperoxides products), through to the propagation phase (chain reactions resulting in tail cleavage to form alkoxy radicals, and alpha, beta-unsaturated aldehydes formation), and a termination phase (cross linking and production of polymerization end products). The ¹H LF NMR transverse relaxation approach, monitors both the covalent bond's strong forces (100–400 kJ mol⁻¹) in LSO oxidative aging decomposition, as well as secondary relatively weak interactive forces by hydrogen bonds (~70 kJ mol⁻¹), and electrostatic bonds (0–50 kJ mol⁻¹) contributing to secondary crosslinking interactions leading to a LSO viscous gel of polymerized products in the termination phase. In the present paper, we show that LSO tail segments mobility in terms of T₂ multi-exponential energy relaxation time decays, generated by data reconstruction of ¹H transverse relaxation components are providing a clear, sharp, and informative understanding of LSO sample's autoxidation aging processes. To support T₂ time domain data analysis, we used data from high-field band-selective ¹H NMR pulse excitation for quantification of hydroperoxides and aldehydes of the same LSO samples treated under the same thermal conditions (25, 40, 60, 80, 100, 120 °C) with pumped air for 168 hours. Peroxide value, viscosity, and self-diffusion analyses, as well as fatty acids profile and by-products determined by GC–MS on the same samples were carried out, and correlated with the LSO tail T₂ energy relaxation time results. From these results, it is postulated that selective determination of LSO tail T₂ time domain can be used as a rapid evaluation marker for following omega-3 PUFA-rich oils oxidative aging process within industrial and commercial products.     

A 0.18-μm 256-Mb DDR-SDRAM with low-cost post-mold tuning methodfor DLL replica

A 200-MHz double-data-rate synchronous-DRAM (DDR-SDRAM) was developed. The chip contains a delay-locked loop (DLL) which performs over a wide range of operating conditions. Post-mold-tuning allows precise replica programming. A 200-MHz intra-chip data bus is suitable for DDR operation     

Corrosion behavior of Eurofer 97 and ODS-Eurofer alloys compared to traditional stainless steels

In the present work, the corrosion resistance of ferritic-martensitic EUROFER 97 and ODS-EUROFER steels was tested in solutions containing NaCl or H₂SO₄ and KSCN, both at 25 °C. The results were compared to those of AISI 430 ferritic and AISI 410 martensitic conventional stainless steels. The as-received samples were tested by electrochemical techniques, specifically, electrochemical impedance spectroscopy, potentiodynamic polarization curves, and double-loop electrochemical potentiokinetic reactivation tests. The surfaces were observed by scanning electron microscopy after exposure to corrosive media. The results showed that EUROFER 97 and ODS-EUROFER alloys present similar corrosion resistance but lower than ferritic AISI 430 and martensitic 410 stainless steels.     

A CAD-suitable approach for the analysis of nonuniform MMIC andMHMIC transmission lines

A new method of moment-based formulation for the solution of the telegraphist's equations in nonuniform transmission lines is presented. Entire domain basis functions that build in a frequency variation are used to cover wider frequency and physical dimension ranges. The results obtained using the proposed formulation are validated by comparison to those obtained by a CAD package and to measured data. Different nonuniform lines in microstrip and coplanar technologies on monolithic microwave/millimeter wave integrated circuit (MMIC) and miniaturized hybrid microwave integrated circuit (MHMIC) substrates are investigated with an application to the design a matched taper transition in a MMIC coplanar line