Impact of Phosphoethanolamine Reverse Micelles on Lipid Oxidation in Bulk Oils

Phospholipids are important minor components in edible oil that play a role in lipid oxidation. Surface active phospholipids have an intermediate hydrophilic–lipophilic balance value, which allows them to form association colloids such as reverse micelles in bulk oil. These association colloids can influence lipid oxidation since they create lipid–water interfaces where prooxidants and antioxidants can interact with triacylglycerols. In this study, we examined the formation of reverse micelles in a stripped oil system by dioleoyl phosphoethanolamine (DOPE) and the effect of these physical structures on lipid oxidation kinetics. The critical micelle concentration (CMC) of DOPE was approximately 200 µmol/kg oil at 45 °C. Oxidation kinetics studies showed that DOPE was prooxidative when it was above its CMC (400 and 1,000 µM), reducing the lag phase from 14 days (control) to 8 days. The addition of combinations of DOPE and dioleoyl phosphocholine (DOPC) resulted in formation of mixed micelles with a CMC of 80 µmol/kg oil at 45 °C. These mixed micelles were also prooxidative when concentrations (100 and 500 µM) were above the CMC, decreasing the lag phase from 14 to 8 days. These findings provide a better understanding of the role of phospholipids in lipid oxidation of edible oil and could contribute to better antioxidant solutions.     

Finite element modeling of resistive surface layers by micro-contact impedance spectroscopy

Micro-contact impedance spectroscopy (MCIS) is potentially a powerful tool for the exploration of resistive surface layers on top of a conductive bulk or substrate material. MCIS employs micro-contacts in contrast to conventional IS where macroscopic electrodes are used. To extract the conductivity of each region accurately using MCIS requires the data to be corrected for geometry. Using finite element modeling on a system where the resistivity of the surface layer is at least a factor of ten greater than the bulk/substrate, we show how current flows through the two layers using two typical micro-contact configurations. This allows us to establish if and what is the most accurate and reliable method for extracting conductivity values for both regions. For a top circular micro-contact and a full bottom counter electrode, the surface layer conductivity (σ_s) can be accurately extracted using a spreading resistance equation if the thickness is ~10 times the micro-contact radius; however, bulk conductivity (σ_b) values can not be accurately determined. If the contact radius is 10 times the thickness of the resistive surface, a geometrical factor using the micro-contact area provides accurate σ_s values. In this case, a spreading resistance equation also provides a good approximation for σ_b. For two top circular micro-contacts on thin resistive surface layers, the MCIS response from the surface layer is independent of the contact separation; however, the bulk response is dependent on the contact separation and at small separations contact interference occurs. As a consequence, there is not a single ideal experimental setup that works; to obtain accurate σ_s and σ_b values the micro-contact radius, surface layer thickness and the contact separation must all be considered together. Here we provide scenarios where accurate σ_s and σ_b values can be obtained that highlight the importance of experimental design and where appropriate equations can be employed for thin and thick resistive surface layers.     

Preventing Wetting Between Liquid Copper and Solid Steel: A Simple Extraction Technique

Metallurgical and Materials Transactions B - Copper contamination of end-of-life steel scrap is the main barrier to high-quality recycling. Preferential melting of copper from solid steel scrap is...     

Impact of dietary fiber coatings on behavior of protein-stabilized lipid droplets under simulated gastrointestinal conditions

Multilayer emulsions containing lipid droplets coated by lactoferrin (LF) - anionic polysaccharide layers have improved resistance to environmental stresses (such as pH, salt, and temperature), but their behavior within the gastrointestinal tract (GIT) is currently unknown. The objective of this research was therefore to monitor changes in the physicochemical properties and digestibility of these systems under simulated GIT conditions. Primary emulsions (5% corn oil, 0.5% LF) were prepared using a high-pressure homogenizer. Secondary emulsions (5% corn oil, 0.5% LF, 0.5% polysaccharide) were prepared by incorporating alginate, low methoxyl pectin (LMP) or high methoxyl pectin (HMP) into primary emulsions. Emulsions were then subjected to simulated gastric fluid (SGF) and simulated intestinal fluid (SIF) conditions in sequence. LF, LF-LMP and LF-HMP emulsions were stable to droplet aggregation in the stomach but aggregated in the small intestine, whereas LF-alginate emulsions aggregated in both the stomach and small intestine. The presence of a dietary fiber coating around the initial lipid droplets had little influence on the total extent of lipid digestion in SIF, but LF-alginate emulsions had a slower initial digestion rate than the other emulsions. These results suggest that the dietary fiber coatings may become detached in the small intestine, or that they were permeable to digestive enzymes. Pepsin was found to have little influence on the physical stability or digestibility of the emulsions. The knowledge obtained from this study is important for the design of delivery systems for encapsulation and release of lipophilic bioactive ingredients.     

Modulation of physicochemical properties of emulsified lipids by chitosan addition

Electrostatic interactions between polysaccharides and proteins at oil–water interfaces alter the physicochemical properties and stability of emulsions. In this research, we studied the influence of chitosan addition on the properties of oil-in-water emulsions containing whey protein-coated lipid droplets. Experiments were carried out under conditions where the protein and polysaccharide had similar charges (pH 3.0) or opposite charges (pH 6.5). At pH 3.0, chitosan addition (0–0.025%) had little influence on droplet charge, aggregation, creaming stability or shear viscosity of whey protein emulsions, which was attributed to the fact that the cationic chitosan molecules did not adsorb to the cationic droplet surfaces due to electrostatic repulsion. At pH 6.5, chitosan addition caused a decrease in particle negative charge, an increase in particle size, a decrease in creaming stability, and an increase in viscosity. These effects were attributed to droplet aggregation caused by charge neutralization and bridging resulting from attraction of cationic chitosan molecules to anionic patches on the protein-coated droplet surfaces. Addition of cationic polyelectrolytes to protein-stabilized emulsions may be utilized to control their physicochemical properties, stability and biological fate, which may be useful for developing commercial products with novel or improved functional properties.     

The p53-, Bax- and p21-dependent inhibition of colon cancer cell growth by 5-hydroxy polymethoxyflavones

Scope: Previously, we reported that 5‐hydroxy polymethoxyflavones (5OH‐PMFs) isolated from orange, namely 5‐hydroxy‐6,7,8,3′,4′‐pentamethoxyflavone, 5‐hydroxy‐3,6,7,8,3′,4′‐hexamethoxyflavone (5HHMF) and 5‐hydroxy‐6,7,8,4′‐tetramethoxyflavone (5HTMF), potently induced apoptosis and cell‐cycle arrest in multiple human colon cancer cells. Herein, using isogenic variants of HCT116 human colon cancer cells, we investigated the effects of p53, Bax and p21 on the apoptosis and cell‐cycle arrest induced by different 5OH‐PMFs. Methods and results: Annexin V/PI co‐staining assay demonstrated that 5HHMF and 5HTMF significantly induced apoptosis in HCT116 (p53^+/+) cells but not in HCT116 (p53^?/?) cells. Furthermore, 5HHMF and 5HTMF significantly induced apoptosis in HCT116 (Bax^+/?) cells, whereas their pro‐apoptotic effects on HCT116 (Bax^?/?) cells were marginal. All three 5OH‐PMFs increased G0/G1 cell population of HCT116 (p53^+/+) cells, and these effects were abolished in HCT116 (p53^?/?) and HCT116 (p21^?/?) cells. Immunoblotting analysis showed that 5HHMF and 5HTMF increased the levels of cleaved caspase‐3, cleaved PARP in both HCT116 (p53^+/+) and HCT116 (Bax^+/?) cells and these effects were much weaker in HCT116 (p53^?/?) and HCT116 (Bax^?/?) cells. Conclusion: Our results demonstrated that 5OH‐PMFs, especially 5HHMF and 5HTMF, induce apoptosis and cell‐cycle arrest by p53‐, Bax‐ and p21‐dependent mechanism.     

Role of physical structures in bulk oils on lipid oxidation

Lipid oxidation is important to food manufacturers especially when they increase unsaturated lipids in their products to improve nutritional profiles. Unfortunately, the number of antioxidants available to food manufacturers to control oxidative rancidity is limited and the approval of new antioxidants is unlikely due to economic barriers in obtaining government approval for new food additives. Therefore, new antioxidant technologies are needed for food oils. This paper reviews the current knowledge of lipid oxidation in foods with emphasis on how physical properties of food systems impact oxidation chemistry. In particular, the role of association colloids in bulk oils on lipid oxidation chemistry is discussed in an attempt to understand mechanisms of oxidation. Increasing the understanding of how physical properties impact lipid oxidation could lead to the development of novel antioxidant technologies that not only protect the oil against oxidation and increase shelf-life but also allow food manufacturers to include more nutritionally beneficial fatty acids in their products.     

Manufacture and measurement of combinatorial libraries of dielectric ceramics: Part II. Dielectric measurements of Ba1−xSrxTiO3 libraries

Applying combinatorial methods to materials science offers the opportunity to accelerate the discovery of more efficient dielectric ceramics. High-throughput methods have the potential to investigate the effects of a wide range of dopants on the dielectric properties, and to optimise existing systems, encouraging the short innovation cycles that the communications technology industry requires. The London University Search Instrument (LUSI) is a fully automated, high-throughput combinatorial robot that has the potential capability to produce large numbers of sintered bulk ceramic samples with varying composition in 1 day, as combinatorial libraries on alumina substrates. Ba_1−xSr_xTiO₃ (BST) libraries were produced by LUSI as a proof-of-principle, with x = 0–1 in steps of 0.1, and fired to 1350 and 1400 °C for 1 h. Part I of this paper described the manufacture and physical characterisation of BST libraries, showing a regular change in composition with x across the libraries. In this second part, the dielectric properties of BST libraries produced by LUSI are assessed at frequencies between 100 Hz and 1 MHz, and at temperatures between 150 and 500 K. Local piezoelectric properties were also characterised by scanning probe microscope (SPM). All measurements showed evidence of a clear functional gradient varying with x across the library, with measured _r corresponding to expected values for BST.