Analyses of lipids and oxidation products by partition chromatography: Hydroxy fatty acids and esters

A liquid-partition chromatographic procedure was used to separate hydroxy fatty acids, their methyl esters, and reduced fatty ester hydroperoxides. Mixtures of methyl stearate, mono- and dihydroxystearate, and mixtures of the corresponding free fatty acids were easily separated. Chromatographic determinations for ricinoleate in castor oils compared favorably with the chemical and infrared analyses. The chromatographic procedure was used to separate hydroxy fatty acids inDimorphotheca andStrophanthus seed oils. The methyl ester of dimorphecolic acid, the principal hydroxy fatty ester ofDimorphotheca oil, behaved like reduced methyl linoleate hydroperoxide and showed a polarity intermediate between methyl 12-hydroxystearate and methyl 9,10-dihydroxystearate. The 9-hydroxy-12-octadecenoic ester ofStrophanthus oil had a larger retention volume than methyl ous hydroxy fatty esters isolated chromatographically. The diene content of the reduced hydroperoxides agrees well with values reported in the literature (1,5,16). The diene content of the chromatographed methyl dimorphecolate is higher than reported by Smithet al. (20) for their preparations but agrees well with the value reported by Chipault and Hawkins (6) for puretrans-trans conjugated methyl linoleate. The extinction coefficient of methyl 12-hydroxystearate at 2.8 μ is higher than that reported for ricinoleate and the absorption band is much sharper. Because of these two conditions no association of the hydroxyl groups is indicated. These results also confirm the purity of the hydroxy fatty esters obtained by LPC. This method has been a valuable adjunct to the study of various oxygen-containing fatty acid and esters and was used to characterize the hydroxy esters obtained from the hydrogenation of methyl linolenate hydroperoxides (9). This work offers a basis for the development of analytical methods to determine the hydroxy and other polar acid content of fatty glycerides and their derivatives.     

Chemistry of mandibular and Dufour's gland secretions of ants in genusMyrmecocystus

Males of several species ofMyrmecocystus produce mandibular gland secretions that contain 2,4-dimethyl-2-hexenoic acid and a variety of monoterpenes that include neral, geranial, citronellol, limonene, and 2,6-dimethyl-5-hepten-1-ol. Other components identified include methyl anthranilate, octanal, octanol, octyl octanoate, and 2-hexyl-2-decenal. Methyl salicylate has been identified as a mandibular gland constituent of workers of several species in addition to mellein and monoterpenes such as cymene, limonene, and the isomers of citral. The Dufour's gland secretions of workers and females of 14 species contain typical formicine alkanes (e.g., undecane), 2-alkanols (e.g., 2-tridecanol), and 2-alkanones (e.g., 2-tridecanone). Two species in the subgenusEremnocystus produce secretions that are distinguished by the presence of significant quantities of tridecyl esters. The functions of these compounds as well as their possible chemosystematic significance in the genusMyrmecocystus are discussed.     

Adhesion of Polyethylene to Copper: Importance of Substrate Topography

In order to get good adhesion between polyethylene and copper previous workers have oxidized the metal in alkaline solution to give a matt black oxide film. In this paper it is shown that the good adhesion obtained is associated with the very rough, fibrous nature of the matt black oxide film. Adhesion rises as the layer develops on the copper. If the fibres are damaged to alter the topography without changing the chemical nature of the substrate, the adhesion falls markedly. If the chemical nature of the oxide film is changed by electrolytic reduction, with minimum change in topography, the adhesion is still substantial. Adhesion to these matt black oxide films is still good if oxidation of the polymer is suppressed either by incorporation of stabilizers or by coating in a nitrogen atmosphere. This further points to the importance of topography in adhesion to these surfaces.     

Long term storage of soybean and cottonseed salad oils

Commercially prepared and packaged soybean and cottonseed salad oils from several different processors were evaluated periodically during storage for 12 months. Partially hydrogenated and winterized soybean oils, as well as unhydrogenated soybean salad oils, were stored in bottles and cans at 78 and 100 F. Control samples of all oils were held at 0 F during the entire test. Some lots in bottles and cans were packaged under nitrogen to improve storage stability. Agreement was good between organoleptic and oxidative evaluation of aged oils. After 26 weeks of storage at 100 F, the flavor of partially hydrogenated-winterized oils packaged under nitrogen showed a minimum loss. These same oils did not exhibit much, if any, reduction in their oxidative stability as indicated by storage peroxide values (active oxygen method). Soybean oil not protected with nitrogen demonstrated progressive flavor deterioration at 100 F. After 10 weeks of storage, the deterioration became marked and the flavor score was below 5. From limited observations, bottled oils appear to have a better stability than oils packaged in screw-cap tin cans. Hydrogenated oils packaged under nitrogen in cans had good oxidative stability, but some lowering of the flavor score was observed. Nonhydrogenated soybean oils packaged in tin cans not under nitrogen exhibited the most rapid flavor deterioration of all lots of oil investigated. Presented in part at the AOCS meeting, New York, October 1968 ARS, USDA     

The Oxidation of NdFeB Magnets

The oxidation kinetics in air of a commercial NdFeB magnet have been investigated over the temperature range 335–500°C. The oxide microstructure has been characterized by SEM, XRD and cross-sectional TEM. The results show that the external scale formed consists of an outer layer of Fe₂O₃ and an inner layer of Fe₃O₄ but that the principal degradation process is the formation of an extensive zone of internal oxidation. HREM has been used to show that this zone contains NdO particles embedded in an -Fe matrix. These particles are discrete and very small, approximately 2 nm in diameter, and have an amorphous structure. The -Fe matrix has a columnar grain structure with a grain width of approximately 100 nm. It is argued that the high rates of internal oxidation arise because the external-oxide layers are not protective at the oxidation temperature, and oxygen penetrates to the zone front by fast diffusion along the columnar -Fe grain boundaries.     

On the mechanical performance of closed cell Al alloy foams

The mechanical properties of three different commercially available closed cell Al alloys all made by foam casting are examined. The objective is to assess the roles of cell morphology and of imperfections in governing the basic properties: stiffness, yield strength and fracture resistance. This assessment provides goals for manufacturing strategies that enable attainment of good mechanical performance with affordable process technologies. A prevalent role of curves and wiggles in the cell walls on stiffness and strength (anticipated by models) is affirmed by the present measurements. Systematically larger stiffnesses and yield strengths found in tension than in compression are consistent with a prominent role exerted by such imperfections. Moreover, foam casting is apparently capable of cell morphologies that impart properties approaching the best achievable values for an isotropic closed cell solid, devoid of imperfections. There are associated implications for performance and affordability. Fracture measurements indicate crack growth occurring along the cell walls by a mechanism analogous to the plastic tearing of thin sheets. The crack growth resistances are in the range of 1 kJm⁻². This mechanism infers a toughness that scales with the cell wall thickness and its yield strength.     

Computer-aided methods in bespoke breast prosthesis design and fabrication

This case study presents a method of utilizing computer-aided design technologies to provide bespoke, external breast prostheses. The technique is illustrated through a case study of a mastectomy patient. Photogrammetry methods were used to capture the breast form when supported by a brassiere and the unsupported breast and defect side. Computer-aided design techniques were used to generate a digital prosthesis based upon the supported breast shape and with a fitting surface that matched the defect side. Furthermore, a two-part mould was designed and fabricated using rapid prototyping methods. A colour-matched prosthesis was then fabricated in a gel-based, platinum-cured silicone.     

Children and careers in IT

David Evans, BCS government relations, looks at what it couldtake to convince kids that the hard stuff is worth doing.     

Model-based 3-D segmentation of multiple sclerosis lesions in magnetic resonance brain images

Human investigators instinctively segment medical images into their anatomical components, drawing upon prior knowledge of anatomy to overcome image artifacts, noise, and lack of tissue contrast. The authors describe: 1) the development and use of a brain tissue probability model for the segmentation of multiple sclerosis (MS) lesions in magnetic resonance (MR) brain images, and 2) an empirical comparison of the performance of statistical and decision tree classifiers, applied to MS lesion segmentation. Based on MR image data obtained from healthy volunteers, the model provides prior probabilities of brain tissue distribution per unit voxel in a standardized 3-D "brain space". In comparison to purely data-driven segmentation, the use of the model to guide the segmentation of MS lesions reduced the volume of false positive lesions by 50-80%