MODIFICATION OF MEMBRANE COMPOSITION, EICOSANOID METABOLISM, AND IMMUNORESPONSIVENESS BY DIETARY OMEGA-3 AND OMEGA-6 FATTY ACID SOURCES, MODULATORS OF ULTRAVIOLET-CARCINOGENESIS

Dietary sources of lipids containing predominantly n-3 or n-6 fatty acids (FA) have been examined for effect upon several potential pathophysiologic parameters. Epidermal, plasma, and red blood cell (RBC) membrane FA composition exhibited marked differences between animals fed the respective dietary lipid sources. Reduced levels of 18:1, 20:3 and 20:4 occurred in the n-3 FA fed animals which exhibited significantly higher levels of 20:5 and 22:6. Approximately equal levels of 18:2 were present in animals fed either diet. Despite marked differences in RBC membrane FA composition, only marginal effect upon osmotic fragility occurred. Lower levels of 20:3 and 20:4 found in n-3 fed animals could result from a deficit of elongase and/or delta 5-desaturase activity. Whether lower 20:4 levels in n-3 fed animals could rate-limit eicosanoid metabolism is unknown, but epidermal capacity to metabolise arachidonic acid in these animals was found to be closely related to n-6 FA intake. Animals fed n-3 FA exhibited markedly lower levels of plasma PGE2, even when the diet was supplemented with n-6 FA. In addition, UV-radiated animals receiving the n-3 FA source demonstrated a reduced (approximately 30%) response to inflammatory stimulus and a greater (4.5-fold) delayed hypersensitivity (DH) to dinitrochlorobenzene than animals fed the n-6 FA source. These data demonstrate that dietary lipid strongly influences tissue FA composition, eicosanoid metabolism, and, in the case of DH, at least one type of T-cell mediated immune response in UV-irradiated animals.     

The dynamical motion of atoms at the Ni(111) surface

One atom phonon spectral densities are presented for the vibrations of atoms at the Ni(111) surface both parallel and perpendicular to the surface. They are also presented for perpendicular motion of an adsorbed oxygen atom and the nickel atom immediately below it. The results are obtained using a continued fraction technique. They are compared with recent EELS data obtained by Ibach and Bruchmann.     

Converging flow of a viscoelastic liquid

Two-dimensional creeping sink flow of a Maxwell fluid is an accurate approximation to a bounded converging flow of contraction ratio at least 5 : 1 and covergence half-angles of up to 45°. In this range, a perturbation expansion in Weissenberg number can be used over most of the flow field in the range where stable processing can be carried out.     

Influence of dietary menhaden oil upon carcinogenesis and various cutaneous responses to ultraviolet radiation

Abstract Recent reports suggest that eicosapentaenoic acid (EPA) inhibits growth of transplanted tumors and the formation of various chemically induced cancers in animals. Menhaden oil is a source of polyunsaturated lipid with a high content of EPA, an omega-3 fatty acid. We sought to explore the effects of menhaden oil on photocarcinogenesis by employing the hairless mouse/UV-carcinogenesis model. Five groups of 40 SKH-Hr-1 mice received (a) a semipurined equicaloric diet containing either 0.75% corn oil, 4% corn oil. 4% menhaden oil or 12% menhaden oil and (b) an escalating regimen of UV radiation to a cumulative dose of 70 J/cm². Additional animals were employed to further examine the role of menhaden oil in acute cutaneous responses to UV, i.e., erythema, edema, and ornithine decarboxylase (ODC) induction. After a 2-week feeding period UV-induced ODC activity in mice receiving 12 or 20% menhaden oil was 3 to 13-fold lower than that of corn oil fed animals. Further studies showed that edema was also markedly decreased. Animals receiving menhaden oil required twice the level of irradiance to evoke a comparable erythema as that which occurred in corn oil fed animals. Menhaden oil exerted significant influence upon carcinogenic expression, as manifested in significantly longer tumor latent periods and lower tumor multiplicities when compared to corn oil fed animals. Although the mechanism(s) of these menhaden oil effects remains unknown, it is clear that this unique lipid has a pronounced influence upon cutaneous photoresponses. 15th Annual Meeting of the American Society for Photobiology, Bal Harbor, FL, June, 1987.     

Synthesis of macrocyclic ligands containing the indole ring system

2,7-Diformyl-3-methyl-4,6-dimethoxyindole (6) has been synthesized and converted by metal template reactions into the macrocyclic complexes (10–12).     

Catalytic electronic activation as a tool for the addition of stabilised nucleophiles to allylic alcohols

This paper describes the activation of 2-cyclohexen-1-ol (1) and 2-cyclopenten-1-ol (11) through the use of aluminium-catalysed transfer hydrogenation. The electronically activated substrates are demonstrated to undergo facile conjugate addition and, when the alcohol functional group is subsequently restored in a one-pot procedure, this leads to an indirect addition of nucleophiles to allylic alcohols. This novel methodology has been termed catalytic electronic activation.The aluminium tert-butoxide catalysed conversion of 2-cyclohexen-1-ol (1) into 2-(3-hydroxycyclohexyl)-2-methylmalononitrile (18) and 2-cyclopenten-1-ol (11) into 2-(3-hydroxycyclopentyl)-2-methylmalononitrile (16) in 90 and 60% yield, respectively has been demonstrated through an efficient domino Oppenauer/Michael addition/Meerwein-Ponndorf-Verley process.     

Registering the Amica electronic structure code in the extensible computational chemistry environment

We describe the integration and use of the Amica software package ("Atoms & Molecules In Chemical Accuracy") within the Extensible Computational Chemistry Environment (Ecce). Amica is capable of accurately solving the electronic Schrodinger equation of small atoms and molecules using terms that are linear in the interelectronic distances, r(12), on multireference level of theory, but it requires expert knowledge to configure and execute its algorithms. Ecce is a comprehensive suite of tools that support the computational chemistry research processes of computation setup, execution, and analysis through a convenient graphical user interface. Additionally, Ecce was architected with mechanisms to integrate alternative electronic structure codes. The successful integration of Amica within Ecce validates the architecture of the latter and brings the high-accuracy capabilities of Amica to a wider audience.