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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 775-791 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Diffusion coefficients for H, D, and T on a Ni(100) surface and in bulk Ni are calculated using variational transition state theory with semiclassical ground-state transmission coefficients using two potential energy surfaces obtained by the embedded atom method (EAM). The original EAM potential reproduces experimental bulk diffusion coefficients, but greatly overestimates the diffusion coefficients for H and D on Ni(100). By refining the empirical potential parameters, a new EAM potential is developed that accurately reproduces both the bulk and surface diffusion coefficients. The variational transition state theory calculations are used to analyze the unusually low (compared to gas phase) H/D kinetic isotope effects for diffusion in bulk and on the Ni(100) surface. For the temperature range for which experiments have been carried out, quantum mechanical tunneling contributes negligibly to the diffusion and, in these cases, the kinetic isotope effect is determined largely by the change in zero-point energy between the reactant equilibrium binding sites and the transition state. A near equality of the reactant and transition state zero-point energies leads to the unusually low kinetic isotope effects. Using the same refined EAM potential energy surface, the energetics of diffusion on the Ni(111) and Ni(110) surfaces are also presented. The barriers for diffusion on these two surfaces are sufficiently low, about 1.0 kcal/mol, that the approximation of uncorrelated hops needed to relate the computed hopping rate to the diffusion coefficient is suspect. Although diffusion coefficients were not computed, based upon an analysis of the zero-point energies at the reactants and saddle points, we predict that the H/D kinetic isotope effects for diffusion on these two surfaces will also be close to unity.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Journal of natural products 53 (1990), S. 375-381 
    ISSN: 1520-6025
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Journal of natural products 53 (1990), S. 429-435 
    ISSN: 1520-6025
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Oxford, UK : Blackwell Publishing Ltd
    Annals of the New York Academy of Sciences 606 (1990), S. 0 
    ISSN: 1749-6632
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Natural Sciences in General
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 1573-1561
    Keywords: Lubber grasshopper ; Romalea guttata (microptera) ; Orthoptera ; Acrididae ; sequestration ; catnip ; Nepeta cataria ; cyclopentanoid monoterpenes ; phenolics ; generalist herbivore ; defensive secretion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Adults of a generalist herbivore, the lubber grasshopper,Romalea guttata, can be converted to functional specialists by feeding them exclusively on catnip,Nepeta cataria. No obvious adverse effects on adult development resulted from this enforced monophagy. Notwithstanding the fact thatR. guttata has had no coevolutionary relationship with this Eurasian mint, it readily sequesters compounds that are identical to or derived from the terpenoid lactones that are characteristic ofN. cataria. R. guttata appears to both biomagnify minor allelochemicals and to sequester metabolites of theNepeta terpenes in its paired defensive glands. The levels of autogenously produced phenolics are not affected by feeding onN. cataria and the defensive secretions of catnip-fed grasshoppers are more repellent to ants than those of wild-fed acridids. Metabolites of theN. cataria monoterpenes are sequestered in the defensive glands when catnip is added to the natural diet ofR. guttata. The ability of a generalist,R. guttata, to facilely bioaccumulate a potpourri of foreign allelochemicals when feeding in a specialist mode is analyzed in terms of its biochemical, physiological, and functional significance. Sequestration is examined as a response to the enteric effronteries represented by the phytochemicals that can be characteristic of the “overload” in a monophagous diet.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 1573-1561
    Keywords: Polymorphism ; chemotaxonomy ; Reticulitermes flavipes ; Reticulitermes santonensis ; Isoptera ; termites ; cuticular hydrocarbons ; defensive compounds ; terpenes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Colonies ofReticulitermes flavipes andR. santonensis were collected from the southeastern United States (Georgia) and the southwest of France (Charente-maritime). Defensive compounds and cuticular hydrocarbons were identified by gas chromatography-mass spectrometry and quantified by gas chromatography using an internal standard for each caste and all colonies. These analyses show that although the cuticular hydrocarbons ofR. santonensis in Europe andR. flavipes in Georgia are identical, their relative proportions are different. However, the defensive compounds synthesized by their soldiers are different. A strong chemical polymorphism between sympatric colonies ofR. flavipes in the SW United States was detected in terms of both the hydrocarbons of the workers and soldiers and in the defensive secretions of the soldiers. The six defensive secretion phenotypes are based on the presence or absence of terpenes whereas the cuticular hydrocarbon phenotypes are based on significant differences in the proportions of the various components. A multivariate analysis (analysis of principal components) clearly permitted discrimination of four phenotypes (three inR. flavipes and one inR. santonensis) without intermediates. The hydrocarbons responsible for these variations were identified, and it was shown that the variations are neither seasonal nor geographic. The phenotypes of the cuticular hydrocarbons (workers and soldiers) and defensive compounds are linked in each colony, forming in three groups inR. flavipes Georgia, one subdivided into four subgroups according to the defensive secretion phenotypes. The role of these polymorphisms is discussed and ethological tests indicate that the chemical polymorphism do not determine aggressive behavior. The taxonomic significance of these results is considered and two hypothesis are formulated: (1) We only detected a strong genetic polymorphism in one unique species, and we believe thatR. santonensis was introduced into Europe in the last century from oneR. flavipes colony. (2) Chemical variability characterizes the sibling species that can be grouped into the same subspeciesR. flavipes. Unknown mechanisms of reproductive isolation separate them.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Journal of chemical ecology 16 (1990), S. 1-2 
    ISSN: 1573-1561
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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