2,996 research outputs found
X-ray structural studies of lanthanide macrocycles and biological molecules
The work described in this thesis is broadly divided into two sections. The structural study on the lanthanide macrocyclic complexes was afforded by means of X-ray crystallography In this chapter, the molecules dota, the cationic enantiopure tetraamide europium and dysprosium complexes, the sodium complexes of the tetranaphthylamide and quinoyl derivative, the enantiopure gadolinium and europium complexes of the tetraamide series with esteratic sidechains, the lanathanum and ytterbium complexes of the dota derivative with benzyl phosphinate sidechains, and the tetracarboxyethyl series both as three uncomplexed stereoisomer and complexes of the RRRR stereoisomer with europium, gadolinium and terbium. These complexes exhibit quite a lot of structural diversity. Chapter five deals with experiments carried out at ultra low temperatures. A phase transition that the molecule benzil undergoes is investigated on the Fddd diffractometer, a study of the interesting 1,12-dicarbonyl borane was undertaken to obtain precise values for the carbonyl bond lengths and the unprecedented structure of its hydrate was revealed to be a carbene diol and not the expected carboxylic acid complex The standard for macromolecular tests for diffraction, chicken egg white lysozyme, was crystallised and used to optimise conditions for low-temperature data acquisition from macromolecular samples The work described in this Thesis was carried out in the Department of Chemistry, Durham University from October 1995 to January 1999, under the supervision of Professor J.A.K. Howard. All of the work is my own, unless stated to the contrary, and it has not been submitted previously for a degree at this or any other university
SELF-FORGIVENESS IN ROMANTIC RELATIONSHIPS: THE IMPACT ON THE PERPETRATOR AND THE RELATIONSHIP
Two studies were conducted to determine how self-forgiveness and other perpetrator reactions influence the perpetrator and the victim after a romantic relationship transgression. Study 1 used a longitudinal design to determine how guilt and shame predicted the trajectory of self-forgiveness, self-excusing, and self-punishing in participants who had recently been the perpetrator of a romantic relationship transgression.
Those experiencing higher guilt at baseline had higher self-forgiveness starting out and those lower on guilt starting out had a greater change in self-forgiveness. Those experiencing more guilt at baseline experienced less change in self-forgiveness over time. Shame was not significantly related to self-forgiveness over time. Those experiencing higher shame at baseline were higher in self-excusing starting out. Those lower on shame starting out had a greater increase in self-excusing over time and those experiencing more shame at baseline experienced less increase in self-excusing over time. Guilt was not significantly related to self-excusing over time. Neither guilt nor shame predicted change in self-punishment over time.
In Study 2, couples came into the lab and wrote about the same offense. One participant wrote from the perspective of the perpetrator and the other from the perspective of the victim. Victims reported their forgiveness and perception of their partnersâ reactions to wrongdoing. Perpetrators reported their perception of their partnersâ feelings of forgiveness and their feelings of self-forgiveness, self-excusing, and self-punishing. Both members reported their relationship satisfaction and commitment.
Overall, self-forgiveness by the perpetrator was not a strong predictor of perpetrator satisfaction or commitment. Victims were more satisfied and committed when perceiving self-forgiveness from their partner, even though their partnersâ self-forgiveness did not have an effect. Self-forgiveness only positively predicted perpetratorsâ satisfaction and commitment when participants reported decisional self-forgiveness.
Victimsâ perceptions of the perpetratorsâ self-excusing and perpetratorsâ self-punishing negatively predicted victim commitment and satisfaction. Victimsâ perceived perpetrator self-punishing positively predicted perpetratorsâ commitment. Perpetrator perceived victim forgiveness and victim forgiveness both positively predicted satisfaction for the perpetrator and the victim. This suggests that perpetratorsâ perceptions of victim forgiveness may be more important for the perpetrator than the victim actually forgiving them
Experimental Tests of the New Paradigm for Laser Filamentation in Gases
Since their discovery in the mid-1990s, ultrafast laser filaments in gases
have been described as products of a dynamic balance between Kerr self-focusing
and defocusing by free electric charges that are generated via multi-photon
ionization on the beam axis. This established paradigm has been recently
challenged by a suggestion that the Kerr effect saturates and even changes sign
at high intensity of light, and that this sign reversal, not free-charge
defocusing, is the dominant mechanism responsible for the extended propagation
of laser filaments. We report qualitative tests of the new theory based on
electrical and optical measurements of plasma density in femtosecond laser
filaments in air and argon. Our results consistently support the established
paradigm.Comment: 4 pages, 4 figure
Nutritive value of forage legumes used for grazing and silage
peer-reviewedLegume forages have an important position in ruminant production in Western Europe
and with further development can play an even larger role. Red clover for silage and white
clover in grazed swards lead to enhanced growth rate and milk yield in comparison with
pure grasses. Much of the production benefit of these legumes relates to enhanced intake
since digestibilities are not markedly different to grasses. The higher intake of legume
silages reflects differences in the cell structure of legume plants which combined with
high fermentation rates means that they break down into small particles in the rumen,
and leave the rumen more rapidly than perennial ryegrass. Ease of ingestion leads to
high rates of intake, which explains higher intakes for grazed legumes. A further benefit
of legumes is the reduced rate of decline in digestibility with advancing maturity. Whilst
legumes have limited effects on gross milk composition or carcass characteristics, there
are marked increases in levels of beneficial nâ3 PUFA. Legumes have often led to a reduction
in methane production from the rumen and again, this relates to both physical and
chemical differences between forage species. The high rates of release of soluble protein
and of breakdown to small particles from clovers and lucerne is associated with susceptibility
to bloat, which is a limitation to further exploitation in grazing systems. The high
concentration of rapidly degraded protein in legumes also leads to inefficient utilisation
of dietary N and increased urinary N output. Research with tanniniferous forages, such
as birdsfoot trefoil and sulla, demonstrates the potential for future legumes with reduced
environmental and health effects, though these particular forage legumes are not well
adapted to temperate regions of Western Europe that are the focus of this review
An examination of the molecular mechanisms controlling the tissue accumulation of conjugated linoleic acid (CLA) in cattle
End of project reportLong chain n-3 polyunsaturated fatty acids (n-3 PUFA) and conjugated linoleic acid (CLA) have demonstrable and potential human health benefits in terms of preventing cancer, diabetes, chronic inflammation, obesity and coronary heart disease. Supplementation of cattle diets with a blend of oils rich in n-3 PUFA and linoleic acid have a synergistic effect on the accumulation of ruminal and tissue concentrations of trans vaccenic acid (TVA), the main substrate for ?-9 desaturase which is responsible for de novo tissue synthesis of the cis 9, trans 11 isomer of CLA. This dietary strategy translates into increases in milk concentrations of CLA in dairy cows; however, concentrations in the muscle of beef animals have not always been increased. There is an apparent paradox in that n-3 PUFA supplementation enhances ruminal synthesis of trans-vaccenic acid (TVA), but then inhibits its conversion to CLA possibly through altering the activity of ?-9 desaturase. Recently, the promoter regions of the bovine ?- 9 desaturase gene has been isolated and analysed and has been shown to contain a conserved PUFA response region
Dynamically accelerated cover times
Among observables characterizing the random exploration of a graph or lattice, the cover time, namely, the time to visit every site, continues to attract widespread interest. Much insight about cover times is gained by mapping to the (spaceless) coupon collector problem, which amounts to ignoring spatiotemporal correlations, and an early conjecture that the limiting cover time distribution of regular random walks on large lattices converges to the Gumbel distribution in d ⼠3 was recently proved rigorously. Furthermore, a number of mathematical and numerical studies point to the robustness of the Gumbel universality to modifications of the spatial features of the random search processes (e.g., introducing persistence and/or intermittence, or changing the graph topology). Here we investigate the robustness of the Gumbel universality to dynamical modification of the temporal features of the search, specifically by allowing the random walker to âaccelerateâ or âdecelerateâ upon visiting a previously unexplored site. We generalize the mapping mentioned above by relating the statistics of cover times to the roughness of 1 / f Îą Gaussian signals, leading to the conjecture that the Gumbel distribution is but one of a family of cover time distributions, ranging from Gaussian for highly accelerated cover, to exponential for highly decelerated cover. While our conjecture is confirmed by systematic Monte Carlo simulations in dimensions d > 3 , our results for acceleration in d = 3 challenge the current understanding of the role of correlations in the cover time problem
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