3 resultados para 03241052 TM-9
em CaltechTHESIS
Resumo:
Part I: An approach to the total synthesis of the triterpene shionone is described, which proceeds through the tetracyclic ketone i. The shionone side chain has been attached to this key intermediate in 5 steps, affording the olefin 2 in 29% yield. A method for the stereo-specific introduction of the angular methyl group at C-5 of shionone has been developed on a model system. The attempted utilization of this method to convert olefin 2 into shionone is described.
Part II: A method has been developed for activating the C-9 and C-10 positions of estrogenic steroids for substitution. Estrone has been converted to 4β,5β-epoxy-10β-hydroxyestr-3-one; cleavage of this epoxyketone using an Eschenmoser procedure, and subsequent modification of the product afforded 4-seco-9-estren-3,5-dione 3-ethylene acetal. This versatile intermediate, suitable for substitution at the 9 and/or 10 position, was converted to androst-4-ene-3-one by known procedures.
Resumo:
The reaction 7Li(3He, p)9Be has been used to measure excitations and intrinsic widths of levels in 9Be below the 7Li + d threshold. Previously unreported levels have been found at excitations of (13.78 ± .03) MeV and (16.671 ± .008) MeV with widths of (590 ± 60) keV and (41 ± 4) keV respectively. Two overlapping levels have been found at (11.81 ± .02) MeV and (11.29 ± .03) MeV with widths of (400 ± 30) keV and (620 ± 70) keV respectively. Branching ratios from 9Be levels populated in this reaction to the ground and first excited states of 8Be have been measured by observing the associated protons in coincidence with the decay neutrons. Branching ratios were found to be:
Excitation in 9Be .... Branching Ratio.......... Final Nucleus.........
(MeV) .......................... (percent) .....................................
.. 2.43 ........................... 7.5 ± 1.5 .............. 8Be(g.s.)
.. 3.03 ........................... 87 ± 13......................................
.. 4.65 ........................... 13 ± 4.......................................
.. 6.76 .............................. ≤ 2 ......................................
.. 11.29 ...............................≤ 2 ......................................
.. 11.81 ...............................≤ 3 ......................................
.. 6.76 ........................... .41 ≤ B.R. ≤ .69 ....... 8Be(2+)
.. 11.29 ........................... 14 ± 4 .......................................
.. 11.81 ........................... 12 ± 4 .......................................
Corresponding reduced widths for neutron emission are calculated and a comparison of the results with the expectations of current nuclear models is made. In particular the measured branching ratio to 8Be(g.s.) from 9Be(2.43 MeV) corresponds to an f-wave reduced with θ2f = 2.1 x 10-2, in units of ħ2/mR2, with R = 4.35 fm. A comparison of this value with that predicted by a Nilsson model calculation, in which 9Be is taken to be a deformed nucleus, is discussed. The measured value for θ2f is found to be consistent with that expected on the basis of measured E2-transition rates between rotational levels in 9Be.
Resumo:
Part I. The cellular slime mold Dictyostelium discoideum is a simple eukaryote which undergoes a multi-cellular developmental process. Single cell myxamoebae divide vegetatively in the presence of a food source. When the food is depleted or removed, the cells aggregate, forming a migrating pseudoplasmodium which differentiates into a fruiting body containing stalk and spore cells. I have shown that during the developmental cycle glycogen phosphorylase, aminopeptidase, and alanine transaminase are developmentally regulated, that is their specific activities increased at a specific time in the developmental cycle. Phosphorylase activity is undetectable in developing cells until mid-aggregation whereupon it increases and reaches a maximum at mid-culmination. Thereafter the enzyme disappears. Actinomycin D and cycloheximide studies as well as studies with morphologically aberrant and temporally deranged mutants indicate that prior RNA and concomitant protein synthesis are necessary for the rise and decrease in activity and support the view that the appearance of the enzyme is regulated at the transcriptional level. Aminopeptidase and alanine transaminase increase 3 fold starting at starvation and reach maximum activity at 18 and 5 hours respectively.
The cellular DNA s of D. discoideum were characterized by CsC1 buoyant density gradient centrifugation and by renaturation kinetics. Whole cell DNA exhibits three bands in CsCl: ρ = 1.676 g/cc (nuclear main band), 1.687 (nuclear satellite), and 1.682 (mitochondrial). Reassociation kinetics at a criterion of Tm -23°C indicates that the nuclear reiterated sequences make up 30% of the genome (Cot1/2 (pure) 0.28) and the single-copy DNA 70% (Cot1/2(pure) 70). The complexity of the nuclear genome is 30 x 109 daltons and that of the mitochondrial DNA is 35-40 x 106 daltons (Cot1/2 0.15). rRNA cistrons constitute 2.2% of nuclear DNA and have a ρ = 1.682.
RNA extracted from 4 stages during developmental cycle of Dictyostelium was hybridized with purified single-copy nuclear DNA. The hybrids had properties indicative of single-copy DNA-RNA hybrids. These studies indicate that there are, during development, qualitative and quantitative changes in the portion of the single-copy of the genome transcribed. Overall, 56% of the genome is represented by transcripts between the amoeba and mid-culmination stages. Some 19% are sequences which are represented at all stages while 37% of the genome consists of stage specific sequences.
Part II. RNA and protein synthesis and polysome formation were studied during early development of the surf clam Spisula solidissima embryos. The oocyte has a small number of polysomes and a low but measurable rate of protein synthesis (leucine-3H incorporation). After fertilization, there is a continual increase in the percentage of ribosomes sedimenting in the polysome region. Newly synthesized RNA (uridine-5-3H incorporation) was found in polysomes as early as the 2-cell stage. During cleavage, the newly formed RNA is associated mainly with the light polysomes.
RNA extracted from polysomes labeled at the 4-cell stage is polydisperse, nonribosomal, and non-4 S. Actinomycin D causes a reduction of about 30% of the polysomes formed between fertilization and the 16-cell stage.
In the early cleavage stages the light polysomes are mostly affected by actinomycin.