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published_or_final_version / abstract / Botany / Master / Master of Philosophy

Inconsistent seed germination poses a problem for efficient seedling production of Echinacea species. Evidence suggests that ethylene can be effective for improving germination in Echinacea species. The objectives of this research were: to develop an ethylene pre-germination treatment that enhances germination in Echinacea species that is retained following drying and storage, and to determine if the ethylene effect on enhanced germination was an important mode of action for dormancy release. Four species of Echinacea (E. purpurea, E. tennesseensis, E. angustifolia and E. simulata) treated with 1-aminocyclopropane-1-carboxylic acid (ACC) or ethephon resulted in faster and generally higher germination. Pre-treatment of seeds with ACC or ethephon followed by drying was as effective as chilling stratification for enhancing germination depending on the species. While ethylene pretreatments did increase germination to some extent depending on species, it was concluded that 60-day stratification alone was a more commercially-viable treatment. Ethylene production or perception was not necessary for germination in untreated or stratified seeds as shown by aminoethoxyvinylglycine (AVG), silver thiosulfate (STS), and 1-methylcyclopropene (MCP) treatments. Both stratification and ACC treatment reduced Echinacea seed sensitivity to ABA and could be a common mechanism for enhanced germination. However, it does not appear that the increased germination seen after stratification was mediated through ethylene production because final germination percentages were generally unchanged following inhibition of ethylene production or action. In contrast, inhibition of ethylene production and perception reduced early 3-day germination suggesting that ethylene was more involved in seed vigor than final germination. It was determined that there is no physiological significance of ethylene for dormancy release in these Echinacea species.

The new ligand L1 [2-[(E)-2,6-diisopropylphenyl-phenyimino]-2H-acenaphthylen-(1E)-ylidene]-(2,4,6-trimethyl-phenyl)-amine was prepared by stepwise addition of 2,6-diisopropylaniline and 2,4,6 trimethylaniline to acenaphthenequinone. The L1NiBr2 complex crystallized as a pseudo tetrahedral monomer, as determined by single crystal X-ray diffraction. This new catalyst L1NiBr2 and 3 related catalysts, bis(2,6-diisopropylphenyl)acenaphthenediimineNiBr2 (L2NiBr2), [(N,N'-bis-(2,6-diisopropylphenyl)-phenanthrene-9,10-diylidendiamineNi-η3-C3H4COOCH3)]+.{B[C6H3(CF3)2]4-} [(L3Ni-η3-C3H4COOCH3)]+.{B[C6H3(CF3)2]4-} and N-(2,6-diisopropylphenyl)-N'-(2,4,6-trimethylphenyl)-phenanthrene-9,10-diylidenediamineNiBr2 (L4NiBr2) were tested for activity in ethylene polymerization. The super-bulky α-diimine nickel catalysts [(η3- L3NiC3H4COOCH3)]+.{B[C6H3(CF3)2]4-} and L4NiBr2 successfully produced higher molecular weight polyethylene with a high level of linearity compared to the less bulky α-diimine nickel catalysts (L1NiBr2 and L2NiBr2). The super bulky α-diimine backbone helped to compress the reaction space and therefore impede the ethylene insertion to active centre of the catalyst. For this reason, the catalyst activity for super- bulky backbone ligands (L3 and L4) is lower than for their analogous less-bulky backbone ligands (L1 and L2). In general, for both backbones, the nickel catalysts with all-isopropyl substituents produced higher molecular weight polyethylene with less linearity compared to the nickel catalysts with methyl substituents. Moreover, for the acenaphthene backbone, the nickel catalysts with all isopropyl substituents (L2NiBr2) got a higher activity compared to the nickel catalysts with methyl substituents (L1NiBr2). A similar catalyst activity trend was not observed for phenanthrene backboned catalysts. In contrast, L4NiBr2 showed a higher activity compared to [(η3- L3NiC3H4COOCH3)]+.{B[C6H3(CF3)2]4-} For all catalysts, the majority of branches, as characterized by 13C nuclear magnetic resonance, were methyl branches. Polymers with a high level of branches showed a sharp intensity in the loss modulus measured by dynamic mechanical analysis due to a high level of interfacial chains. A reduction in catalyst activity was observed with all nickel catalysts when supported on silica. However, supporting nickel catalysts helps to improve the linearity of the polymer. The same ligands L3 and L4 were used with palladium and successfully produced two new catalysts [L3PdCH3NCCH3]+.{B[C6H3(CF3)2]4-} and [L4PdCH3NCCH3]+.{B[C6H3(CF3)2]4-. Catalyst [L3PdCH3NCCH3]+.{B[C6H3(CF3)2]4-} was more active and produced higher molecular weight and less branched polymer than catalyst [L4PdCH3NCCH3]+.{B[C6H3(CF3)2]4-} in the polymerization of ethylene.

The purpose of this investigation was to determine the effect of the operating variables of type of reactor, catalyst, ethylene feed concentration, temperature, and contact time on the products of oxidation of ethylene to ethylene oxide; and together with subsequent hydrolysis to evaluate the commercial feasibility of the manufacture of ethylene glycol. The review of the literature contained 10 references. The equipment employed was arranged as indicated in a general flow diagram for the system. A silver catalyst activated by barium peroxide was employed and prepared on No.7 and No.3 Valencia pumice as the carrier according to Wiseman. For the analysis of ethylene oxide the procedure employed was a modification of that suggested by Vaughan and Wiseman. The carbon dioxide content of the product gases was determined by absorption of the carbon dioxide by ascarite; moisture was removed by means of drierite. Data and Results: A summation was made of operating conditions, yields and conversion in the air oxidation of ethylene in a fixed bed and fluidized bed reactor as a function of type of catalyst, contact time, reactor bath temperature, ethylene feed concentration, employing a barium peroxide activated silver catalyst coated on No.3 and No.7 Valencia pumice , uncoated pumice, and mixtures of these catalysts. It was found advisable to employ a 50% mixture of catalyst-coated and uncoated carrier in the tests because of the tendency toward fusion of the catalyst particles when used alone as the reactor charge . An increase the ethylene feed concentration from 3 to 9 per cent does not seem to appreciably affect either the conversion or yield. / Ph. D.

published_or_final_version / Chemistry / Master / Master of Science

No description available.

No description available.