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Thesis (M.S.)--Rochester Institute of Technology, 1987. / Typescript. Includes bibliographical references (leaves 73-74).

<p>A new method for analysis of acidic herbicides, mostly phenoxy acids and their esters, in cereals with liquid chromatography-tandem quadrupole mass spectrometry (LS-MS/MS) has been developed. Samples were hydrolyzed with sodium hydroxide in order to release covalently bound compounds followed by neutralization and finally extraction with acidified ethyl acetate. The extraction efficiency for both ester formulations and acids were studied. Acceptable results (70-120 %) were obtained for 2,4-D, dichlorprop, MCPA and mecoprop for both esters and acids. However, low recoveries were observed for ester formulations of dicamba, fluroxypyr, fluazifop and haloxyfop, possibly due to the complex structure of the compounds in combination with the matrix and/or incomplete hydrolysis step. The limit of quantification (LOQ) for targeted pesticides was 0.01 mg/kg. The method has been tested in the EU Proficiency Test for cereals with good results.</p>

A new method for analysis of acidic herbicides, mostly phenoxy acids and their esters, in cereals with liquid chromatography-tandem quadrupole mass spectrometry (LS-MS/MS) has been developed. Samples were hydrolyzed with sodium hydroxide in order to release covalently bound compounds followed by neutralization and finally extraction with acidified ethyl acetate. The extraction efficiency for both ester formulations and acids were studied. Acceptable results (70-120 %) were obtained for 2,4-D, dichlorprop, MCPA and mecoprop for both esters and acids. However, low recoveries were observed for ester formulations of dicamba, fluroxypyr, fluazifop and haloxyfop, possibly due to the complex structure of the compounds in combination with the matrix and/or incomplete hydrolysis step. The limit of quantification (LOQ) for targeted pesticides was 0.01 mg/kg. The method has been tested in the EU Proficiency Test for cereals with good results.

Les α-oléfines jouent un rôle très important en tant qu'intermédiaires réactionnels dans l'industrie chimique et pétrochimique. Leur utilisation principale est la production de diverses qualités de polyéthylène dans lequel l'α-oléfine est engagée en tant que co-monomère (butène-1, hexène-1 et octène-1). Les systèmes capables de dimériser, trimériser voir tétramériser sélectivement l'éthylène en α-oléfines supérieures, utilisent principalement le titane et le chrome. Du fait de la toxicité potentielle du chrome, la recherche industrielle et académique s’oriente de plus en plus vers des systèmes à base de titane.Notre objectif dans ce contexte était d’étudier le potentiel des systèmes « phénoxy-tridente » du Ti(IV) pour la trimérisation sélective de l’éthylène en hexène-1. De nombreux systèmes de formules générales [(ArO-X-L)TiCl3] (X=O,P,N et L=O,P,N) ont ainsi été isolés et caractérisés. L’étude de leurs propriétés électroniques et stériques et ses conséquences sur leurs performances en oligomérisation/polymérisation de l’éthylène ont été discutées. Elles mettent en évidence la criticité de l’ensemble des paramètres à la fois électroniques et structuraux du ligand. Un seul système de cette famille est capable de produire sélectivement de l’hexène-1, les autres conduisant à la polymérisation de l’éthylène.Une étude DFT associée à une étude expérimentale des propriétés redox des précurseurs catalytiques ou encore du comportement hémilabile des ligands mis en jeu, nous a conduit à proposer un mécanisme identifiant la phase d’activation comme l’élément clé permettant d’orienter les systèmes étudiés vers la polymérisation ou la production sélective d’hexène-1. / Linear α-olefins (LAOs) are crucial importance for the chemical and petrochemical industry as they are highly valuable feedstock for a variety of process mainly as co-monomer for the production of different grade of polyethylene (1-butene, 1-hexene and 1-octene). Some systems and predominantly chromium and titanium systems have performed selective dimerization, trimerization and tetramerization of ethylene to higher α-olefins. For toxicity reasons, industrial and academic research focus more and more on titanium-based systems.Our objective in this context was the study of potential “tridentate phenoxy” systems of Ti(IV) for selective trimerization of ethylene to 1-hexene. Numerous systems with general formula [(ArO-X-L)TiCl3] (X=O,P,N and L=O,P,N) were described and characterized. The study of electronic and steric properties and their consequences on catalytic performances in oligomerization/polymerization of ethylene were discussed. They showed the criticity of all electronic and structural parameters of ligands. Only one system of this family is able to produce selectively 1-hexene, others give mainly polyethylene.DFT study associated with an experimental study of redox properties on catalytic precursors or the hemilabile behavior of ligands involved, led us to propose a mechanism identifying the activation phase as the key to switch between polymerization or selective trimerization of ethylene.

It has been found that the herbicide 2,4-D has the ability to increase the rate of transport of positive ions of several kinds and inhibit the transport of negatively charged tetraphenylborate ions in lipid bilayer membranes. Only the neutral molecules of 2,4-D are transport active. The ionized 2,4-D molecules do not modify the transport of ions, and do not by themselves permeate through lipid membranes. The results suggest that the enhancement of transport of positively charged ions is dominated by the increase of the ion translocation rate constant. It has been shown that membrane transport of negatively charged tetraphenylborate ions is suppressed by 2,4-D. The effect is dominated by the suppression of translocation of these ions across membrane interior, rather than by the decrease of their adsorption at the membrane surface. It has been shown that the enhancement of nonactin-mediated transport of potassium ions by 2,4-D can be accounted for by a simple carrier model. From the changes of kinetic parameters of nonactin-K('+) transport, membrane conductance due to positively charged tetraphenylarsonium ions and also from the changes of membrane conductance and relaxation time constant due to transport of negatively charged tetraphenylborate ions, the changes of the electric potential of the membrane interior have been estimated. The potential of the membrane interior becomes more negative in the presence of 2,4-D and its change is proportional to the aqueous concentration of 2,4-D. The effect of 2,4-D on ion transport was explained by the hypothesis that a layer of 2,4-D molecules is absorbed within the membrane/water interfacial region, and that the 2,4-D molecules are oriented in such a way that their dipole moment is directed toward the aqueous medium. The results suggest that this layer is located in the hydrocarbon side of the interface. The hypothesis has been confirmed by the measurements of changes of electric potential difference across air/water and air/lipid monolayer/water interfaces. It has been found that the electric potential of the nonpolar side of the interface decreases in the presence of neutral molecules of 2,4-D, which is in agreement with the conclusions drawn from the results of membrane experiments. The effect of the other auxin-type phenoxy herbicides, 2,4,5-T and 2,4-DB on lipid bilayer membranes has been found to be similar to that of 2,4-D. In contrast, the phenoxy acid 2,4,6-T, has very little or no herbicidal activity, and at the same time has small effect on ion transport in membranes. Biologically active 2,4-D derivatives, amino acid conjugates of 2,4-D (isoleucine, leucine and valine conjugates) have been found to be also transport active in a manner similar to 2,4-D. Similar conclusions have been drawn from experiments with natural auxin indole acetic acid. The results obtained in this work suggest the existence of correlation between the biological activity of herbicides acting as plant growth regulators and their ability to enhance transport of positively charged ions across lipid membranes. This work provides insight into the physical origin of such activity.

Ternary blends comprising Polysulphones [Polyethersulphone (PES) and Polysulphone (PSO)], the Polyhydroxyether of bisphenol-A (Phenoxy), and Polyesters [Poly( ethylene terephthlate) (PET) and Poly(butylene terephthlate) (PBT)] have been studied particularly with the aim in mind of elucidating the factors determining their miscibility and morphology. Binary and ternary combinations, including equivalent systems based on a butylene terephthlate-tetramethylene oxide block copolymer (PBT-TMO), were prepared from solution and by mixing in the melt state using both an internal mixer and a twin screw extruder. Scanning electron microscopy was employed to examme the morphology of these blends. A co-continuous, (interpenetrating), dual-phase morphology was displayed by both the PSO/PBT and PSO/PBT-TMO (70/30) combinations. The compatibility was further increased by the addition of Phenoxy, which was evidenced by the formation of a very fine dispersion of the two phases for both PSO/Phenoxy/PBT and PSO/Phenoxy/PBT-TMO blends, in the weight ratio of (60/15/25). A lower level of compatibility was displayed by the equivalent blends based on PES and PET, as a matrix/dispersed particle type of morpholgy was usually observed. Differential thermal analysis and dynamic mechanical analysis measurements were also employed to ascertain the level of miscibility in these systems. A single composition dependent glass transition temperature was displayed by the binary PBT/Phenoxy and PBT-TMO/Phenoxy melt blends, and the binary PES/Phenoxy and _PSO/Phenoxy solution blends. The remaining blends displayed two separate glass transition temperatures that were often broader and closer together than those of the homopolymers. This effect was more significant for blends containing the Phenoxy compatibiliser, confirming that these systems are semi-miscible. Solvent resistance measurements were made on 500μm thick extruded sheets by measuring the time to failure at stress levels corresponding to 30% and 50% of the tensile strength. The blends displaying a matrix/dispersed particle type of morphology revealed poor solvent resistance and mechanical properties. The blends displaying a cocontinuous interpenetrating dual-phase morphology on the other hand displayed a much higher solvent resistance and enhanced mechanical properties.

DNA damage is important to understand since it has the potential to lead to disease if unrepaired. In particular, bulky C8 guanine adducts (addition products) are known to induce a variety of mutations due to their conformational flexibility. C-linked C8-phenoxyl-deoxyguanosine adducts (PhOH-dG) have been poorly understood despite their potential for genotoxicity. This thesis systematically develops a computational model to predict the conformational and base-pairing preferences of PhOH-dG by gradually increasing the size of the system. The structure of PhOH-dG in DNA is determined, where the bulky C8 group induces a syn conformation of the base similar to other C8-adducts. A stabilized guanine mismatch is identified for the syn adducts, which implies that the primary mechanism of genotoxicity may be base-substitution mutations resulting in G→C transversions. This thesis has contributed to a growing body of literature dedicated to understanding the role of conformational heterogeneity in the mutagenicity of bulky C8-adducts. / xix, 192 leaves : ill. (some col.) ; 29 cm

The Ph.D. thesis was focused on EPR study of redox reactions of selected types of phenols, secondary amines and diperoxy coumpounds. Within the study some redox agents were employed in nonpolar, in some special cases also in polar solvents. EPR spectra of generated radical products were interpreted using spectral simulation. Study of radical reactions under participation of phenols was preferentially concentrated on the behavior of para methyl substituted phenols, where the instability of this substituent in relation to the applied redox agents was evaluated. The tendency towards the abstraction of hydrogen from methyl group, representing the paralell mechanism to the hydrogen abstaction from phenolic OH group was proved. The generated benzyl radicals were undirectly detected in the form of adducts with aromatic nitroso compounds. These adducts undergo the consecutive transformations, leading to the formation of new types of phenoxy radicals. The study of the decomposition of NH bonds was performed with substituted N,N´-paraphenylenediamines, 1-anilino-1-phenylpentane-3-ones and amino substituted 1,3-dimethyluracils. By the oxidation with 3-chloroperbenzoic acid the corresponding nitroxyl radicals were prepared. In the case of 1-anilino-1-phenylpentane-3-ones the aminyl radicals were prepared by the oxidation with PbO2, which existence was evidenced by spin trapping method with nitrosobenzene. In the framework of the investigation of the decomposition of -O-O- bonds the oxygen centred radicals, generated from peroxidic compounds of Luperox type using selected redox agents were detected by spin trapping method. The analysis of EPR spectra documented that primary alkoxyl radicals undergo the consecutive fragmentation, which leads in the presence of oxygen to the formation of secondary alkoxyl radicals. The generation of oxygen centred radicals during the decomposition was indirectly proved in the presence of model phenolic compounds, where due to the abstraction of hydrogen from phenolic OH group the phenoxyl radicals are formed.

<p>Quantum chemical methods have been used to provide a better understanding of the photochemistry of astaxanthin and phytochromobilin; the photoenzymic repair of UV-light induced DNA damages; and the formation of lignin. </p><p>The carotenoid astaxanthin (AXT) is responsible for the colouration of lobster shell. In solution, the electronic absorption spectra of AXT peak in the 470-490 nm region, corresponding to an orange-red colouration. Upon binding to the lobster-shell protein-complex α-crustacyanin, the absorption maximum is shifted to 632 nm, yielding a slate-blue colouration. Herein, the structural origin of this bathochromic shift is investigated on the basis of recent experimental work.</p><p>The tetrapyrrole phytochromobilin (PΦB) underlies the photoactivation of the plant photoreceptor phytochrome. Upon absorption of 660-nm light, PΦB isomerizes from a C15-<i>Z,syn</i> configuration (in the inactive form of the protein) to C15-<i>E,anti</i> (in the active form). In this work, a reaction mechanism for this isomerization is proposed. </p><p>DNA photolyases are enzymes that repair DNA damages resulting from far-UV-light induced [2+2] cycloaddition reactions involving pyrimidine nucleobases. The catalytic activity of these enzymes is initiated by near-UV and visible light, and is governed by electron transfer processes between a catalytic cofactor of the enzyme and the DNA lesions. Herein, an explanation for the experimental observation that the repair of cyclobutane pyrimidine dimers (CPD) – the major type of lesion – proceeds by electron transfer from the enzyme to the dimer is presented. Furthermore, the formation of CPD is studied.</p><p>Lignin is formed by dehydrogenative polymerization of hydroxycinnamyl alcohols. A detailed understanding of the polymerization mechanism and the factors controlling the outcome of the polymerization is, however, largely missing. Quantum chemical calculations on the initial dimerization step have been performed in order to gain some insight into these issues.</p>