Thesis (Ph. D.)--University of Wisconsin--Madison, 1963. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 71-74).

Methods for the remotely triggered release of biologically active molecules has been an area of intense research in recent years, as it would allow hard-to-obtain biomolecules to be tested in cell-like environments.1 The removal of polar functional groups from hydrophilic structures upon the application of an external stimulus would generate unfunctionalised molecules, which could then participate in amphiphilic self-assembly. This could be used in the release of bioactive molecules and therefore in the in vitro investigation of drug activity. In this PhD project, diazene chemistry was identified as the optimal method for the generation of unfunctionalised compounds through the removal of polar groups since fragmentation takes place rapidly and without the formation of potentially toxic intermediates or by-products. The synthesis of a range of protected hydrazines is described in this thesis (Scheme 1), in addition to the investigation of the rates of decomposition of various simple sulfonyl hydrazides, which led to the isolation of the product of the decomposition of a sulfonyl hydrazide. The photolysis of NVOC- and NPPOC-protected hydrazine derivatives is discussed.

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xvi, 233 p. : ill. (some col.) A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / The coordination chemistry of iron with N 2 is becoming increasingly important as chemists try to find alternative routes to the production of ammonia. Current biological and industrial processes use iron to catalyze the formation of ammonia from N 2 ; however, huge amounts of energy are required for this conversion. Understanding how dinitrogen and other intermediates of dinitrogen reduction interact with iron could lead to energy efficient processes for the production of ammonia. This dissertation explores the synthesis and reactivity of an iron dinitrogen complex that reacts with acid to produce ammonia at room temperature and pressure. This dissertation also explores the progress toward determining the mechanism of this reaction in hopes of improving the yields of ammonia. Chapter I describes both the biological nitrogen fixation process and the industrial production of ammonia and provides an in-depth look at progress toward an alternative route to ammonia using iron complexes described in the literature thus far. Chapter II details the synthesis, characterization, and reactivity of dihydrogen and dinitrogen complexes of iron. These complexes are precursors to the active ammonia producing complex and are among a handful of dihydrogen and dinitrogen complexes that have been structurally characterized. Chapter III explores the synthesis and stability of Fe(DMeOPrPE) 2 N 2 . This complex produces ammonia and hydrazine upon protonation with a strong acid. Optimizing the yield of ammonia from this protonation is also described. Chapter IV discusses the synthesis and reactivity of several complexes of iron containing intermediates relevant to dinitrogen reduction, including diazene (N 2 H 2 ), hydrazine (N 2 H 4 ), and ammonia. By studying these intermediates, a mechanism of ammonia formation from the protonation of Fe(DMeOPrPE) 2 N 2 is proposed that may also provide insights into the mechanism of nitrogenase. Chapter V provides a summary of this research. This dissertation includes previously published and unpublished co-authored material. / Committee in charge: Darren Johnson, Chairperson, Chemistry; David Tyler, Advisor, Chemistry; Michael Haley, Member, Chemistry; Kenneth Doxsee, Member, Chemistry; Scott Bridgham, Outside Member, Biology

<p> It had been proposed that α-hydroperoxydiazenes decompose by the radical chain abstraction of the hydroxy group. This suggested that these compounds could be used as hydroxyalkylating agents for unsaturated systems. </p> <p> Compounds 15 and 23 were prepared by the autoxidation of the corresponding hydrazone. α-Hydroperoxydiazenes 15 and 23 were used to hydroxyalkylate ethyl vinyl ether and 2-methoxypropene in yields of 62-65%. Mechanisms of the addition reaction are discussed. </p> <p> In an attempt to alkylate a hetero atom system, ·compound 15 was thermolyzed with compound 25. The alkylation product was not obtained. </p> <P> Compound 15 was converted to α-hydroxydiazene 34 by the action of Φ3P. α-Hydroxydiazine have been used synthetically in the hydroalkylation of alkenes. The rate constant of hydrogen abstraction was determined to be in the range of 1.5 x 10^5 M^-ls^-l to 1.5 x 10^7 M^-ls^-l by the use of a radical clock reaction. An upper limit on the rate of rearrangement of the 2-cyanopropyl radical was found to be 3.65 x 10^3 s^-1 . </p> A new compound (23) was prepared / Thesis / Master of Science (MSc)

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Cette these a pour cadre l'optimisation de films minces (1-10 microns) polymeres hybrides pour la realisation de composants passifs et actifs de l'optique integree. Nous avons plus precisement etudie la mobilite de molecules d'azobenzene soumises a des excitations electriques et photoniques dans deux types de matrices sol-gel : - dans une matrice faiblement reticulee, le processus de photo-isomerisation conduit a des phenomenes de migration moleculaire pouvant provoquer des deformations de surface spectaculaires (> 1 micron). Notre etude a porte plus particulierement sur la reponse du materiau vis-a-vis du de l'intensite, de la polarisation et des frequences spatiales de la figure d'illumination (franges d'interferences). On decrit aussi la realisation d'un coupleur a reseau, qui constitue l'un des composants passifs de l'optique integree. - dans une matrice fortement reticulee, l'orientation thermo-assistee des molecules d'azobenzene par un champ electrostatique applique au film permet de briser la centrosymetrie du materiau et de lui conferer des proprietes non-lineaires quadratiques. Les mecanismes d'orientation ont ete plus finement etudies en analysant l'influence de la concentration moleculaire sur l'efficacite du doublage de frequence par le materiau. On montre qu'un moyen d'ecranter les interactions dipolaires et ainsi d'augmenter notablement la mobilite des molecules actives est d'incorporer dans le materiau des groupements steriques passifs. Appliquee a des molecules optimisees par l'ingenierie moleculaire, cette strategie supramoleculaire a permis d'obtenir de forts coefficients electro-optiques stables a temperature ambiante et depassant ceux des meilleurs materiaux inorganiques (> 50 pm/v a 832 nm). Si de plus, les groupements steriques presentent des proprietes de photoconduction, on realise un materiau photorefractif. Nous avons analyse les proprietes originales d'un systeme presentant un effet photorefractif sans champ applique. .