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Thesis (M. Sc.)--York University, 1998. Graduate Programme in Chemistry. / Typescript. Includes bibliographical references (leaves 158-169). Also available on the Internet. MODE OF ACCESS via web browser by entering the following URL:http://wwwlib.umi.com/cr/yorku/fullcit?pMQ27385.

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Thesis advisor: Jeffery A. Byers / Chapter 1. Poly(lactic acid) (PLA) is a biodegradable polymer derived from renewable resources that has garnered much interest in recent years as an environmentally friendly substitute to conventional petroleum-derived engineering polymers. PLA has many applications in textiles, packaging, compostable consumables, and biomedical devices, as PLA displays excellent biocompatibility. This polymer is primarily produced from the ring-opening polymerization of lactide, a cyclic dimer of lactic acid. This introductory chapter highlights mechanistic features of this ring-opening polymerization reaction as well as metal-based catalysts that have been reported for lactide polymerization. In addition, switchable catalysis is an emerging field that has gained interest with polymer chemists for the potential of creating original polymer compositions and architectures. The utilization of redox-switchable catalysis to control lactide polymerization is discussed in this chapter. Chapter 2. Bis(imino)pyridine iron bis(alkoxide) complexes have been synthesized and utilized in the polymerization of (rac)-lactide. The activities of the catalysts were particularly sensitive to the identity of the initiating alkoxide with more electron-donating alkoxides resulting in faster polymerization rates. The reaction displayed characteristics of a living polymerization with production of polymers that exhibited low molecular weight distributions, linear relationships between molecular weight and conversion, and polymer growth observed for up to fifteen sequential additions of lactide monomer to the polymerization reaction. Mechanistic experiments revealed that iron bis(aryloxide) catalysts initiate polymerization with one alkoxide ligand, while iron bis(alkylalkoxide) catalysts initiate polymerization with both alkoxide ligands. Oxidation of an iron(II) catalyst precursor lead to a cationic iron(III) bis(alkoxide) complex that was completely inactive towards lactide polymerization. When redox reactions were carried out during lactide polymerization, catalysis could be switched off and turned back on upon oxidation and reduction of the iron catalyst, respectively. In addition, preliminary investigations of copolymerization reactions of lactide with ethylene are reported. Chapter 3. A cationic iron(III) complex is active for the polymerization of various epoxides, whereas the analogous neutral iron(II) complex is inactive. Cyclohexene oxide polymerization could be "switched off" upon in situ reduction of the Fe(III) complex and “switched on” upon in situ oxidation, which is orthogonal to what was observed previously for lactide polymerization. Conducting copolymerization reactions in the presence of both monomers resulted in block copolymers whose identity can be controlled by the oxidation state of the complex: selective lactide polymerization was observed in the iron(II) oxidation state and selective epoxide polymerization was observed in the iron(III) oxidation state. Evidence for the formation of block copolymers was obtained from solubility differences, GPC, and DOSY-NMR studies.  Chapter 4. Formally iron(I) bis(imino)pyridine monoalkoxide complexes were synthesized through protonolysis of a bis(imino)pyridine iron alkyl species with p-methoxyphenol or neopentyl alcohol. The resulting complexes were characterized by X-ray crystallography, 1H NMR, EPR, and Mössbauer spectroscopy, and preliminary characterization of the electronic structure of these complexes is discussed. These iron complexes were found to be highly active catalysts for the polymerization of various cyclic esters and carbonates, with the iron mono(neopentoxide) complex being much more active and giving more narrow molecular weight distributions than the mono(aryloxide) complex. The bis(imino)pyridine iron neopentoxide complex was highly active in particular for the polymerization of ε-caprolactone (CL), giving full conversion within 10 minutes at room temperature in toluene, making it one of the most active iron complexes reported for this transformation ([Fe]:[CL] = 1:2000). Comparison of the polymerization activity of these iron mono(alkoxide) complexes with the analogous iron(II) bis(alkoxide) complexes is reported. / Thesis (PhD) — Boston College, 2017. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Les nouveaux aspects économiques et écologiques de la chimie moderne (à savoir la gestion des déchets, l’économie d’atome) font de la réduction de liaisons polarisées C=X (X = O, N) catalysée par des complexes organométalliques, une réaction importante en chimie organique. De plus, ces complexes permettent le contrôle de la stéréo-, régio- et chimiosélectivité de ces réactions. Les complexes de fer tricarbonyle à ligand cyclopentadiènone ont montré ces dernières années une excellente réactivité pour les hydrogénations de liaisons C=O et C=N. Grâce à de précédents travaux réalisés au laboratoire, nous avons envisagé l’approche de ces réductions polarisées via l’utilisation de métalloenzymes artificielles incorporant un complexe de fer cyclopentadiènone. Parallèlement à cette étude, une optimisation des performances catalytiques de complexes de fer a été réalisée et a permis de développer l’alkylation de cétones par les alcools, la méthylation d’amines par le méthanol et la réduction de liaisons C=C pour les cétones ,-insaturées. Enfin, grâce à un nouveau complexe aminocyclopentadiènyle de fer, les réactions d’amination réductrice étudiées précédemment au laboratoire ont pu être améliorées. / Environmental and economic concerns within modern chemistry (waste management, atom economy), lead metal-catalyzed reduction of polarized C=X bonds (X= O, N) with organometallic complexes an important reaction in organic chemistry. Additionally, stereo-, regio- and chemoselective reductions can be involved in organometallic catalysis. In the past decade, cyclopentadienone iron tricarbonyl complexes were reported as efficient for the hydrogenation of C=O and C=N bonds. According to previous investigations in the group, we developed a new approach within artificial metalloenzyme involving iron complexes for the hydrogenation of polarized bonds. Simultaneously, we described new reactivities of the complex prepared in the group for ketone alkylation and amine methylation through auto-hydrogen borrowing process, and chemoselctive C=C bonds of enones. We developed as well a new aminocyclopentadienyl iron complex for the enhancement of reductive amination previously described.

The synthetic approach was developed for the preparation of N-bridged diiron phthalocyanines substituted by different electron-withdrawing alkylsulfonyl substituents. Six novel phthalocyanines bearing small (methylsulfonyl, ethylsulfonyl and hexylsulfonyl) and bulky (t-butylsulfonyl, adamantylsulfonyl and cyclohexylsulfonyl) substituents have been prepared and characterized by electrospray ionization mass spectrometry (ESI-MS), UV-Vis, FT-IR and EPR. Two complexes (with hexylsulfonyl and t-butylsulfonyl substituents) were characterized in addition by Mössbauer techniques, X-ray photoelectron spectroscopy (XPS) and Fe K-edge X-ray absorption spectroscopy (XANES, EXAFS, high resolution Kβ emission spectroscopy). It has been evidenced that the electronic state of iron in these complexes depends on the size of the substituents. While N-bridged diiron phthalocyanines having methylsulfonyl, ethylsulfonyl and hexylsulfonyl substituents are cationic (PcFeIVNFeIVPc)+N3- complexes, N-bridged diiron phthalocyanines with bulkier t-butylsulfonyl, adamantylsulfonyl and cyclohexylsulfonyl substituents are formally neutral PcFeIIINFeIVPc species. The catalytic properties of six N-bridged diiron phthalocyanines have been studied, using tert-butyl hydroperoxide (tBuOOH) as the oxidant in the oxidation of toluene, p-xylene as well as in the oxidation of various alcohols. This thesis demonstrates the efficiency of N-bridged diiron phthalocyanines substituted by electron-withdrawing alkylsulfonyl groups as oxidation catalysts, in conditions required by environmental and industrial preoccupations

Certaines métalloenzymes catalysent l’oxydation de petites molécules organiques, dans des conditions douces (par activation du dioxygène à température et pression ambiante). Ce travail a pour but d’améliorer l’utilisation et l’efficacité catalytique des complexes de fer mimant cette activité.D’abord, par fonctionnalisation du ligand, un des complexes les plus efficaces pour catalyser l’oxydation de substrats aromatiques par H2O2, a pu être greffé dans des mésopores de silice. Ce matériau est utilisé comme support de catalyseur, en raison de sa grande surface spécifique et de sa chimie de surface versatile. Par ailleurs, la méthode de synthèse permet de structurer la taille des cavités formées, à l’aide d’un surfactant utilisé comme modèle. Le contrôle du nombre de sites catalytiques sur la surface est rendu possible par la procédure qui exploite le concept du pochoir moléculaire. Le confinement du catalyseur dans les pores pourrait être mis à profit pour former des produits à haute valeur ajoutée. En parallèle, ce complexe a aussi été greffé sur des billes de silices, un matériau moins élaboré pouvant être utilisé pour la dégradation de polluants. L’élaboration de ce type de catalyseurs supportés a nécessité de nombreuses caractérisations : analyses élémentaires, spectroscopies RMN, IR, XPS, UV-vis, RPE, isotherme d’adsorption d’azote, ATG, DRX sur poudre. Différentes méthodes de greffage ont été ainsi développées, et leur efficacité a été comparée. L’activité en catalyse d’oxydation de ces différents systèmes a aussi été évaluée.Concernant le développement des catalyseurs homogènes, le renforcement des positions  des pyridines du ligand a permis l’obtention de nouveaux complexes de fer, possédant une meilleure stabilité pour réaliser des réactions catalytiques en milieu homogène et des propriétés structurales, spectroscopiques, chimiques et catalytiques analogues aux complexes de la même famille.Enfin, un autre complexe de fer a été mis en jeu dans un procédé électrochimique utilisant le dioxygène en présence de protons pour catalyser l’hydroxylation de substrats aromatiques. / Some metalloenzymes catalyze oxidation of small organic molecules in mild conditions (via dioxygen activation at ambient temperature and pressure). This work aims to improve the use and catalytic efficiency of some of the iron complexes mimicking this activity.First, by ligand functionalization, one of the most efficient complexes catalyzing aromatic substrates oxidation by H2O2, was grafted in mesostructured porous silicas. This type of materials was used to support the iron catalyst, because of their large specific area, as well as their versatile surface chemistry. Furthermore, the method of synthesis allows to tune the size of cavities, through the use of surfactant as templates. Control of the number of catalytic sites on surface is made possible by the procedure that exploits the molecular stencil patterning technique. The confinement of catalyst in the pores could be implemented to form products with high added value. In parallel, this complex was also grafted in fumed silicate, a simpler material, that could be used to degradation of polluants. The development of this type of supported catalyst required many caracterisations : elemental analysis, NMR, IR, XPS, UV-vis and EPR spectroscopies, TGA, nitrogen sorption isotherms, powder X-ray diffraction. Different grafting methods have been followed, and their efficacy compared. The catalytic activity of the different systems was also evaluated.Concerning the development of homogenous catalysts, the strengthening of pyridine  positions on the ligand has allowed to obtain new iron complexes, having a better stability to realize catalytic reactions in homogenous condition, and structural, spectroscopic, chemical, catalytic properties similar to the complexes of the same family.Finally, another iron complex has been applied in an electrochemical process using dioxygen in the presence of proton to catalyze hydroxylation of aromatic substrates.

Background: The consequences of poor nutrition are well known and of wide concern. Governments and public health agencies utilise food and diet surveillance data to make decisions that lead to improvements in nutrition. These surveys often utilise complex sample designs for efficient data collection. There are several challenges in the statistical analysis of dietary intake data collected using complex survey designs, which have not been fully addressed by current methods. Firstly, the shape of the distribution of intake can be highly skewed due to the presence of outlier observations and a large proportion of zero observations arising from the inability of the food diary to capture consumption within the period of observation. Secondly, dietary data is subject to variability arising from day-to-day individual variation in food consumption and measurement error, to be accounted for in the estimation procedure for correct inferences. Thirdly, the complex sample design needs to be incorporated into the estimation procedure to allow extrapolation of results into the target population. This thesis aims to develop novel statistical methods to address these challenges, applied to the analysis of iron intake data from the UK National Diet and Nutrition Survey Rolling Programme (NDNS RP) and UK national prescription data of iron deficiency medication. Methods: 1) To assess the nutritional status of particular population groups a two-part model with a generalised gamma (GG) distribution was developed for intakes that show high frequencies of zero observations. The two-part model accommodated the sources of data variation of dietary intake with a random intercept in each component, which could be correlated to allow a correlation between the probability of consuming and the amount consumed. 2) To identify population groups at risk of low nutrient intakes, a linear quantile mixed-effects model was developed to model quantiles of the distribution of intake as a function of explanatory variables. The proposed approach was illustrated by comparing the quantiles of iron intake with Lower Reference Nutrient Intakes (LRNI) recommendations using NDNS RP. This thesis extended the estimation procedures of both the two-part model with GG distribution and the linear quantile mixed-effects model to incorporate the complex sample design in three steps: the likelihood function was multiplied by the sample weightings; bootstrap methods for the estimation of the variance and finally, the variance estimation of the model parameters was stratified by the survey strata. 3) To evaluate the allocation of resources to alleviate nutritional deficiencies, a quantile linear mixed-effects model was used to analyse the distribution of expenditure on iron deficiency medication across health boards in the UK. Expenditure is likely to depend on the iron status of the region; therefore, for a fair comparison among health boards, iron status was estimated using the method developed in objective 2) and used in the specification of the median amount spent. Each health board is formed by a set of general practices (GPs), therefore, a random intercept was used to induce correlation between expenditure from two GPs from the same health board. Finally, the approaches in objectives 1) and 2) were compared with the traditional approach based on weighted linear regression modelling used in the NDNS RP reports. All analyses were implemented using SAS and R. Results: The two-part model with GG distribution fitted to amount of iron consumed from selected episodically food, showed that females tended to have greater odds of consuming iron from foods but consumed smaller amounts. As age groups increased, consumption tended to increase relative to the reference group though odds of consumption varied. Iron consumption also appeared to be dependent on National Statistics Socio-Economic Classification (NSSEC) group with lower social groups consuming less, in general. The quantiles of iron intake estimated using the linear quantile mixed-effects model showed that more than 25% of females aged 11-50y are below the LRNI, and that 11-18y girls are the group at highest of deficiency in the UK. Predictions of spending on iron medication in the UK based on the linear quantile mixed-effects model showed areas of higher iron intake resulted in lower spending on treating iron deficiency. In a geographical display of expenditure, Northern Ireland featured the lowest amount spent. Comparing the results from the methods proposed here showed that using the traditional approach based on weighted regression analysis could result in spurious associations. Discussion: This thesis developed novel approaches to the analysis of dietary complex survey data to address three important objectives of diet surveillance, namely the mean estimation of food intake by population groups, identification of groups at high risk of nutrient deficiency and allocation of resources to alleviate nutrient deficiencies. The methods provided models of good fit to dietary data, accounted for the sources of data variability and extended the estimation procedures to incorporate the complex sample survey design. The use of a GG distribution for modelling intake is an important improvement over existing methods, as it includes many distributions with different shapes and its domain takes non-negative values. The two-part model accommodated the sources of data variation of dietary intake with a random intercept in each component, which could be correlated to allow a correlation between the probability of consuming and the amount consumed. This also improves existing approaches that assume a zero correlation. The linear quantile mixed-effects model utilises the asymmetric Laplace distribution which can also accommodate many different distributional shapes, and likelihood-based estimation is robust to model misspecification. This method is an important improvement over existing methods used in nutritional research as it explicitly models the quantiles in terms of explanatory variables using a novel quantile regression model with random effects. The application of these models to UK national data confirmed the association of poorer diets and lower social class, identified the group of 11-50y females as a group at high risk of iron deficiency, and highlighted Northern Ireland as the region with the lowest expenditure on iron prescriptions.

Electronic excitation triggered by the absorption of light enables numerous chemical, physical and biological processes and transformations. Accordingly, full control over the processes involving excited molecules requires an in-depth knowledge of electronic UV/vis spectra and potential energy surfaces. Unsurprisingly, most electronic spectra are acquired in the condensed phase in which molecules are dissolved and most transformations occur. However, our knowledge of excitation, transformations and processes at the level of isolated molecules is still limited, partly because such studies require unconventional experimental approaches and equipment. This Thesis describes experimental methods for recording electronic spectra of isolated molecules in the gas phase by ion spectroscopy, which combines mass spectrometry with optical spectroscopy. Using these methods, experimental factors which affect the electronic excitation and therefore the electronic spectra of ions were determined and evaluated for various fluorescent xanthene dyes, iron-containing complexes and molecular pho- toswitches. Furthermore, factors which govern photochemical processes, such as photo- oxidation, photoreduction and photoisomerization, were also analyzed in detail, with surprisingly different outcomes from previous studies...