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“Matrix effects” in Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy are the spectroscopic changes induced by intermolecular interactions, providing sensitivity to local structure and order in solids and liquids. This project aims to identify the effect of intermolecular interactions caused by different n-alkane solid state structures on their NEXAFS spectra. Changes to the carbon 1s NEXAFS spectra are studied as a function of their solid state structure and organization. Two experimental approaches were proposed in this project. In the first approach, different n-alkane crystal structures (orthorhombic, monoclinic, etc.) are examined which arise as a function of n-alkane chain length. In the second approach, changes observed through the pre-melting point order-disorder phase transition found in n-alkanes are examined. This work will explore the characteristic spectroscopic differences observed between n-alkanes in different crystalline forms as well as in the disordered phase below the melting points. In this project, well-ordered diamond shape n-alkane single crystals were obtained by solution casting, using experimental conditions optimized for each n-alkane. As circularly polarized radiation will average the effect of molecular orientation, circularly polarized radiation was used to obtain the NEXAFS spectra of n-alkanes. However, in the analysis of the NEXAFS spectra of n-alkanes recorded with the left circularly polarized X-rays, a significant linear polarization contamination was found. Therefore, linearly polarized X-rays were used to acquire angle dependent NEXAFS spectra, where the X-ray polarization was deliberately aligned along the principal axes (X, Y) of the n-alkane crystal. It was observed that the room temperature carbon 1s NEXAFS spectrum of n-octacosane (C28H58) was different from that of the other n-alkanes, n-tetracosane (C24H50), n-tricosane (C23H48) and n-tetracontane (C40H82). This difference can be attributed due to the different crystal packing of n-octacosane (C28H58 - monoclinic) relative to the other n-alkanes (triclinic and orthorhombic), suggesting different intermolecular interactions (matrix effects) in n-octacosane (C28H58). The analysis of the temperature dependent NEXAFS spectra of n-alkanes reveals that samples of the short chain n-alkane crystals, specially n-tricosane (C23H48), n-tetracosane (C24H50) and n-octacosane (C28H58), sublimed in the STXM microscope. Changes observed in the carbon 1s NEXAFS spectra of n-tetracontane (C40H82) with temperature were attributed to the order-disorder transition. This further illustrates the existence of matrix effects in the NEXAFS spectra of n-alkanes.

The versatility of N-heterocyclic carbenes (NHCs) is demonstrated by numerous practical applications in homogeneous transition metal catalysis, organocatalysis and materials science. There remains a paucity of electropositive metal NHC complexes and so this chemistry is poorly developed with respect to that of the late transition metal and main group elements. This thesis describes the synthesis of new alkoxy-tethered NHC proligands, their use in the synthesis of reactive metal amide and metal alkyl complexes, and finally small molecule activation using these complexes. Chapter One introduces NHCs and discusses their use as supporting ligands for early transition metal and f-block complexes. Small molecule activation using organometallic complexes is examined alongside the use of electropositive metal NHC complexes in catalysis. Chapter Two contains the synthesis and characterisation of new alkoxy-tethered NHC proligands and a variety of electropositive MII (M = Mg and Zn), MIII (M = Y, Sc, Ce and U) and MIV (M = Ce and U) amide complexes. X-ray diffraction studies and a DFT study are used to probe the extent of covalency in the bonding of the MIV complexes. Chapter Three investigates the reactivity of the amide complexes prepared in Chapter Two. The MII complexes are shown to be initiators for the polymerisation of raclactide into biodegradable polymers. The MIII complexes are used to demonstrate additionelimination reactivity of polar substrates across the M-Ccarbene bond which allows the formation of new N-E (E = Si, Sn, P or B) bonds. Treatment of the UIII silylamide complex U(N{SiMe3}2)3 with CO results in the reductive coupling and homologation of CO to form an ynediolate core -OC≡CO- and the first example of subsequent reactivity of the ynediolate group. The MIV complexes are used to examine the potential for forming MIV cationic species and alkyl complexes. Chapter Four examines the synthesis of MIII (M = Ce and Sc) aminobenzyl complexes and MIII (M = Y, Sc and U) neosilyl and neopentyl alkyl complexes. The addition-elimination reactivity discussed in Chapter Three is extended to include C-E bond formation (E = Si, Sn, P, B, I or C). Chapter Five provides overall conclusions to the work presented within this thesis. Chapter Six gives experimental and characterising data for all complexes and reactions in this work.

Knowledge of the relationship between rate of nitrification and nitrous oxide (N2O) emission, and between cumulative nitrification and N2O emission is important for developing N2O emission mitigation strategies. Gross nitrification and N2O from nitrification were determined using 15N labelling of inorganic N. N-Serve was added to delay nitrification and results showed an increase in rate of N2O emission with that of apparent nitrification in absence of N-Serve, but there was no relation in its presence. Same amount of cumulative N2O was emitted for same amount of nitrogen (N) apparently nitrified, regardless of N-Serve addition. There was no relation between N2O emission attributed to nitrification and gross nitrification with and without N-Serve. Again, same amount of cumulative N2O was emitted for same amount of gross nitrified N, regardless of N-Serve addition. These results imply that the amount of N nitrified dictates eventual cumulative N2O emitted, regardless of rate of nitrification. / February 2017

This study deals with an important concept in fiqh known as ḍamān. Despite its universal usage in various areas of law, including that of criminal law and law of torts especially in facilitating award of compensation, this study will confine its survey within the bounds of commercial transactions. Ḍamān forms one of the most complicated subject-matters in the Islamic Law of Obligation. In this context, ḍamān is generally perceived as civil liability in the widest meaning, arising from the non-performance of contractual obligation, violation of trust, misrepresentation and unlawful enrichment. Firstly, this study will discuss suretyship, as ḍamān is, to some extent, treated as synonymous with kafālah by the jurists. Secondly, ḍamān will be surveyed as a method of redress of any contractual irregularities under the notion of gharāmah. Such practices are motivated by the Sharī'ah doctrines of maqāṣid shar'iyyah (objectives of the law), upholding the concept of lā ḍarara wa lā ḍirār (no harm shall be inflicted or reciprocated) and respecting the notion of sanctity of legitimate ownership (ḥurmat al-milkiyyah) and freedom of contract (ḥurriyat al-ta'āqud). Methods of establishing liability (ṭuruq ithbāt al-ḍamān) and its waivers (al-i'fā') min al-ḍamān), provision of redress (mabda' al-ta'wīḍ) and the institutional framework which are involved in it are then discussed. The study will be concerned with the prescriptions of the Qur'ān and Sunnah on ḍamān and their explanations in the classical manuals of Islamic Law. In addition, certain post-classical texts offering specific treatment of ḍamān, particularly al-Baghdādī's Majma' al-Ḍamānāt and al-Ma'danī's Taḍmln al-Ṣunnā' will be studied. Also, decisions by juristconsults of various localities, recorded in various collections of fatāwā and court decisions in the literature of adab al-qaḍā, will be examined to enhance our knowledge of the way ḍamān has been treated. For the purpose of systemization, texts of Uṣūl al-Fiqh and Qawā'id Fiqhiyyah are essential. Similarly, evidence on the economic history of Muslim civilization in the form of actual contracts, letters, business records and institutional operations, are examined. The research also relies heavily on the codifications of Islamic law like the Ottoman Majallat al-Aḥkām al-'Adliyyah, Qadrī Bāshā's Murshid al-Ḥayrān and the Ḥanbalīs Majallat al-Aḥkām al-Shar'iyyah. Finally, an analysis of the contemporary legislations in Egypt, the United Arab Emirates and Malaysia will prove that a classical concept like ḍamān is still vital for modem commerce. This also lays stress on the importance of neo-ijtihād to ensure ability and competence to apply ḍamān to fresh problems in commercial life.

Sibyl cycles in Northern and Central Italy, in the Early Renaissance. Previous published scholarship listed twenty-two sites. I now know of forty. Twenty-three of these may be considered Early Renaissance works of art and are the subject of this study. This study is not primarily engaged with history of Art but with the history of Ideas. That is, it is not a study of the painters. their methods and status but rather with the study of the development of the genre. its textual sources, the content of the inscribed oracles. the development of the pictorial conventions and symbolism. the transmission of these and the cultural significance of the genre. The dissertation is concerned with artistic styles and techniques only in so far as they illuminate the pictorial origin of the works and their iconographic significance in terms of the ideas conveyed. It describes and defines regional sub-genres. each with clear rules and conventions. These have not previously been identified and no comprehensive national conspectus exists. Structure of the Dissertation The dissertation is in three parts. The first part addresses the nature and origin of Sibyls (who and what they were) and their significance in cultural history until the Renaissance. Part Two is concerned with the origins and transmission of text and iconographic conventions in the Renaissance Sibyl cyeles. Pari three is a catalogue and survey of each Sibyl cycle site in Central and Northern Italy, along with a comprehensive photographic record. Great destruction of some cycles has taken place since the 1960s and the compilation of a complete photographic record is urgent and a significant aim of the present work. There are few published coloured photographs of the full cycles. none complete except for Siena. This dissertation is wide in scope and is in large part a catalogue and survey of all known Italian Sibyl cycles. Because of the limitations of a Doctoral dissertation. at times the transition from one site to another may appear abrupt and disjunct. Nonetheless, the structure is logical and careful. Sites are arranged chronologically, according to genre. The reader is directed to the detailed table of contents, if a review of structure and order be required. Research Method The method of research was to form a comprehensive list of Sibyl sites in Italy by consulting published English and Continental books. journals and locally produced historical papers as well as word of mouth advice in Italy. I visited all the sites and made a photographic record. Origin and transmission of text was established by consulting contemporary manuscripts that either specify the oracle text or describe the original Orsini. and other, frescos. These manuscripts are widely scattered in Europe and difficult of access so, where possible, a significant example of each kind of manuscript is reproduced in photographs or photocopy, transcribed and translated in the Appendices to the dissertation.

The generalisability of case study findings is heavily criticised in the scientific community. This study attempts to answer to what extent generalisation is possible, through a literature review. Resources were collected by searching in databases and in reference lists. A presentation of arguments from both sides will follow, finding that generalisation is possible to almost the same extent as quantitative research, if done correctly and carefully, with great concern and accuracy.

The purpose of this paper is to explore some of the properties of the Cantor set and to extend the idea of this set to metric spaces, in general, and to other sets of real numbers and sets in N-dimensional Euclidean space, in particular.

The purpose of the experiment was to investigate other paramagnetic salts to determine whether the W. B. perchlorate type peak was more common than previously suspected. An organic salt, picryl-n-amino-carbazyl, was chosen.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.