The aim of the thesis is to study differences between sexes of rats in tumour growth, the difference in immune response between rats with progressing and spontaneously regressing tumours compared to control rats and verification of immunological memory. We used Lewis rat model with subcutaneously inoculated sarcoma. Peripheral blood of males showed a higher number of red blood cells, a higher concentration of haemoglobin and higher haematocrit compared to females. Experimental females with inoculated sarcoma had higher levels of CD161 (NK) cells at the beginning of experiment in comparison with the experimental and control males and control females. A strong infiltration of NK cells was observed in tissue sections of spontaneously regressing sarcoma compared to progressing tumours tissue. Important factors that can influence if the animal will show tumour progression or spontaneous regression are neutrophil granulocytes (they can induce both tumour-supporting and anti-tumour response), vascularization and extent of necrosis in tumour tissue. We have verified immunological memory in a small group of females by the secondary inoculations of the same tumour cells after complete disappearance of primary, spontaneously regressing tumour. No sarcoma repeatedly evolved in any of the females. Results obtained in the present work brought new insights into the problems of tumour in the Lewis rat sarcoma model with inoculated sarcoma. These results may have significance also for area of clinical oncology due to similarities with the behaviour of some human cancers.

Neste trabalho foi investigada a utilização de InCIs (Tricloreto de índio) como ácido de Lewis na ativação de aldiminas e na geração "in situ" de cátions imínio e N-acilimínio cíclicos para promover a formação da ligação C-C (1- nitrogênio a partir da adição de nucleófilos de carbono, estabelecendo assim um novo método para a preparação de compostos p-aminocarbonílicos através da Reação de Mannich Bimolecular. O primeiro estudo realizado utilizou aldiminas 94 na presença de quantidades catalíticas (10 moi %) de Inels nas reações com nucleófilos de carbono como o silil enoléter 95 e o silil cetenoacetal 96, levando à formação das f3-aminocetonas 99 e f3-aminoésteres 100 em bons rendimentos. Em seguida estudou-se a habilidade do InCI3 (80 moi %) em promover "in situ" a formação de cátions N-acilimínio cíclicos a partir dos respectivos precursores 5-acetoxilactamas 103 e posterior captura destes cátions por nucleófilos sililados de carbono como o silil enoléter 95, o silil cetenoacetal96 e o aliltrimetilsilano 97, levando à obtenção dos respectivos adutos 106-108. A reação dos cátions N-acilimínio cíclicos obtidos à partir dos precursores 103b-c com faces diastereotópicas levaram à obtenção de uma mistura de dois isômeros cujas proporções foram determinadas através de cromatografia gasosa. A estereoquímica relativa trans dos produtos majoritários foi inferida através dos dados espectroscópicos de RMN-1 H. / In this present work, the use of InCb (Indium Trichloride) as Lewis acid in the activation of aldimines and "in situ" generation of N-acyliminium ions was investigated. The respective cationic species were trapped by sylilated carbon nucleophiles achieving a new method to synthesize J}-aminocarbonyl compounds. Firstly, the catalytic amounts of InCI3 (10 moi %) and aldimines 94 was reacted with silylated carbon nucleophiles such as the silylenolether 96 and silylketeneacetal 97, affording the respective J}-aminoketones 99 and 13- aminoesters 100 in good yields. After, the ability of InCb (80 moi %) to promote the "in situ" generation of the cyclic N-acyliminium cations from the respective 5-acetoxylactams 103 was studied. These cations were trapped by sylilated carbon nucleophiles such as the silylenolether 96, silylketeneacetal 97 and allyltrimethylsilane 98, affording to the respective adducts 106-108. The reaction of precursors 103b-c with diastereotopic faces and silylated carbon nucleophiles 95-97 produced an isomeric mixture of the two possible diastereoisomers which the isomeric ratio was determined by G.C. analysis. The relative trans stereochemistry of the major diastereoisomer was inferred by the spectroscopy data from the 1H -NMR spectra.

Neste trabalho foi investigada a utilização de InCIs (Tricloreto de índio) como ácido de Lewis na ativação de aldiminas e na geração "in situ" de cátions imínio e N-acilimínio cíclicos para promover a formação da ligação C-C (1- nitrogênio a partir da adição de nucleófilos de carbono, estabelecendo assim um novo método para a preparação de compostos p-aminocarbonílicos através da Reação de Mannich Bimolecular. O primeiro estudo realizado utilizou aldiminas 94 na presença de quantidades catalíticas (10 moi %) de Inels nas reações com nucleófilos de carbono como o silil enoléter 95 e o silil cetenoacetal 96, levando à formação das f3-aminocetonas 99 e f3-aminoésteres 100 em bons rendimentos. Em seguida estudou-se a habilidade do InCI3 (80 moi %) em promover "in situ" a formação de cátions N-acilimínio cíclicos a partir dos respectivos precursores 5-acetoxilactamas 103 e posterior captura destes cátions por nucleófilos sililados de carbono como o silil enoléter 95, o silil cetenoacetal96 e o aliltrimetilsilano 97, levando à obtenção dos respectivos adutos 106-108. A reação dos cátions N-acilimínio cíclicos obtidos à partir dos precursores 103b-c com faces diastereotópicas levaram à obtenção de uma mistura de dois isômeros cujas proporções foram determinadas através de cromatografia gasosa. A estereoquímica relativa trans dos produtos majoritários foi inferida através dos dados espectroscópicos de RMN-1 H. / In this present work, the use of InCb (Indium Trichloride) as Lewis acid in the activation of aldimines and "in situ" generation of N-acyliminium ions was investigated. The respective cationic species were trapped by sylilated carbon nucleophiles achieving a new method to synthesize J}-aminocarbonyl compounds. Firstly, the catalytic amounts of InCI3 (10 moi %) and aldimines 94 was reacted with silylated carbon nucleophiles such as the silylenolether 96 and silylketeneacetal 97, affording the respective J}-aminoketones 99 and 13- aminoesters 100 in good yields. After, the ability of InCb (80 moi %) to promote the "in situ" generation of the cyclic N-acyliminium cations from the respective 5-acetoxylactams 103 was studied. These cations were trapped by sylilated carbon nucleophiles such as the silylenolether 96, silylketeneacetal 97 and allyltrimethylsilane 98, affording to the respective adducts 106-108. The reaction of precursors 103b-c with diastereotopic faces and silylated carbon nucleophiles 95-97 produced an isomeric mixture of the two possible diastereoisomers which the isomeric ratio was determined by G.C. analysis. The relative trans stereochemistry of the major diastereoisomer was inferred by the spectroscopy data from the 1H -NMR spectra.

Neste trabalho foi investigada a utilização de InCIs (Tricloreto de índio) como ácido de Lewis na ativação de aldiminas e na geração "in situ" de cátions imínio e N-acilimínio cíclicos para promover a formação da ligação C-C (1- nitrogênio a partir da adição de nucleófilos de carbono, estabelecendo assim um novo método para a preparação de compostos p-aminocarbonílicos através da Reação de Mannich Bimolecular. O primeiro estudo realizado utilizou aldiminas 94 na presença de quantidades catalíticas (10 moi %) de Inels nas reações com nucleófilos de carbono como o silil enoléter 95 e o silil cetenoacetal 96, levando à formação das f3-aminocetonas 99 e f3-aminoésteres 100 em bons rendimentos. Em seguida estudou-se a habilidade do InCI3 (80 moi %) em promover "in situ" a formação de cátions N-acilimínio cíclicos a partir dos respectivos precursores 5-acetoxilactamas 103 e posterior captura destes cátions por nucleófilos sililados de carbono como o silil enoléter 95, o silil cetenoacetal96 e o aliltrimetilsilano 97, levando à obtenção dos respectivos adutos 106-108. A reação dos cátions N-acilimínio cíclicos obtidos à partir dos precursores 103b-c com faces diastereotópicas levaram à obtenção de uma mistura de dois isômeros cujas proporções foram determinadas através de cromatografia gasosa. A estereoquímica relativa trans dos produtos majoritários foi inferida através dos dados espectroscópicos de RMN-1 H. / In this present work, the use of InCb (Indium Trichloride) as Lewis acid in the activation of aldimines and "in situ" generation of N-acyliminium ions was investigated. The respective cationic species were trapped by sylilated carbon nucleophiles achieving a new method to synthesize J}-aminocarbonyl compounds. Firstly, the catalytic amounts of InCI3 (10 moi %) and aldimines 94 was reacted with silylated carbon nucleophiles such as the silylenolether 96 and silylketeneacetal 97, affording the respective J}-aminoketones 99 and 13- aminoesters 100 in good yields. After, the ability of InCb (80 moi %) to promote the "in situ" generation of the cyclic N-acyliminium cations from the respective 5-acetoxylactams 103 was studied. These cations were trapped by sylilated carbon nucleophiles such as the silylenolether 96, silylketeneacetal 97 and allyltrimethylsilane 98, affording to the respective adducts 106-108. The reaction of precursors 103b-c with diastereotopic faces and silylated carbon nucleophiles 95-97 produced an isomeric mixture of the two possible diastereoisomers which the isomeric ratio was determined by G.C. analysis. The relative trans stereochemistry of the major diastereoisomer was inferred by the spectroscopy data from the 1H -NMR spectra.

The inverse demand hetero Diels-Alder reaction has been shown to be catalysed by commercially available, air-sensitive lanthanide Lewis acid catalysts such as Yb(fod)₃ . To date there have been no reported examples of enantioselective Lewis acid catalysed reactions of ethyl vinyl ether with crotonaldehyde, the inverse demand hetero Diels-Alder reaction of interest. This Diels-Alder reaction yields dihydropyran products which are key in the synthesis of a number of natural product target molecules, such as carbohydrates. The lack of stereospecificity achieved with known chiral NMR shift reagents has been attributed to fluxional behaviour of the ligands on the large lanthanide metal centre. This lack of conformational rigidity was proposed to be controlled by the use of sterically demanding C₃ symmetric multidentate ligand systems. By carefully designing a suitable ligand system the binding of the crotonaldehyde moiety in the Lewis acid catalysed reaction was anticipated to occur with facial selectivity, resulting in enantioselective Diels-Alder products. It was determined that lanthanide complexes of fluorinated β-diketone ligands with sufficiently low pKa's effectively catalyse the desired inverse demand hetero Diels-Alder reaction. These functionalities were incorporated into a multidentate, achiral, C₃ symmetric ligand system which upon lanthanide complexation was shown to be an air-stable efficient Lewis acid catalyst. Two chiral C₃ symmetric ligand systems were also prepared but were shown to be unsuitable for lanthanide substitution due to insufficiently robust functionalities present in the ligand framework, such as sulfonyl esters and Molecular modelling studies of these ligand systems reveal that the incorporation of camphor into the ligand framework is ideal for the preparation of a facially selective aldehyde binding site. Thus, concluding work probed other possible ligand functionalities which would result in camphor containing, chiral, C₃ symmetric ligand systems that are stable as lanthanide Lewis acid complexes. This new class of ligand promises to be of interest as chiral C₃ symmetric ligand systems for substitution on lanthanide metal centres have yet to be reported. This work summarises several useful synthetic strategies for the preparation of chiral C₃ symmetric ligands in multigram quantities. The application of these higher order symmetry ligands in enantioselective catalysis remains an important area of research. / Graduate

M.Sc. (Chemistry) / The work in this thesis describes some catalytic reactions of aluminium triflate. This Lewis acid has been shown to be of great value in the catalysis of several types of organic transformations. These include but are not limited to the alcoholysis and aminolysis of epoxides, uses in methoxycarbonylation catalysis and in esterification reactions. Therefore, aluminium triflate holds promise for application in both the bulk and fine chemistry industries. Aluminium triflate has received little interest compared to some other, more costly triflates such the lanthanide triflates. Oxetanes were used in various catalysis experiments during this study, yet few are commercially available. Therefore, various synthetic approaches to the synthesis of 2-phenyl-oxetane were explored. There were many failed attempts, but the preparation was eventually successful using a sulfur ylide route with good yield. The next part of this thesis explores the boundaries of ring-opening reactions of oxetanes. Lewis acid ring-opening of oxetanes has been neglected compared to that of epoxides, likely because it is a more difficult undertaking. Yet, alcoholysis reactions showed good yields with a variety of different alcohol substrates. Some of the alcohols contained functionality which could provide access to further modification. Furthermore, the aminolysis and thiolysis of oxetanes were explored, essentially without success. However, with an activated oxetane it was shown that oxetanes could be opened with good yield under mild conditions with amines and thiols...

>Doctor Literarum - DLit / Roy Campbell was once a key figure in the South African literary canon. In recent years, his poetry has faded from view and only intermittent studies of his work have appeared. However, as the canon of South African literature is redefined, I argue it is fruitful to consider Campbell and his work in a different light. This thesis aims to re-read both the legend of the literary personality of Roy Campbell, and his prose and poetry written during the period of “high” modernism in England (the 1920s and 1930s), more closely in relation to modernist concerns about language, meaning, selfhood and community. It argues that his notorious, purportedly colonial, “hypermasculine” personae, and his poetic and personal explorations of “selfhood”, offer him a point of reference in a rapidly changing literary and social environment. Campbell lived between South Africa and England, and later Provence and Spain, and this displacement resonated with the modernist theme of “exile” as a necessary condition for the artist. I will suggest that, like the Oxford dandies whom he befriended, Campbell’s masculinist self-styling was a reaction against a particular set of patriarchal traditions, both English and colonial South African, to which he was the putative heir. His poetry reflects his interest in the theme of the “outsider” as belonging to a certain masculinist literary “tradition”. But he also transforms this theme in accordance with a “modernist” sensibility.

Chapter One ("Amongst The Ruins") attempts to survey contemporary society through Lewis' eyes. The main characteristics of the age are these: (1) the extent to which the machine dominates the life of our times, and the economic, social, and psychological maladjustments which result; (2) the tragedy of recurring war; (3) the decay of religious orthodoxy and the quest for spiritual reassurance Chapter Two (The Appetite For Wholeness) deals with Lewis' attempt to achieve singleness of mind as related in his spiritual autobiography, Transitional Poem. This poem is especially important for the expression of certain germinal ideas which later develop into fundamental concept These germinal ideas are the polarity of flesh and spirit: the duality of physical and spiritual love; a carpe diem conception of pleasure; the acceptance of pain; the worship of hero in his role of decisive action; and the decision to take the side of the proletariat in the class struggles of the age. Chapter Three (The Spendthrift Fire the Holy Fire) examines the poetry of love and sex. From Feathers To Iron relates the thoughts and feelings of the poet during the nine months which precede the birth of his first child. This poem is considered from three different levels; as a human story, as a pageant of nature, as a political allegory on the birth of a new world. Other lyrics of love and sex deal with sex perversion, and the change which time brings to the marriage relationship, while others are in the mood of cavalier dalliance. Chapter Four (Inertia and Stimulants) presents Lewis’ argument that the key to the sickness of society is a divorce between flesh and spirit. This divorce brings about frustration and inertia, as exemplified by the various "Defendants" of The Magnetic Mountain, and leads to attempts at artificial stimulation, as exemplified by the four "Enemies" of the same book. Chapter Five (The Shape of Man’s Necessity) contends that The Magnetic Mountain offers socialism as a political solution which will heal the divorce of flesh and spirit. The enthusiasm of The Magnetic Mountain and Noah and the Waters gives way in later poems to a disappointment tempered by the faith that the socialist solution, though delayed, will eventually come. Chapter Six (In The Act of Decision) presents Lewis’ ideas of tradition and shows that the hero is one who acts decisively because his knowledge of necessity has united the desires of flesh and the desires of spirit. "A Time To Dance" and "Nabara" are epic stories which may be regarded as example of men in the act of decision. Chapter Seven (The Unique Minute) discusses the dual nature of Lewis’ philosophy of acceptance, The acceptance of joy becomes a carpe diem philosophy; the acceptance of suffering shows that the poet recognizes the complementary nature of joy and pain. Chapter Eight (Defend The Bad Against The Worse) examines the war poems which fall into three categories: (1) prophetic poems written before 1939; (2) poems about England at war; (3) poems about the prospect of lasting peace in the future. Chapter Nine (Emotional Logic) deals with the technique of the poems. Some of the conclusions drawn are these: (1) Soth logical and emotional coherence are used, hut the former predominates; (2) In matters of rhythm and rhyme, the influence of Anglo-Saxon versification, Hopkins, Owen, Eliot and Auden is present, but as not as great as is commonly supposed; (3) in general Lewis Is not an obscure poet; (4) In his latest poems (Short Is The Time) Lewis reveals that technically he is both versatile and accomplished, and that his poetry does not lack the purposeful ambiguity or qualities of "occlusion" which is a mark of great poetry. / Arts, Faculty of / English, Department of / Graduate

Complexes made by hosts that completely surround their guests provide a mean to stabilize reactive chemical intermediates, transfer biologically active cargo to a diseased cell, and construct molecular scale devices. By the virtue of inorganic host-guest self-assembly, the nucleation processes in the cavity of a {P8W48}-archetype phosphotungstate has afforded a nanoscale 16-GaIII-32-oxo cluster that contain the largest number of GaIII ions yet found in polyoxometalate chemistry. Catalytic activity via thus “Metal-Oxo Cluster within Cluster” Assembly has been preliminarily investigated. Besides, the hybrid aggregates composed of the inorganic {P8W48} and orgainc cyclic moiety has been studied.

Thesis advisor: Masayuki Wasa / Thesis advisor: Amir H. Hoveyda / This dissertation describes the development of cooperative catalyst systems for the regio- and enantio-selective α- and β-amino C-H functionalization of N-alkylamines, inspired by the concepts of frustrated Lewis pairs (FLPs). Prior to this dissertation research, the development of effective and broadly applicable catalytic protocol to transform amino C-H bonds with high enantioselectivity remained as a formidable problem. In Chapter 1, the recent advances in the field of amino C-H functionalization through hydride transfer process that served as intellectual foundations for this dissertation research is presented. As highlighted in the first chapter, key challenges of amino C-H functionalization are: (1) unreactive nature of α, β- and/or γ-amino C-H bonds, (2) requirement for the use of precious metal-based catalysts and external oxidants under acidic/basic and harsh conditions, (3) use of directing groups for regioselectivity, and (4) poor functional group tolerance. Inspired by the unique capability of FLPs to activate otherwise unreactive molecules while disfavoring undesirable acid-base complexation, we have developed a protocol for enantioselective α-amino C-H functionalization of N-alkylamines, where chiral and achiral Lewis acid catalysts work cooperatively (Chapter 2). The application of the cooperative catalyst system comprising of B(C6F5)3, a chiral Lewis acid, and a Brønsted base to the enantioselective β-amino C-H functionalization is described in Chapter 3. / Thesis (PhD) — Boston College, 2021. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.