The Subtext project seeks to make programming fundamentally easier by altering the nature of programming languages and tools. This paper defines an operational semantics for an essential subset of the Subtext language. It also presents a fresh approach to the problems of mutable state, I/O, and concurrency.Inclusions reify copy & paste edits into persistent relationships that propagate changes from their source into their destination. Inclusions formulate a programming language in which there is no distinction between a program’s representation and its execution. Like spreadsheets, programs are live executions within a persistent runtime, and programming is direct manipulation of these executions via a graphical user interface. There is no need to encode programs into source text.Mutation of state is effected by the computation of hypothetical recursive variants of the state, which can then be lifted into new versions of the state. Transactional concurrency is based upon queued single-threaded execution. Speculative execution of queued hypotheticals provides concurrency as a semantically transparent implementation optimization.

The synthesis, reactivity, and spectroscopic properties of a series of triangular phosphido-bridged rhodium, iridium, palladium and platinum clusters are described. Throughout the project, X-ray diffraction and 31P{1H} NMR spectroscopy are the main techniques for characterizing compounds. In the first part of this report, the lability of μ-X and terminal phosphines in [M3(μ-X)(μ-PPh2)2(PPh3)3)[BF4](M= Pd, X= Cl; M=Pt, X= H) is utilized to prepare a number of compounds where the integrity of the triangular framework is maintained. The molecular structures of three representative examples: [Pd3(μ-SCH2Ph)(μ-PPh2)2(PEt3)3][BF4] [Pt3(μ-Cl)(μ-PPh2)2(PR3)3][BF4) (R= Ph, Et) were determined and are described. Reaction of these palladium and platinum trinuclear clusters with chelating ligands, R’2PYPR”2 (Y= O, CH2), results in unusual cluster fragmentation to give novel dinuclear monocations, [M2(μ-PP2)(μ-R’2PYPR”2) (PR3)2)+ (M= Pd, Pt) in which a metal-metal bond is supported by both dppm and phosphido bridges. These dimers are very inert failing to react with a number of reagents including C4H6, HCCCO2Me, CH2N2, CO, CH3I (when M= Pd), H2, HBF4 and CH2I2. The cluster, [Pt3(μ-H)(μ-PPh2)2(PPh3)3] [BF4], also reacts with ButNC to afford the dinuclear species (Pt2(μ-PPh2)2(ButNC)(PPh3)3]+. The crystal structures of fragmentation products [Pd2(μ-PPh2)( μ-Pri2PCH2PPh2)(PPh3)2] [BF4], (Pt2(μ-PPh2)( μ-Me2PCH2PMe2)(PPh3)2]2 [C2O4] and (Pt2(μ-PPh2)(ButNC)(PPh3)3]2(C2O4) are reported and discussed. In the last part, the synthesis of a novel trinuclear iridium cluster, [Ir3(μ-PPh2)3(CO)5], is described, and the reactions of this cluster and its previously reported rhodium analogue, [Rh3(μ-PPh2)3(PPh3)2(CO)3], with dppm afford not fragmentation, but substitution products. The complex (Ir3(μ-PPh2)3(CO)5] also reacts with ButNC to yield [Ir3(μ-PPh2)3(CO)5(ButNC)2]. The crystal structures of the compounds, [M3(μ-PPh2)3(μ-dppm)(CO)3] (M= Rh, Ir) and (Ir3(μ-PPh2)3(CO)5(ButNC)2], are also reported. / Graduate

Mining has been one of the main industries in the course of the development of human civilization and economies of various nations. However, every industry has issues, and one of the problems the mining industry has faced is the management of waste, especially sulphide-bearing tailings, which are considered to be a global environmental problem. This issue puts pressure on the mining industry to seek alternative approaches for tailings management. Among the several different types of methods used, cemented paste backfilling is one of the technologies that offers good management practices for the disposal of tailings in underground mines worldwide. Cemented paste backfill (CPB) is a cementitious composite made from a mixture of mine tailings, water and binder. This technology offers several advantages, such as improving the production and safety conditions of underground mines. Among these advantages, CPB is a promising solution for the management of sulphidic tailings, which are considered to be reactive materials (i.e., not chemically stable in an atmospheric condition) and the main source of acid mine drainage, which constitutes a serious environmental challenge faced by mining companies worldwide. Such tailings, if they come into direct contact with atmospheric elements (mainly oxygen and water), face oxidation of their sulphidic minerals, thus causing the release of acidic drainage (i.e., acid mine drainage) and several types of heavy metals into surrounding water bodies and land. Therefore, the reactivity of sulphidic tailings with and without cement content can be considered as a key indicator of the environmental behavior and durability performance of CPB systems. For a better understanding of the reactivity, it is important to investigate the influencing factors. In this research, several influencing factors are experimentally studied by conducting oxygen consumption tests on different sulphidic CPB mixtures as well as their tailings under different operational and environmental conditions. These factors include time, curing temperature, initial sulphate content, curing stress, mechanical damage, binder type and content, and the addition of mineral admixtures. In addition, several microstructural techniques (e.g., x-ray diffraction and scanning electron microscopy) are applied in order to understand the changes in the CPB matrices and identify newly formed products. The results reveal that the reactivity of CPB is affected by several factors (e.g., curing time, initial sulphate content, ageing, curing and atmospheric temperature, binder type and content, vertical curing stress, filling strategy, hydration and drainage, etc.), either alone or in combination. These factors can affect reactivity either positively or negatively. It is observed that CPB reactivity decreases with increasing curing time, temperature (i.e., curing and atmospheric temperatures), curing stress, binder content, the addition of mineral admixtures, degree of saturation, and the binder hydration process, whereas reactivity increases with increases in sulphide minerals (e.g., pyrite), initial sulphate content, mechanical damage, and with decreased degrees of saturation and binder content. The effect of sulphate on the reactivity of CPB is based on the initial sulphate content as well as curing time and temperature. It is concluded that the reactivity of CPB systems is time- and temperature-dependent with respect to other factors. Also, binders play a significant role in lowering CPB reactivity due to their respective hydration processes.

Made available in DSpace on 2014-06-11T19:25:26Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-02-25Bitstream added on 2014-06-13T20:32:59Z : No. of bitstreams: 1 quaglio_aev_me_botib.pdf: 425313 bytes, checksum: 2483f9db556c10ebc5c1a2db7f971fa3 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A Doença Inflamatória Intestinal (DII) engloba, fundamentalmente, duas doenças distintas: a Doença de Crohn (DC) e a Retocolite Ulcerativa (CU), ambas caracterizadas por uma inflamação crônica do intestino, com períodos de exacerbação seguidos de intervalos prolongados de remissão dos sintomas. Apesar da DII ser objeto de pesquisa há várias décadas, a sua etiologia ainda é desconhecida e a principal limitação no entendimento dos mecanismos fisiopatológicos desta doença é a disponibilidade de modelos experimentais adequados que mimetizem o caráter crônico e de recidiva da DII em humanos e que possam ser de baixo custo, reprodutível, fácil de induzir e que apresente características clínicas e histopatológicas, respostas terapêuticas e mediadores inflamatórios similares ao que ocorre com a doença em humanos. Dentre os vários modelos experimentais disponíveis, o modelo de colite induzida por ácido trinitrobenzenosulfônico (TNBS) em ratos tem sido considerado o mais adequado para a avaliação de novos fármacos, assim como aquele que melhor mimetiza esta doença em humanos. Assim sendo, a caracterização do papel de diferentes mediadores do processo inflamatório intestinal neste modelo permitiria a determinação de novos alvos terapêuticos, assim como geraria informações importantes da fisiopatologia desta doença. Neste sentido, o presente projeto teve como objetivo determinar a participação da HSP70, Heparanase e HPRT, mediadores do processo inflamatório intestinal em humanos, na fase aguda do processo inflamatório intestinal induzido TNBS em ratos, assim como estudar os efeitos de fármacos das três principais classes farmacológicas usadas no tratamento da DII em humanos, os aminossalicilatos (sulfassalazina), os glicocorticóides (prednisolona) e os imunomoduladores (azatioprina) sobre esses mediadores. Este estudo demonstrou que HSP70, Heparanase... / The idiopatic inflammatory bowel diseases comprise two types of chronic intestinal disorders: Crohn’s disease and ulcerative colitis that are characterized by a chronic inflammation of the intestine, with periods of remission and reactivation of the inflammatory process. Although IBD is the subject of research for several decades, its etiology remains unknown, and the major limitation to understanding the IBD pathophysiology is the availability of experimental models that mimic the chronic and relapse of human IBD. Is still important that experimental models can be inexpensive, reproducible, easy to induce and present clinical and histopathological features, therapeutic responses and inflammatory mediators similar to what occurs in humans. Among experimental models available, the model of colitis induced by trinitrobenzenesulphonic acid (TNBS) in rats has been considered the most suitable for the evaluation of new drugs, as well as the one that best mimics the disease in humans. Therefore, the involvement of different IBD mediators in this experimental model would allow the determination of new therapeutic targets, as well as generate important information on the pathophysiology of this disease. In light of this, the aim of present study was to determine the participation of HSP70, Heparanase and HPRT, mediators of intestinal inflammatory process in humans, in acute phase of inflammatory process induced by TNBS in rats, as well as, to study the effects of drugs of the three main classes used in the treatment of human IBD, i.e., aminosalicylates (sulphasalazine), glucocorticoids (prednisolone) and immunomodulators (azathioprine) on these mediators. This study showed that HSP70, Heparanase and HPRT participate as mediators of intestinal inflammation induced by TNBS since these mediators are increased in colitic animals when compared to healthy animals... (Complete abstract click electronic access below)

Chlorination of 2-methyl-2-aryloxypropanoic acids with aqueous hypochlorous acid gives spiro chloro adducts in moderate to high yields. In chlorination of 2-methyl-2-(2-methylphenoxy)propanoic acids, 1,2-adducts are formed, while in the case of 2-methyl-2-(4-methylphenoxy)propanoic acids, 1,4-adducts are obtained. In addition to the spiro adducts, 2-methyl-2-(4-chlorophenoxy)propanoic acids in the former case, and 2-methyl-2-(2-chlorophenoxy)propanoic acids in the latter case are formed, respectively. No 6-chlorosubstituted products are detected on chlorination of any of the substrates. Chlorination of 2-methyl-2-(2,4-dimethylphenoxy)propanoic acid affords only the 1,4-adduct. However, chlorination of 2-methyl-2-(5-chloro-2,4-dimethylphenoxy)propanoic acid gives both the 1,2- and the 1,4-adduct. 2-Methyl-2-(3,5-di-t-butylphenoxyl)propanoic acid on chlorination yields the diastereomeric secondary chloro adduct, 8-chloro-7,9-di-t-butyl-3,3-dimethyl-1,4-dioxaspiro (4,5) deca-6,9-dien-2-one. Under neutral and non-polar conditions, most of the 1,2-adducts undergo a thermal rearrangement of the chlorine which is shown to be a (1,5) sigmatropic chlorine shift. The rearrangement rates are highly dependent on the nature of the substituents in the diene systems. Under acidic and non-nucleophilic conditions, most of the 1,4-adducts undergo an intramolecular 1,2 chlorine shift followed by aromatization to give the 3-chloro-substituted products. For the dienes in which the 3-position is originally substituted, successive 1,2 chlorine migrations and/or side chain substitution are observed. On the other hand, the 1,2-adducts under similar reaction conditions undergo an intermolecular 1,4 chlorine shift to give the 5-chlorosubstituted products. In the case that the 5-position is substituted by a methyl group, side chain substitution at the 5-methyl takes place. In the presence of added base, solvolyses of the 1,4-adducts in methanol affords simple solvolysis products and/or 1,2 carboxyl rearranged products. The kinetic studies of the solvolyses of the 1,4-adducts have been carried out. The results reveal the substituent effects on both the simple solvolysis displacement and the rearrangement reactions. / Graduate

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Submitted by BRUNO NOGUEIRA DE OLIVEIRA LIMA null (limanogueirabruno@hotmail.com) on 2017-06-19T15:53:30Z No. of bitstreams: 1 Diss_Bruno_Nogueira_de_Oliveira_Lima.pdf: 928712 bytes, checksum: f772bde0ef17c470822f47584ca868ec (MD5) / Approved for entry into archive by Luiz Galeffi (luizgaleffi@gmail.com) on 2017-06-21T13:07:39Z (GMT) No. of bitstreams: 1 lima_bno_me_jabo.pdf: 928712 bytes, checksum: f772bde0ef17c470822f47584ca868ec (MD5) / Made available in DSpace on 2017-06-21T13:07:39Z (GMT). No. of bitstreams: 1 lima_bno_me_jabo.pdf: 928712 bytes, checksum: f772bde0ef17c470822f47584ca868ec (MD5) Previous issue date: 2017-05-22 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Em todos os esportes equestres é comum que os animais sejam testados com grande variação de obstáculos, percursos e ambientes. Essas dificuldades impostas nas provas equestres justificam o foco em um dos aspectos mais importantes do temperamento dos cavalos: sua reatividade ou comportamento de fuga ("flightness"). A reatividade dos potro pode ser caracterizada pela aproximação ou fuga de determinado estímulo. Este estudo teve como objetivo verificar a existência da variabilidade na expressão do comportamento de um grupo de potros Brasileiro de Hipismo (BH) frente à novo objeto e se existe alguma associação entre a reatividade dos animais durante o teste do novo objeto e a presença do polimorfismo de nucleotídeo único (SNP - Single Nucleotide Polymorphism) A758T do gene DBH. O teste do novo objeto (feito com a utilização de um guarda-chuva aberto) foi realizado em 260 potros Brasileiro de Hipismo (BH) sem nenhum treinamento montado. A avaliação da reatividade e rapidez de habituação foi feita por avaliação qualitativa do comportamento (QBA - Qualitative Behavior Analysis) durante o teste de novo objeto. Foi possível observar grande variabilidade fenotípica entre os potros, sendo que os animais foram divididos em um grupo com altos valores para as variáveis RELAXADO, FOCADO, CONFIANTE e POSITIVAMENTE CURIOSO e outro grupo de animais com altos valores para PRECAVIDO, AGITADO, CONFUSO e DESESPERADO. Também foi observado que os criatórios diferiram entre si quanto à adoção de seleção direcional ou não para a reatividade dos animais. Apesar disso, a presença de animais que podem ser caracterizados como "patologicamente ansiosos", evidencia a necessidade de maior atenção por parte dos criatórios nacionais na seleção de animais com menor reatividade. O nosso estudo evidenciou também que a SNP A758T no gene DBH não estava presente no subgrupo de 20 animais genotipados dentro da população estudada. Esse subgrupo de 20 animais genotipados era não aparentado e possuía fenótipo representativo da população, portanto, desestimula pesquisas futuras com a SNP A758T na raça BH. / In all the equestrian sports it is common that the animals are tested with a great variation of obstacles, courses and environments. These difficulties imposed in the equestrian sports justify the focus in one of the aspects of a horse's temperament: his reactivity or flight behavior (“flightiness”). The horse's reactivity can be characterized by his approach or escape of determined stimulus. This study aimed to verify the existence of behavior variability in Brazilian Sport Horse fillies and colts and if there is any association between that behavior and the presence of the DBH SNP A758T. In order to accomplish this, we tested 260 Brazilian Sport Horse fillies and colts, without any mounted training, in a novel object test using an umbrella. The horse’s reactivity and habituation speed was analyzed through a QBA- Qualitative Behavior Analysis during the novel object test. It was possible to observe a great phenotypic variability between the animals and divide them in a group with high values for the variables RELAXED, FOCUSED, CONFIDENT and POSITIVELY CURIOUS and another group of animals with high values for CAUTIOUS, AGITATED, CONFUSED and DESPAIRED. We also observed that the breeders differed with respect to the adoption of a directional selection or not for the animals' reactivity. In spite of this, the presence of animals that can be characterized as "pathologically anxious", shows the need for a greater attention on the part of national breeders in the selection of animals with less reactivity. Moreover, our study also showed that SNP A758T in the DBH gene was not present in a subgroup of 20 animals within the study population. This subgroup of 20 genotyped animals were unrelated and had a phenotype representative of the population, therefore discourages future research with SNP A758T in Brazilian Sport Horses.

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M.Sc. (Chemistry) / Please refer to full text to view abstract

No description available.