Thesis advisor: James P. Morken / The development of boron and palladium ligands for conjunctive cross-coupling provides access to new reactivity. Some of these advances are outlined in this dissertation. Chapter one describes an enantioselective and diastereoselective palladium catalyzed conjunctive cross-coupling of β-substituted alkenyl boron “ate” complexes to afford contiguous benzylic stereocenters. “Mac” diol was discovered as a useful boron ligand in conjunctive cross-coupling by reducing unwanted Suzuki-Miyaura cross-coupling. Chapter two describes the utilization of “mac” diol in the enantioselective conjunctive cross-coupling of α-substituted alkenyl boron “ate” complexes with carbamoyl chlorides. This transformation affords tertiary, β-boryl amides, which provide a complementary approach to Mannich, aldol, and conjugate borylation products. Water was an essential additive to enable high yield and high enantioselectivity, and its reaction role was investigated. The synthetic utility of this cross-coupling was demonstrated with the asymmetric synthesis of (+)-adalinine. Chapter three describes the thought process behind discovering a new palladium ligand for conjunctive cross-coupling. Phosphinooxazolines (PHOX) are useful and inexpensive ligands for enantioselective palladium-catalyzed conjunctive cross-coupling. A stereochemical model of this cross-coupling with this ligand was examined. / Thesis (PhD) — Boston College, 2021. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

We consider the overlap between reasoning involved in <em>conjunctive query optimization</em> (CQO) and in tableaux-based approaches to reasoning about subsumption in <em>description logics</em> (DLs). In both cases, an underlying graph is created, searched and modified. This process is determined by a given <em>query</em> and <em>database schema</em> in the first case and by a given <em>description</em> and <em>terminology</em> in the second. The opportunities for overlap derive from an abundance of reductions of various schema languages to terminologies for common DL dialects, and from the fact that descriptions can in turn be viewed as queries that compute a single column. <br /><br /> Our main contributions are as follows. We present the design and implementation of a common graph utility that integrates the requirements for both CQO and DL reasoning. We then verify this model by also presenting the design and implementation for two drivers, one that implements a query optimizer for a conjunctive query language extended with descriptions, and one that implements a complete DL reasoner for a feature based DL dialect.

We consider the overlap between reasoning involved in <em>conjunctive query optimization</em> (CQO) and in tableaux-based approaches to reasoning about subsumption in <em>description logics</em> (DLs). In both cases, an underlying graph is created, searched and modified. This process is determined by a given <em>query</em> and <em>database schema</em> in the first case and by a given <em>description</em> and <em>terminology</em> in the second. The opportunities for overlap derive from an abundance of reductions of various schema languages to terminologies for common DL dialects, and from the fact that descriptions can in turn be viewed as queries that compute a single column. <br /><br /> Our main contributions are as follows. We present the design and implementation of a common graph utility that integrates the requirements for both CQO and DL reasoning. We then verify this model by also presenting the design and implementation for two drivers, one that implements a query optimizer for a conjunctive query language extended with descriptions, and one that implements a complete DL reasoner for a feature based DL dialect.

Made available in DSpace on 2014-06-11T19:31:08Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-07-14Bitstream added on 2014-06-13T20:41:24Z : No. of bitstreams: 1 barbosa_vt_dr_jabo.pdf: 445036 bytes, checksum: 7be58e66156743e0a9907a1b3018df87 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A leishmaniose ocular canina envolve um complexo de alterações decorrentes da atuação do agente nos diversos tecidos oculares. Valendo-se de cães com sorologia positiva para a doença, portadores (G1) ou não (G2) de alterações oftálmicas, com este estudo avaliou-se: o exame parasitológico de esfregaço a partir de swab conjuntival, a presença do parasito, pela PCR, em fragmento conjuntival e no humor aquoso (HA) e as concentrações protéicas, pela eletroforese, no HA. O parasitológico de esfregaço a partir do swab conjuntival foi positivo em 60% e 38,1% dos animais do G1 e do G2, respectivamente, com a oddsratio de 2,438 para positividade em tal parâmetro nos cães do G1, comparativamente aos do G2. A positividade na PCR de fragmento conjuntival foi maior no G1 (p < 0,005), com oddsratio igual a 17,31 quando comparados G1 e G2. O parasito não foi detectado no HA de qualquer dos grupos. Houve correlação fracopositiva entre as concentrações de IgG e de albumina séricas e do HA. Diferenças significativas foram encontradas entre os grupos, quando comparadas as proteínas totais, IgG, e proteína de peso molecular 33 kDa no HA. A haptoglobina foi detectada apenas no HA dos cães do G1. Os dados apontam para uma tendência dos cães com sinais oftálmicos serem positivos no parasitológico de esfregaço a partir do swab conjuntival e na PCR de conjuntiva, podendo, o método ser útil no diagnóstico parasitológico da leishmaniose visceral canina. Proteínas de fase aguda merecem mais avaliações quanto ao seu valor diagnóstico para esta enfermidade / Canine ocular leishmaniasis involves several ophthalmic alterations owing to the action of the parasite in numerous ocular tissues. Therefore, dogs serologically positive for leishmaniasis either presenting (G1) or not (G2) ocular alterations were enrolled in this study to evaluate the conjunctival cytology as a method for the diagnosis of this disease, the detection of the parasite in conjunctival tissue samples and in the aqueous humor using PCR, as well as the serum and aqueous humor protein concentrations determined by electrophoresis. The parasitological evaluation of the swabs disclosed 60% and 38.1% of positivity in dogs of groups 1 and 2, respectively, with a calculated oddsratio of 2.438 for a single animal testing positive in this procedure when ocular changes existed. The documented PCR results were more expressive in G1 dogs (P<0,005), with an oddsratio of 17,81 for the animals of this group testing positive using this method as compared to G2. The parasite was not found in the aqueous humor of either group. A weak positive correlation was calculated between the serum and aqueous humor IgG and albumin concentrations, and significant differences were found to exist between groups regarding total protein, IgG, and 33 kDa protein measured in the aqueous humor. Also, haptoglobin was detected only in the aqueous humor of G1 dogs. Our data suggest a tendency of dogs with ocular signs testing positive on the conjunctival swab exams and PCR, being these methods useful in the diagnosis of canine leishmaniasis. However, acute phase proteins require a more detailed evaluation concerning its diagnostic value for this disease

Orientador: José Luis Laus / Banca: Aline Adriana Bolzan / Banca: Leucio Camara Alves / Banca: Fábio Luiz da Cunha Brito / Banca: Newton Nunes / Resumo: A leishmaniose ocular canina envolve um complexo de alterações decorrentes da atuação do agente nos diversos tecidos oculares. Valendo-se de cães com sorologia positiva para a doença, portadores (G1) ou não (G2) de alterações oftálmicas, com este estudo avaliou-se: o exame parasitológico de esfregaço a partir de swab conjuntival, a presença do parasito, pela PCR, em fragmento conjuntival e no humor aquoso (HA) e as concentrações protéicas, pela eletroforese, no HA. O parasitológico de esfregaço a partir do swab conjuntival foi positivo em 60% e 38,1% dos animais do G1 e do G2, respectivamente, com a oddsratio de 2,438 para positividade em tal parâmetro nos cães do G1, comparativamente aos do G2. A positividade na PCR de fragmento conjuntival foi maior no G1 (p < 0,005), com oddsratio igual a 17,31 quando comparados G1 e G2. O parasito não foi detectado no HA de qualquer dos grupos. Houve correlação fracopositiva entre as concentrações de IgG e de albumina séricas e do HA. Diferenças significativas foram encontradas entre os grupos, quando comparadas as proteínas totais, IgG, e proteína de peso molecular 33 kDa no HA. A haptoglobina foi detectada apenas no HA dos cães do G1. Os dados apontam para uma tendência dos cães com sinais oftálmicos serem positivos no parasitológico de esfregaço a partir do swab conjuntival e na PCR de conjuntiva, podendo, o método ser útil no diagnóstico parasitológico da leishmaniose visceral canina. Proteínas de fase aguda merecem mais avaliações quanto ao seu valor diagnóstico para esta enfermidade / Abstract: Canine ocular leishmaniasis involves several ophthalmic alterations owing to the action of the parasite in numerous ocular tissues. Therefore, dogs serologically positive for leishmaniasis either presenting (G1) or not (G2) ocular alterations were enrolled in this study to evaluate the conjunctival cytology as a method for the diagnosis of this disease, the detection of the parasite in conjunctival tissue samples and in the aqueous humor using PCR, as well as the serum and aqueous humor protein concentrations determined by electrophoresis. The parasitological evaluation of the swabs disclosed 60% and 38.1% of positivity in dogs of groups 1 and 2, respectively, with a calculated oddsratio of 2.438 for a single animal testing positive in this procedure when ocular changes existed. The documented PCR results were more expressive in G1 dogs (P<0,005), with an oddsratio of 17,81 for the animals of this group testing positive using this method as compared to G2. The parasite was not found in the aqueous humor of either group. A weak positive correlation was calculated between the serum and aqueous humor IgG and albumin concentrations, and significant differences were found to exist between groups regarding total protein, IgG, and 33 kDa protein measured in the aqueous humor. Also, haptoglobin was detected only in the aqueous humor of G1 dogs. Our data suggest a tendency of dogs with ocular signs testing positive on the conjunctival swab exams and PCR, being these methods useful in the diagnosis of canine leishmaniasis. However, acute phase proteins require a more detailed evaluation concerning its diagnostic value for this disease / Doutor

Thesis advisor: James P. Morken / This thesis will describe the development of two transition metal catalyzed syntheses of organoboronic compounds. The first section describes relevant concepts and precedents for the conjunctive coupling reaction. In the second section of this thesis, nickel catalyzed conjunctive coupling reaction of carboxylic acid derivatives with 9-BBN derived ate complexes will be discussed, where beta-trialkylboryl ketones are obtained as the product. In the third section, the development of alkyl group migration in nickel-catalyzed conjunctive coupling with C(sp3) electrophiles will be discussed. Enantioenriched secondary boronic esters can be prepared from this reaction, and two alkaloid syntheses are disclosed as the application of the method. / Thesis (MS) — Boston College, 2020. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis advisor: James P. Morken / This dissertation describes three methods towards the stereoselective synthesis of organoboronates, and their application towards pharmacological targets of interest. The first chapter describes the use of alkyl migrating groups and alkyl electrophiles in the synthesis of secondary boronic esters through a highly selective nickel-catalyzed three component conjunctive cross-coupling reaction. Products from this conjunctive cross-coupling reaction are then converted to two alkaloids through boron amination and annulation processes. The second chapter describes the platinum-catalyzed diastereoselective diboration of carbocyclic, heterocyclic, and bicyclic alkenes. This reaction proceeded under air and both a homogeneous and heterogeneous catalyst was employed. Application of this reaction towards synthesis of the nucleoside analog Aristeromycin is also described. The final chapter details the development of an inexpensive and easily synthesized chiral diazaborinine that provides stereoinduction across a wide range of concerted and stepwise cycloaddition processes, affording heterocyclic-boron containing products in high yield and selectivity. Transformations of resulting organoboronates are also described. / Thesis (PhD) — Boston College, 2022. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Syftet med studien är att analysera frekvensen av den svenska s-participen i skönlitteraturgenren och att jämföra dess användningar med en lista på kriterier för ”konverbskap”. Definitionen av konverb är baserad på källor som Haspelmath 1995 och Nedjalkov 1990. S-participen studeras för att undersöka hur den har använts de senaste 180 åren, och skönlitteraturgenren valdes då den förväntas ha många s-participer. Eftersom konverb är vanligare i skriftspråk, eller åtminstone används mer varierat där, studeras inte talspråket. En korpusstudie har gjorts som täcker in fem subkorpora av Språkbankens Korp. Resultet filtrerades med hjälp av konverbkriterierna. Efter filtreringen räknades andelen s-participer ut för varje subkorpora och utifrån det drogs slutsatser. Resultatet visar att s-participen tycks ha varit mer vanlig i äldre litteratur, men andelen är ungefär densamma i ”Strindberg”, som täcker åren 1869-1912 och ”Bonnierromaner 1980-81”. Resultaten slogs ihop så att ”Strindberg” hamnade i den äldre tidsperioden och de tre efterkommande subkorpora i den yngre. För övrigt var skillnaden mellan de båda tidsperiodernas antal av s-participen statistiskt signifikant, men antalet funna s-participer behöver inte tyda på en historisk nedgång. / The aim of the study is to analyze the frequency tables of the Swedish s-participle in the literature genre and to compare its uses with a list of criteria of converbhood. The definition of a converb is based on sources such as Haspelmath 1995 and Nedjalkov 1990. The s-participle is studied in order to discover how it has been used throughout the last 180 years, and the literature genre is chosen since it is expected to have a lot of s-participles. The method was as follows: five subcorpora were searched through in Språkbanken’s Korp. The results were filtered using the converb criteria. When the filtering had been done, the ratio of s-participles was to be calculated for each subcorpora and from that, conclusions were to be drawn. The results show that the s-participle seems to have been more common in earlier literature, but the ratio is about the same in ”the August Strindberg” corpus covering the years 1869-1912 and ”Bonnier Novels 1980-81”. Moreover, the difference between the number of s-participles betweens the two periods were statistically significant, but the numbers do not need to amount to a historical decline in s-participles.

Constraint Satisfaction Problems (CSPs) are NP-complete in general, however, there are many tractable subclasses that rely on the restriction of the structure of their underlying hypergraphs. It is a well-known fact, for instance, that CSPs whose underlying hypergraph is acyclic are tractable. Trying to define “nearly acyclic” hypergraphs led to the definition of various hypergraph decomposition methods. An important member in this class is the hypertree decomposition method, introduced by Gottlob et al. It possesses the property that CSPs falling into this class can be solved efficiently, and that hypergraphs in this class can be recognized efficiently as well. Apart from polynomial tractability, complexity analysis has shown, that both afore-mentioned problems lie in the low complexity class LOGCFL and are thus moreover efficiently parallelizable. A parallel algorithm has been proposed for the “evaluation problem”, however all algorithms for the “recognition problem” presented to date are sequential. The main contribution of this dissertation is the creation of an object oriented programming library including a task scheduler which allows the parallelization of a whole range of computational problems, fulfilling certain complexity-theoretic restrictions. This library merely requires the programmer to provide the implementation of several classes and methods, representing a general alternating algorithm, while the mechanics of the task scheduler remain hidden. In particular, we use this library to create an efficient parallel algorithm, which computes hypertree decompositions of a fixed width. Another result of a more theoretical nature is the definition of a new type of decomposition method, called Balanced Decompositions. Solving CSPs of bounded balanced width and recognizing such hypergraphs is only quasi-polynomial, however still parallelizable to a certain extent. A complexity-theoretic analysis leads to the definition of a new complexity class hierarchy, called the DC-hierarchy, with the first class in this hierarchy, DC1 , precisely capturing the complexity of solving CSPs of bounded balanced width.

[pt] Com base no conceito de conjunção de Halliday e Hasan, esta pesquisa de caráter psicolinguístico busca verificar o processamento de relações conjuntivas causais internas e externas, bem como o papel dos conectivos nesse processamento. Para isso, primeiro foi feita uma atividade exploratória de produção textual junto a alunos de sétimo e oitavo anos do Ensino Fundamental, para verificar se nessa faixa de escolaridade eles já utilizam relações conjuntivas causais internas e externas, e se as realizam léxico-gramaticalmente por meio de conectivos. Confirmado o uso dessas relações, foram realizados testes de compreensão leitora off-line e teste cloze em turmas do oitavo e nono do Ensino Fundamental, respectivamente. O resultado da análise estatística dos dados indicou que as relações conjuntivas causais sob investigação apresentam custos de processamento distintos. Nos testes de compreensão, em que a tarefa do participante consistiu na verificação de afirmativas relativas ao conteúdo depreendido do texto, as relações conjuntivas causais externas foram mais facilmente processadas. No teste cloze, em que o estabelecimento de relações entre orações é feito pelo aluno e, nesse sentido, mais dependente de seu conhecimento extralinguístico e do tipo de conectivo que pode expressar adequadamente tais vínculos semânticos, as relações externas parecem ter trazido mais custo para o processamento do que as internas. No caso das internas, além da identificação do caráter argumentativo do texto, pistas de ordem linguística, tais como emprego de recursos modalizadores, em especial de adjetivos, e tempo/modo verbal, podem ter facilitado o reconhecimento do tipo de relação (independentemente de ter-se efetuado uma compreensão mais efetiva do texto). Em relação à presença ou ausência de conectivo, não foi verificado efeito principal dessa variável em nenhum dos experimentos, o que pode, em princípio, ser relacionado à força da relação causal entre as orações, que, mesmo na ausência do conectivo, é possível ser recuperada pelo aluno nos textos utilizados. Este trabalho representa uma contribuição para a questão da leitura em sala de aula, particularmente no que tange à compreensão de textos de natureza argumentativa, em que as relações conjuntivas causais internas e externas comparecem substancialmente, e devem, portanto, ser mais bem abordadas nas aulas de todas as disciplinas, trabalhando-se uma interpretação que vá além da superfície textual. / [en] Based on the concept of conjunction as presented by Halliday and Hasan, this research, which has a psycholinguistic character, aims to verify the processing of internal and external causal conjunctive relations, as well as the role of connectives in this processing. For this, it was first made an exploratory activity of writing with students from 7th and 8th grades of elementary school , to see whether in this level of schooling they already use internal and external causal conjunctive relations, and if they do it lexical- grammatically through connectives . Having confirmed the use of these relations, we performed the off -line reading comprehension test and cloze test in classes from the 8th and 9th grades of Elementary Education, respectively. The result of statistical analysis of the data indicated that the causal conjunctive relationships under investigation have different processing costs. In the comprehension tests, where the task of the participant was the verification of statements about the content inferred from the text, external causal conjunctive relations were more easily processed . In the cloze test , in where the establishment of relations between sentences is done by the student and, thus , depend more on its extra-linguistic knowledge and on the type of connective that can appropriately express such semantic links, external relations seem to have brought more cost to the processing than the internal ones. In the case of the internal ones, beyond identifying the argumentative character of the text, linguistic cues, such as the use of modal resources, especially adjectives and the use of certain verb tenses and moods, may have favored the recognition of the type of relation (regardless of having had a more effective understanding of the text). Regarding the presence or absence of connective it was not observed a main effect of this variable in any of the experiments, which can, at first, be related to the strength of the causal relationship between clauses, which even in the absence of connective can be retrieved by the student in the texts used. This work brings a contribution to the question of reading in the classroom, particularly with regard to text comprehension of argumentative nature, in which internal and external causal conjunctive relations appear substantially, and should therefore be best addressed in class from all subjects, exercising an interpretation that goes beyond the surface of the text.