Thesis advisor: James P. Morken / This dissertation will present four main projects focused on stereoselective construction of borylated compounds as well as their applications in asymmetric syntheses. The first two projects describe the development of a catalytic conjunctive cross-coupling reaction. By merging three simple starting materials, an organolithium reagent, an organoboronate, and an organic electrophile, a synthetically valuable secondary boronate is furnished by the conjunctive cross-coupling in an efficient and enantioselective fashion. Next, this strategy is expanded to synthesize severely hindered tertiary boronates, a synthetic challenging but powerful building block to access a variety of quaternary stereocenters. The third project presents a platinum-catalyzed enantioselective diboration of alkenyl boronates to furnish a broad range of 1,1,2-tris(boronates) products. A deborylative alkylation of the 1,1,2-tris(boronates) leads to a variety of internal vicinal bis(boronates) with high diastereoselectivity. In the final chapter, a general and practical synthesis of alkenyl boronates via the boron-Wittig reaction is disclosed. Utilizing readily accessible geminal bis(boronates) and aldehydes, a broad range of disubstituted and trisubstituted alkenyl boronates are afforded with good yield and stereoselectivity. / Thesis (PhD) — Boston College, 2017. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Recent research has shown that it is often preferable to encode real-world problems as propositional satisfiability (SAT) problems and then solve using a general purpose SAT solver. However, much of the valuable information and structure of these realistic problems is flattened out and hidden inside the corresponding Conjunctive Normal Form (CNF) encodings of the SAT domain. Recently, systematic SAT solvers have been progressively improved and are now able to solve many highly structured practical problems containing millions of clauses. In contrast, state-of-the-art Stochastic Local Search (SLS) solvers still have difficulty in solving structured problems, apparently because they are unable to exploit hidden structure as well as the systematic solvers. In this thesis, we study and evaluate different ways to effectively recognise, model and efficiently exploit useful structures hidden in realistic problems. A summary of the main contributions is as follows: 1. We first investigate an off-line processing phase that applies resolution-based pre-processors to input formulas before running SLS solvers on these problems. We report an extensive empirical examination of the impact of SAT pre-processing on the performance of contemporary SLS techniques. It emerges that while all the solvers examined do indeed benefit from pre-processing, the effects of different pre-processors are far from uniform across solvers and across problems. Our results suggest that SLS solvers need to be equipped with multiple pre-processors if they are ever to match the performance of systematic solvers on highly structured problems. [Part of this study was published at the AAAI-05 conference]. 2. We then look at potential approaches to bridging the gap between SAT and constraint satisfaction problem (CSP) formalisms. One approach has been to develop a many-valued SAT formalism (MV-SAT) as an intermediate paradigm between SAT and CSP, and then to translate existing highly efficient SAT solvers to the MV-SAT domain. In this study, we follow a different route, developing SAT solvers that can automatically recognise CSP structure hidden in SAT encodings. This allows us to look more closely at how constraint weighting can be implemented in the SAT and CSP domains. Our experimental results show that a SAT-based mechanism to handle weights, together with a CSP-based method to instantiate variables, is superior to other combinations of SAT and CSP-based approaches. In addition, SLS solvers based on this many-valued weighting approach outperform other existing approaches to handle many-valued CSP structures. [Part of this study was published at the AAAI-05 conference]. 3. Finally, we propose and evaluate six different schemes to encode temporal reasoning problems, in particular the Interval Algebra (IA) networks, into SAT CNF formulas. We then empirically examine the performance of local search as well as systematic solvers on the new temporal SAT representations, in comparison with solvers that operate on native IA representations. Our empirical results show that zChaff (a state-of-the-art complete SAT solver) together with the best IA-to-SAT encoding scheme, can solve temporal problems significantly faster than existing IA solvers working on the equivalent native IA networks. [Part of this study was published at the CP-05 workshop].

Irrigation practices in the Rincon Valley and Mesilla Basin of the Lower Rio Grande have evolved over the last century into a complex setting of transboundary conjunctive use. Three major water users have surface and groundwater appropriation rights regulated by compact, treaty, and operating rules and agreements. The analysis of complex relationships between supply/demand components and the effects of surface-water and groundwater use requires an integrated hydrologic model to track all of the use and movement of water. Models previously developed for the region relied on a priori estimates of net irrigation flux or externally-calculated landscape water budgets. This study instead utilizes a MODFLOW model with the Farm Process (MF-FMP), which directly couples the surface-water and groundwater regimes through simulation of landscape processes. This allows the assessment of stream-aquifer interactions in the context of fulfilling irrigation demands with variable supplies of surface water allotments and supplemental groundwater pumping. MF-FMP also simulates direct uptake of groundwater by crops, an important utility for modeling a region with significant acreage dedicated to pecan orchards, a phreatophytic crop. The abilities and limitations of this new model are explored through scenario simulations meant to estimate streamflow depletions caused by historic pumping levels.

Univ., Diss.--Hamburg, 2004.

My dissertation sought to expand the study of victimization by examining non-linear relationships across victim, offender, and offense characteristics within a routine activities theory framework. Moreover, my goals were to assess victimization risk using a more realistic approach through the implementation of a situational perspective approach and conjunctive analysis. Conjunctive analysis is an analytical with both quantitative and qualitative properties, which allowed for interpretations that were detail oriented and summative. Utilizing data from the National Crime Victimization Survey, several victim (e.g., demographic factors), offender (e.g., victim-offender relationship), and offense (contextual factors) characteristics were analyzed. Conjunctive analysis was estimated for incidents by victimization type and by race/ethnicity. The results indicated the presence of main (linear) effects and interaction (non-linear) effects. Main effects by victimization type provided support for prior research on victimization risk, such as the majority of victims emerging as young, white, and male. Interaction effects revealed young and female victims were vulnerable to attacks from non-stranger offenders; whereas, older and male victims were prone to stranger attacks. When estimated by race and ethnicity, whites and blacks were also more likely to be attacked by someone with whom they were familiar; whereas, victims categorized as other were more likely to be attacked by strangers. Theoretical and policy implications were discussed.

Thesis advisor: James P. Morken / This dissertation details three main projects that focus on stereoselective synthesis of organoboron reagents and their application to total synthesis studies. The first chapter describes the development of an enantioselective palladium-catalyzed conjuntive cross-coupling of bis(alkenyl)borates to access chiral allylboron reagents. These reagents are of high synthetic value that is demonstrated through various applications. The second chapter describes the development of a diastereoselective amine-modified boron-Wittig reaction with ketone electrophiles to access trisubstituted alkenyl boronic esters. The synthetic utility of these trisubstituted alkenyl boronic esters is demonstrated through a novel palladium-catalyzed cross-coupling reaction. The third chapter encompassess studies toward the total synthesis of natural products amphidinolides C and F. It highlights the application of methods developed in the Morken laboratory in the context of challenging total synthesis. It also highlights the potential for newly developed conjunctive cross-coupling and boron-Wittig reactions to solve problems in total synthesis. / Thesis (PhD) — Boston College, 2020. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

The Cooperative Game Theory is a scientific discipline which offers rich mathematical apparatus for describing complex situations in the social reality. Its apparatus includes an extension to hierarchical structures and therefore can be applied to numerous research problems from the International Relations field. However, a cooperative game theoretical approach is very scarcely used. The main goal of the diploma thesis is to demonstrate, on the research problem of decision making in participation in local conflicts, the benefits of results that can be achieved by the application of the Cooperative Game Theory. In the first part of the thesis, theoretical foundations are laid and basic concepts are introduced. The second part is focused on forming a series of models of cooperative games with hierarchical structures from four local conflict situations, which are subsequently restricted in order to describe authoritative relations in structure. Restricted games are solved, the results are interpreted and evaluation of how these results can contribute to addressing the research problem follows.

Thesis advisor: Marc M. Snapper / Thesis advisor: James J. Morken / This dissertation will present three main projects focusing on the catalytic enantioselective synthesis and stereospecific functionalization of tertiary alkylboronates. In the first project, acyl chlorides were incorporated as a new class of electrophile in conjunctive cross-coupling, from which, a variety of tertiary β-boryl amides were successfully synthesized with high enantioselectivity. The utility of the tertiary alkylboronates products was also demonstrated through several orthogonal functionalizations of the boronic ester group and amide groups. The project culminated in the enantioselective total synthesis of natural product (+)-adalinine that leveraged this newly developed methodology. In the second project, a conjunctive cross-coupling enabled ring closure was developed to synthesize tertiary alkylboronates residing on carbocyclic and heterocyclic scaffolds. A Phosphinooxazoline (Phox) ligand was identified as a non-expensive ligand that catalyzed the conjunctive cyclization reaction with high enantioselectivity. A Series of synthetically challenging enantimerically enriched spirocyclic and aryl bicyclic tertiary alkylboronates were efficiently generated using this method, and several cyclopentyl boronic esters with two continuous stereogenic centers were synthesized with high diastereoselectivity. In the third project, a Rh-catalyzed diboration reaction was successfully employed to diborate monosubstituted cyclobutenes with excellent enantioselectivity. The less sterically hindered secondary boronic ester units in the diboron products can be regioselectively functionalized using the newly developed tert-butyllithium activation-transmetallation strategy. As a result, a variety of stereochemically defined β-substituted cyclobutyl tertiary boronic esters were synthesized with high efficiency. / Thesis (PhD) — Boston College, 2024. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Dans cette thèse, nous nous intéressons au problème d'interrogation de bases de connaissances composées de données et d'une ontologie, qui représente des connaissances générales sur le domaine d'application. Parmi les différents formalismes permettant de représenter les connaissances ontologiques, nous considérons ici un fragment de la logique du premier ordre appelé règles existentielles (aussi connues sous le nom de ``tuple generating dependencies'' et Datalog+/-). Le problème fondamental de conséquence logique au cœur de cette thèse demande si une requête conjonctive est conséquence d'une base de connaissances. Les règles existentielles étant très expressives, ce problème est indécidable. Toutefois, différentes restrictions sur les ensembles de règles ont été proposées afin d'obtenir sa décidabilité.La contribution de cette thèse est double. Premièrement, nous proposons un outil qui nous permet d'unifier puis d'étendre la plupart des classes de règles connues reposant sur des notions d'acyclicité assurant la finitude du chaînage avant. Deuxièmement, nous étudions la compatibilité des classes décidables de règles existentielles connues avec un type de connaissance souvent nécessaire dans les ontologies: la transitivité de relations binaires. Nous aidons à clarifier le paysage des résultats positifs et négatifs liés à cette question et fournissons une approche permettant de combiner la transitivité avec les règles existentielles linéaires. / In this thesis we investigate the issue of querying knowledge bases composed of data and general background knowledge, called an ontology. Ontological knowledge can be represented under different formalisms and we consider here a fragment of first-order logic called existential rules (also known as tuple-generating dependencies and Datalog+/-).The fundamental entailment problem at the core of this thesis asks if a conjunctive query is entailed by an existential rule knowledge base. General existential rules are highly expressive, however at the cost of undecidability. Various restrictions on sets of rules have been proposed to regain the decidability of the entailment problem.Our specific contribution is two-fold. First, we propose a new tool that allows to unify and extend most of the known existential rule classes that rely on acyclicity conditions to tame infinite forward chaining, without increasing the complexity of the acyclicity recognition. Second, we study the compatibility of known decidable rule classes with a frequently required modeling construct, namely transitivity of binary relations. We help clarifying the picture of negative and positive results on this question, and provide a technique to safely combine transitivity with one of the simplest, yet useful, decidable rule classes, namely linear rules.

L'objectif du problème appelé "Ontology-based data access" (OBDA) est d'améliorer la réponse à des requêtes en prenant en compte des connaissances d'ordre général durant l'évaluation des requêtes. Ces connaissances générales sont représentées à l'aide d'une ontologie, qui est exprimée dans cette thèse grâce à des formules logiques du premier ordre, appelées règles existentielles, et aussi connues sous le nom de "tuple-generating dependencies" et Datalog+/-. L'expressivité des formules utilisées est telle que l'évaluation de requêtes devient un problème indécidable, et cela a conduit la communauté à définir de nombreux cas décidables, c'est-à-dire des restrictions sur les ensembles de règles existentielles considérés. La contribution de cette thèse est double : tout d'abord, nous proposons une vue unifiée sur une grande fraction des cas décidables connus, et fournissons par là même une analyse de complexité et un algorithme optimal dans le pire des cas. Nous considérons également l'approche couramment utilisée de réécriture de requêtes, et proposons un algorithme générique qui permet de surmonter certaines causes évidentes d'explosion combinatoire qui rendent les approches classiques pratiquement inapplicables. / Ontology-based data access (OBDA) aims at enriching query answering by taking general background knowledge into account when evaluating queries. This background knowledge is represented by means of an ontology, that is expressed in this thesis by a very expressive class of first-order formulas, called existential rules (sometimes also tuple-generating dependencies and Datalog+/-). The high expressivity of the used formalism results in the undecidability of query answering, and numerous decidable classes (that is, restrictions on the sets of existential rules) have been proposed in the literature. The contribution of this thesis is two-fold: first, we propose a unified view of a large part of these classes, together with a complexity analysis and a worst-case optimal algorithm for the introduced generic class. Second, we consider the popular approach of query rewriting, and propose a generic algorithm that overcomes trivial causes of combinatorial explosion that make classical approaches inapplicable.