The products and mechanisms of some photo-reactions of indenes and naphthalene with acrylonitrile have been studied. Indene reacts with acrylonitrile with the hydrocarbon absorbs light, or when a triplet sensitizer is absorbing. Photolysis under the former condition yields 2-(1-indenyl)- and 2-(3-indenyl)propionitrile, and 6-cyano-2,3-benzobicyclo[3,2,0]hep-2-ene. Base-catalyzed isomerizations of the substituted indenes are reported. On sensitization, cis- and trans-isomers of 7-cyano-2,3-benzobicyclo[3,2,0]hep-2-ene are formed; the known indene dimer is a minor product. Adducts 1,1-dimethyl- and 1,1-diphenylidene with acrylonitrile are also described. Naphthalene adds to acrylonitrile on photolysis to afford trans-8-cyano-2,3-benzobicyclo[4.2.0] octa-2,4-diene and 1- and 2-naphthyl-2-propionitriles. Sensitization gives no detectable products. Studies on fluorescence quenching, solvent effect and deuterium-labelling indicates that exciplexes are formed between acrylonitrile and the excited hydrocarbons. Inter- or intra-molecular protonation of the exciplexes with subsequent reaction of the carbonium ion formed, is suggested to produce indenes or naphthalenes. Possible mechanisms for the formation of other products are proposed. / Thesis / Doctor of Philosophy (PhD)

How do we handle buildings from the past? Do we preserve, do we change, do we remove? Is it possible to make additions to buildings that most times is being left alone? And what new qualities could it bring? In this project I wanted to explore the possibility of doing something other. To try out and see if something new could be added to an environment that by default is left alone. I believe old buildings should be used, not kept as museums, and sometimes that means things have to be altered to meet present demands. I worked on a site in my hometown of Landskrona, which led me out on a journey not only through the history of the site, but through the history of my home, and my own relation to it. There is a lot of inspiration to get from the places closest to oneself, even if they are at most times overlooked, or even invisible, to us. By being responsive, yet bold, could there be a building that no one has considered before?

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The study of the polymerization of alkyl vinyl ethers initiated by HI/I₂ catalyst is directed into two areas: the kinetics of the polymerization and the strategy of amine functionalized prepolymer synthesis. The polymerization reactions show living behavior in nonpolar solvents at low temperatures. The observed rate of polymerization under reaction conditions is linearly dependent on the initial concentration of hydrogen iodide and iodine, respectively. However, the monomer concentration does not influence the rate of polymerization(apparent zero-order). Two possible reaction schemes are proposed from the observed rate equation and attempts are made to distinguish them by using UV/visible spectroscopy and carbon-13 NMR spectroscopy. In both schemes a reversible interaction between a monomer and an iodine molecule is postulated as a necessary elemental reaction to fit the observed expression for the rate of polymerization. From spectroscopic analysis results, the interaction between the iodide compound(chain end) and the iodine molecule seems to be very weak compared to the interaction between the monomer and the iodine molecule. A synthetic strategy for amine functionalized prepolymer synthesis has been developed via a series of model reactions. Incorporation of a styrenic monomer at the propagating chain end of living poly(alkyl vinyl ethers) provides a convenient intermediate synthesis of a relatively stable amine functionalized prepolymer. Proper selection of substituents at the styrenic monomer optimizes the cross addition reaction and amination reactions. Linear alkylamines with lower carbon numbers are used in the amination reaction in order to promote the nucleophilic substitution reaction and to minimize possible elimination reactions. A series of amine functionalized oligomers are synthesized by employing the synthetic strategy in combination with the previous kinetic result of the homopolymerization. For oligomers, incorporation of a few units of ethyl vinyl ethers at the chain end facilitates the cross addition reaction. Synthesized amines are characterized by various spectroscopic methods. Then, titrated molecular weights show good agreement with their theoretical molecular weights in several cases. / Ph. D.

Under den verksamhetsförlagda tiden väcktes intresset för huvudräkning hos mig, ef­tersom eleverna valde att använda sig av miniräknare trots att de hade kunskap om olika huvudräk­ningsstrategier. Enligt skolverket (2011b) skall eleverna vid huvudräkning ta del av olika strategier för att stärka självsäkerheten och tilltron till sin förmåga. Syftet med studien var att undersöka vilken eller vilka strategier som några elever i grundskolan föredrog vid huvudräk­ning inom addition och subtraktion. Undersökningen byggde på en kvalitativ metod och her­meneutiken som teoretisk forskningsansats. Urvalet bestod av ett målinriktat urval kombinerat med ett bekvämlighetsurval och resulterade i tre elever från vardera tre olika skolor och skol­områden. Huvudräkningsuppgifter samt intervjuer användes som datainsamlingsmetod. Data­bearbetningen av intervjuerna har utförts under inspiration av hermeneutiken som bygger på tolkningar. Resultatet av studien visade att inom addition är det strategin talsorter var för sig, algoritm och dubbla som elever föredrar helst. Inom subtraktion varierade eleverna mer vid valet av huvudräkningsstrategier, där de helst föredrar räkna uppåt, algoritm, jämföra, tals­orter var för sig, komplettera, lägga till och räkna neråt. Resultatet visade även att skillnaden mellan skolorna inte var så stor, dock fanns det en liten skillnad mellan skola II och skola III vad gäller strategin räkna uppåt. Skillnaden var att skola II föredrar flera olika strategier av­seende subtraktion. Det framgår tydligt att eleverna har en god kunskap om olika huvudräk­ningsstrategier vid addition och subtraktion. Enligt eleverna är det på grund av att lärarna i sin undervisning hade gått igenom olika strategier inom huvudräkning. / During my practical training periods I became interested in mental arithmetic because I expe­rienced that the students chose calculators despite their knowledge of mental arithmetic strat­egies. According to skolverket (2011b) students shall take part of different strategies to strengthen their selfconfidence and belief in their own ability. The purpose of this study was to identify which strategies some students in middle school choose when they are practising mental arithmetic in addition and subtraction. The study was based on a qualitative method and hermeneutic as a theoretical approach. The sample consisted of a targeted selection in combination with a convenience selection and resulted in three students from each of three different schools and school areas. Mental arithmetic tasks and interviews were used as data collection method. Data processing of the interviews has been processed using hermeneutics method and is based on interpretation. The result of the study showed that partitioning num­bers, algorithm and double was the most common mental arithmetic strategies in addition. When it comes to strategies in subtraction the students varied more and the most common was counting upwards, algorithm, compare, partitioning numbers, complementary addition and counting back from. The result also showed that there was no significant difference between the schools except school II and III when it comes to the strategy counting upwards. The dif­ference was that school II uses several different strategies when performing subtractions. It was rather clear that the students in this study had a good knowledge of various mental arithmetic strategies for addition and subtraction, and according to themselves it was a consequence of the various strategies in mental arithmetics, that their teachers had taught them.

Thesis advisor: James P. Morken / The catalytic allylation of aldehydes, ketones, and imines is a very useful reaction for the formation of a new carbon-carbon bond in synthetic organic chemistry. There have been several successful reports of catalytic asymmetric reactions that use aldehydes as the substrate. However, there have been very few successful examples with ketones. Herein, a nickel-catalyzed allylation of dienones with the pinacol ester of allylboronic acid is presented. Based on 3,3’-reductive elimination, the relationship between the dienone structure and 1,2- and 1,6-regioselectvity has been studied. The development of a catalyzed asymmetric 1,2 allylation of dienones is also presented. / Thesis (MS) — Boston College, 2008. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Notre thèse s'intéresse à l'étude de séquences réactionnelles permeettant la création de carbones quaternaires. Deux séquences de réactions sont envisagées : - La première s'inscrit dans le prolongement des travaux de J-M. Adam et combine une réaction d'allylmétallation asymétrique et une réaction de cycloaddition [2+2] intramoléculaire. Elle conduit à des cyclobutanones bicycliques portant un substituant méthyle en tête de pont. La réaction d'allylmétallation a tout d'abord été étudiée en version catalytique pour la réaction modèle d'addition d'un dérivé d'allylsilane, le 1,3-bis-triméthylsilylpropène, sur le benzaldéhyde, en présence d'une quantité catalytique d'inducteur de chiralité. Différents catalyseurs ont pour ce faire été envisagés. La réaction d'allylmétallation asymétrique en version non catalytique a ensuite été reprise en vue de la synthèse de différents alcools homoallyliques porteurs d'un groupement silylé en a de la fonction hydroxyle. Deux inducteurs de chiralité différents ont été testés : le (R,R)-ClCpTiTADDOL et le (-)-(b)-méthoxydiisopinocamphéylborane. Dans cette réaction, la sélectivité est contrôlée par les ligands chiraux du métal. La réaction de cycloaddition [2+2] intramoléculaire a lieu entre une oléfine terminale et un cation cétène-iminium formé in situ ; elle conduit à des cyclobutanones bicycliques. Le contrôle de la sélectivité de cette étape est régi par l'effet b du silicium. Nous avons étudié les limitations de la méthode en synthétisant des cyclobutanones bicycliques de différentes tailles et porteuses d'un carbone quaternaire en tête de pont. - La seconde séquence étudiée implique une addition de Michaël, suivie d'une cyclopentannélation symétrique. Dans cette partie de notre travail, nous avons poursuivi les travaux de P. Schanen en vue de la catalyse organique de la réaction d'addition de Michaël. Nous avons étudié la réaction d'addition de différents nucléophiles sur la cyclohexénone en présence de catalyseurs dérivés de la (L)-proline ou d'imidazolidinone. Une étude de la variation de la nature du nucléophile ainsi que du contre-ion est proposée. / Our thesis studies reactions sequences leading to the formation of quaternary carbons. Two reactions sequences are envisaged: - The first one follows the work done by J-M. Adam and combines an asymmetric allylmetallation and an intramolecular [2+2] cycloaddition. This sequence leads to bicyclic cyclobutanones bearing a methyl substituent in bridgehead position. The allylmetallation has first been studied catalytically for the model reaction of addition of 1,3-bis-triméthylsilylpropene on benzaldehyde in the presence of a catalytic amount of chiral inducer. Various catalysts have been tested. The non catalytic asymmetric allylmetallation has then been used towards the synthesis of various homoallylic alcohols bearing a silyl group poistioned a to the hydroxyl function. Two chiral inducers have been tested: (R,R)-ClCpTiTADDOL and (-)-(b)-methoxydiisopinocampheylborane. At this step, selectivity is directed by chiral ligands on the metal. The intramolecular [2+2} cycloaddition reaction takes place between a terminal olefin and a ketene iminium cation formed in situ. This reaction leads to bicyclic cyclobutanones. The selectivity control at this step is directed by the b-effect of silicon. We have studied the limitations of the method by synthesizing bicyclic cyclobutanones of various sizes and bearing a bridgehead quaternary carbon. -The second reaction sequence combines a Michael addition and an asymmetric cyclopentannulation. In this part, we have pursued the work done by P. Schanen and studied the organic catalysis of the Michael addition reaction. We heva studied the addition reaction of various nucleophiles on cyclohexenone in the presence of catalysts derived from (L)-proline or imidazolidinone. A study of the variation of the nature of thee nucleophile as well as of the counter-ion is proposed.

La recherche constante de nouvelles stratégies pour la construction de liaisons carbone-carbone et le désir d’imiter la nature dans son extraordinaire habileté à former des polycycles complexes nous ont mené à étudier la réaction de polycyclisation anionique. Jouant sur des modifications autour d’une structure de type sorbate, divers précurseurs ont pu être synthétisés en vue d’une cascade réactionnelle. Parmi ceux-ci, les précurseurs possédant une fonction malonate ont efficacement mené à la formation de polycycles fonctionnalisés, au travers d’une séquence tandem d’oléfination de Horner-Emmons suivie immédiatement d’une polycyclisation anionique incluant une addition de Michael intramoléculaire et une condensation de Dieckmann. Enfin, l’étude d’une variante pour rendre la séquence plus polyvalente a été débutée. Celle-ci se base sur l’initiation de la cascade réactionnelle par une addition de Michael intermoléculaire.

Achieving high performance is one of the most difficult challenges in designing digital circuits. Flip-flops and adders are key blocks in most digital systems and must therefore be designed to yield highest performance. In this thesis, a new high performance serial adder is developed while power consumption is attained. Also, a statistical framework for the design of flip-flops is introduced that ensures that such sequential circuits meet timing yield under performance criteria. Firstly, a high performance serial adder is developed. The new adder is based on the idea of having a constant delay for the addition of two operands. While conventional adders exhibit logarithmic delay, the proposed adder works at a constant delay order. In addition, the new adder's hardware complexity is in a linear order with the word length, which consequently exhibits less area and power consumption as compared to conventional high performance adders. The thesis demonstrates the underlying algorithm used for the new adder and followed by simulation results. Secondly, this thesis presents a statistical framework for the design of flip-flops under process variations in order to maximize their timing yield. In nanometer CMOS technologies, process variations significantly impact the timing performance of sequential circuits which may eventually cause their malfunction. Therefore, developing a framework for designing such circuits is inevitable. Our framework generates the values of the nominal design parameters; i.e., the size of gates and transmission gates of flip-flop such that maximum timing yield is achieved for flip-flops. While previous works focused on improving the yield of flip-flops, less research was done to improve the timing yield in the presence of process variations.

Achieving high performance is one of the most difficult challenges in designing digital circuits. Flip-flops and adders are key blocks in most digital systems and must therefore be designed to yield highest performance. In this thesis, a new high performance serial adder is developed while power consumption is attained. Also, a statistical framework for the design of flip-flops is introduced that ensures that such sequential circuits meet timing yield under performance criteria. Firstly, a high performance serial adder is developed. The new adder is based on the idea of having a constant delay for the addition of two operands. While conventional adders exhibit logarithmic delay, the proposed adder works at a constant delay order. In addition, the new adder's hardware complexity is in a linear order with the word length, which consequently exhibits less area and power consumption as compared to conventional high performance adders. The thesis demonstrates the underlying algorithm used for the new adder and followed by simulation results. Secondly, this thesis presents a statistical framework for the design of flip-flops under process variations in order to maximize their timing yield. In nanometer CMOS technologies, process variations significantly impact the timing performance of sequential circuits which may eventually cause their malfunction. Therefore, developing a framework for designing such circuits is inevitable. Our framework generates the values of the nominal design parameters; i.e., the size of gates and transmission gates of flip-flop such that maximum timing yield is achieved for flip-flops. While previous works focused on improving the yield of flip-flops, less research was done to improve the timing yield in the presence of process variations.