Frustrierte Lewis-Paare (FLPs) bestehen aus einer Lewis-Säure und -Base, die an der gegenseitigen Neutralisierung gehindert werden und so erfolgreich zur Aktivierung kleiner Moleküle eingesetzt werden konnten. Als Elektronenpaarakzeptoren wurden bislang vorwiegend Borane erforscht. Aluminiumbasierte Systeme, insbesondere intramolekularer Art, sind trotz ihrer ausgeprägten Lewis-Acidität unterrepräsentiert. In der vorliegenden Dissertation wurde untersucht, welche Syntheserouten sich zur Darstellung intramolekularer Phosphor/Aluminium-FLPs mit großer räumlicher Trennung der Lewis-Funktionen eignen und welche Reaktivität diese aufweisen. An einem Xanthenrückgrat mit Diphenylphosphineinheit konnten durch Lithiierung und Metathese Dimesityl- und Bis(pentafluorphenyl)alaneinheiten eingeführt werden und die resultierenden P/Al-FLPs sind in der Lage, Tetrahydrofuran zu öffnen. Das perfluorierte Derivat wies dabei eine zehnfach höhere Geschwindigkeitskonstante der Ringöffnungsreaktion auf. Mittels quantenchemischer Rechnungen konnte dies auf die gesteigerte Lewis-Acidität des Aluminiumzentrums zurückgeführt werden. Durch den Zinn-Aluminium-Austausch eines trimethylstannylierten Xanthenvorläufers mit Methylaluminiumverbindungen konnten P/Al-FLPs aufgebaut werden, die durch ein weiteres Äquivalent des Alanpräkursors stabilisiert werden. Die Verbindungen sind imstande, Kohlenstoffdioxid zu aktivieren, wobei die CO2-Addukte der verschiedenen Derivate mit zunehmender Anzahl elektronegativer Substituenten an den Aluminiumzentren eine zunehmende thermodynamische Stabilisierung erfahren. Die neuartige Syntheseroute konnte auch zur Darstellung eines biphenylengebundenen P/Al-FLPs genutzt werden. In diesem Fall ist das Aluminiumzentrum durch die Wechselwirkung mit dem Phosphandonor ausreichend gesättigt, um die Isolierung der gespannten Verbindungen in monomerer Form zu ermöglichen. Dennoch weist das Alan eine hohe Lewis-Acidität auf und der FLP reagiert mit CO2 und Propadien. / Frustrated Lewis pairs (FLPs) consist of a Lewis acid and base, which are prevented from neutralising each other and in turn could be successfully used to activate small molecules. Boranes have been predominantly explored as electron pair acceptors. In contrast, aluminium-based systems, in particular intramolecular ones, are underrepresented despite their pronounced Lewis acidity. The aim of the present dissertation was to fathom which synthetic route is suitable for the preparation of intramolecular phosphorus/aluminium FLPs with large spatial separation of the Lewis functions and to investigate their reactivity. On a xanthene backbone bearing a diphenylphosphine moiety, dimesityl and bis(pentafluorophenyl)alane units could be introduced by lithiation and metathesis, and the resulting P/Al-FLPs are able to open tetrahydrofuran. The perfluorinated derivative exhibited a tenfold higher rate constant of the ring opening reaction. Using quantum chemical calculations, this could be attributed to the increased Lewis acidity of the aluminium centre. Using a tin-aluminum exchange on a trimethylstannylated xanthene precursor with methylaluminium compounds, P/Al-FLPs could be constructed, which are stabilised by another equivalent of the aluminium precursor. The compounds are capable of activating carbon dioxide, and the CO2 adducts of the various derivatives become increasingly stabilised as the number of electronegative substituents at the aluminium centres increases. The novel synthetic route could also be applied for the synthesis of a P/Al-FLP on the biphenylene linker. In this case, the aluminium centre is sufficiently saturated by an interaction with the phosphane donor to permit the isolation of the strained compounds in monomeric form. Nevertheless, the alane exhibits high Lewis acidity and the FLP reacts with CO2 and propadiene.

Ruthenium-based homogenous catalysis is a broad and extremely useful branch of transition metal catalysis. Surely, the most famous example is olefin metathesis, for which Yves Chauvin, Robert Grubbs and Richard Schrock were awarded the 2005 Chemistry Nobel Prize. Although some of the most well-known catalysts are widely used and considered benchmark catalysts, the research around this topic has not stopped. The modification of known systems to achieve better performance and better understanding of the catalytic mechanism is very important and an example of such modification is reported in this thesis. The newly synthesised catalysts were compared to the parent commercially available catalyst showing better reactivity. Ruthenium catalysis, though, is not limited to olefin metathesis and C-H activation, for example, it has become a useful approach to the functionalisation of organic molecules. In this field, the deuteration of C-H bonds is an interesting transformation, which has many applications. The synthesis of new hydridosilylruthenium complexes and their application in the deuteration of a variety of substrates is reported in this manuscript. The unprecedented synthesis of tetradeuterated Ketoprofene is also reported. Recently, ruthenium-based catalysts have found application in the dehydrogenation of suitable compounds, such as formic acid, ammonia-borane and other hydrogen-rich substances. The driving force behind these discoveries is the use of H2 as an energy vector in place of fossil fuels. A hydrido-ruthenium catalyst was shown to catalyse the decomposition of formic acid in CO2 and H2 and to catalyse the reduction of olefinic substrates. The released CO2 from the reaction did not interfere with the fuel cell due to its inertness. This property makes its employment as C1 source very challenging, although its use would also be extremely attractive because of the abundance of this gas. In these regards, both frustrated Lewis pairs (FLPs) and gold catalysts have shown interesting reactivity in the activation of CO2. A new FLP and a silica supported gold catalyst were synthesised to test them in CO2 activation and the results are reported in this manuscript.

This dissertation develops efficient solution techniques for general and problem-specific applications within nonconvex optimization, exploiting the constructs of the Reformulation-Linearization Technique (RLT). We begin by developing a technique to enhance general problems in nonconvex optimization through the use of a new class of RLT cuts, called semidefinite cuts. While these cuts are valid for any general problem for which RLT is applicable, we demonstrate their effectiveness in optimizing a nonconvex quadratic objective function over a simplex. Computational results indicate that on average, the semidefinite cuts have reduced the number of nodes in the branch-and-bound tree by a factor of 37.6, while decreasing solution time by a factor of 3.4. The semidefinite cuts have also led to a significant reduction in the optimality gap at termination, in some cases producing optimal solutions for problems that could not be solved using RLT alone. We then narrow our focus to the class of mixed-integer programming (MIP) problems, and develop a modification of Benders' decomposition method using concepts from RLT and lift-and-project cuts. This method is particularly motivated by the class of two-stage stochastic programs with integer recourse. The key idea is to design an RLT or lift-and-project cutting plane scheme for solving the subproblems where the cuts generated have right-hand sides that are functions of the first-stage variables. An illustrative example is provided to elucidate the proposed approach. The focus is on developing a first comprehensive finitely convergent extension of Benders' methodology for problems having 0-1 mixed-integer subproblems. We next address a specific challenging MIP application known as the facility layout problem, and we significantly improve its formulation through outer-linearization techniques and concepts from disjunctive programming. The enhancements produce a substantial increase in the accuracy of the layout produced, while at the same time, providing a dramatic reduction in computational effort. Overall, the maximum error in department size was reduced from about 6% to nearly zero, while solution time decreased by a factor of 110. Previously unsolved test problems from the literature that had defied even approximate solution methods have been solved to exact optimality using our proposed approach. / Ph. D.

Στην εργασία αυτή γίνεται μια αναφορά αρχικά στα GSM δίκτυα κινητής τηλεφωνίας (χαρακτηριστικά-λειτουργίες). Στη συνέχεια περιγράφεται ο τρόπος υπολογισμού της κυτταρικής ακτίνας με βάση τα μοντέλα Okumura-Hata και Ikegami. Τέλος αναφέρονται παραδείγματα υπολογισμού της ακτίνας των κυττάρων αλλά και διαστασιοποίησης των καναλιών σε αυτά ώστε να εξυπηρετείται συγκεκριμένη τηλεπικοινωνιακή κίνηση. / The purpose of this project is to examine the major steps in cell planning process such as cell coverage, frequency planning and calculations of traffic and channel needs for the given areas.

The aim of this study is to present the views of some English-speaking parents and their children based in Sweden on the relationship between language learning and family language policies. To this end, interviews were conducted with six families living in Sweden who had spoken English at home with their children. The data was analysed using a thematic approach, which involves a close analysis of the collected data. I specified major and common points from the participants that were in line with my research questions. The results showed that the participating parents wanted their children to be able to speak with their English-speaking relatives and therefore felt that it was important to teach and maintain English. They also mention how English is a useful language to know because it is spoken all around the world. Some parents point out that consistency is important for the child’s language development in English, while others explain how there is no need for strict rules because it can lead to a resistance in speaking English. The most common strategies the parents employ are one- parent-one-language strategy, encouraging watching TV and films, reading books, repetition- and minimal grasp strategy and mother tongue tuition. The children emphasise the importance of knowing English when they talk with their relatives. However, the children find it difficult when learning a third language in school because they are used to acquiring a language instead of consciously learning it. The implications from my research may potentially help policy makers, researchers, and bilingual families in the process of teaching and maintaining a language at home.

No description available.

No description available.

No description available.

The phosphatidylinositol 3' kinase (PI3K) pathway is involved in many cellular processes including cell proliferation, survival, and glucose transport, and is implicated in various disease states such as cancer and diabetes. Though there have been numerous studies dissecting the role of PI3K signaling in different cell types and disease models, the mechanism by which PI3K signaling regulates embryonic stem (ES) cell fate remains unclear. It is believed that in addition to proliferation and tumorigenicity, PI3K activity might also be important for self-renewal of ES cells. Paling et al. (2004) reported that the inhibition of PI3K led to a reduction in the ability of leukemia inhibitory factor (LIF) to maintain self-renewal causing cells to differentiate. Studies in our lab have revealed that ES cells completely lacking GSK-3 remain undifferentiated compared to wildtype ES cells. GSK-3 is negatively regulated by PI3K suggesting that PI3K may play a vital role in maintaining pluripotency in ES cells through GSK-3. By using a modified Flp recombinase system, we expressed activated alleles of PDK-1 and PKB to create stable, isogenic ES cell lines to further study the role of the PI3K signaling pathway in stem cell fate determination. In vitro characterization of the transgenic cell lines revealed a strong tendency towards maintenance of pluripotency, and this phenotype was found to be independent of canonical Wnt signal transduction. To assess growth and differentiation capacity in vivo, the ES cell lines were grown as subcutaneous teratomas. The constitutively active PDK-1 and PKB ES cell lines were able to form all three germ layers when grown in this manner – in contrast to ES cells engineered to lack GSK-3. The resulting PI3K pathway activated cells exhibited a higher growth rate which resulted in large teratomas. In summary, PI3K signaling is sufficient to maintain self-renewal and survival of stem cells. Since this pathway is frequently mutationally activated in cancers, its effect on suppressing differentiation may contribute to its oncogenicity.

The phosphatidylinositol 3' kinase (PI3K) pathway is involved in many cellular processes including cell proliferation, survival, and glucose transport, and is implicated in various disease states such as cancer and diabetes. Though there have been numerous studies dissecting the role of PI3K signaling in different cell types and disease models, the mechanism by which PI3K signaling regulates embryonic stem (ES) cell fate remains unclear. It is believed that in addition to proliferation and tumorigenicity, PI3K activity might also be important for self-renewal of ES cells. Paling et al. (2004) reported that the inhibition of PI3K led to a reduction in the ability of leukemia inhibitory factor (LIF) to maintain self-renewal causing cells to differentiate. Studies in our lab have revealed that ES cells completely lacking GSK-3 remain undifferentiated compared to wildtype ES cells. GSK-3 is negatively regulated by PI3K suggesting that PI3K may play a vital role in maintaining pluripotency in ES cells through GSK-3. By using a modified Flp recombinase system, we expressed activated alleles of PDK-1 and PKB to create stable, isogenic ES cell lines to further study the role of the PI3K signaling pathway in stem cell fate determination. In vitro characterization of the transgenic cell lines revealed a strong tendency towards maintenance of pluripotency, and this phenotype was found to be independent of canonical Wnt signal transduction. To assess growth and differentiation capacity in vivo, the ES cell lines were grown as subcutaneous teratomas. The constitutively active PDK-1 and PKB ES cell lines were able to form all three germ layers when grown in this manner – in contrast to ES cells engineered to lack GSK-3. The resulting PI3K pathway activated cells exhibited a higher growth rate which resulted in large teratomas. In summary, PI3K signaling is sufficient to maintain self-renewal and survival of stem cells. Since this pathway is frequently mutationally activated in cancers, its effect on suppressing differentiation may contribute to its oncogenicity.