Zugl.: Köln, Fachhochsch., Diplomarbeit, 2007

Zugl.: Dortmund, Techn. Univ., Diss., 2008

Zugl.: Innsbruck, Universiẗat, Habil.-Schr., 2001.

No description available.

The main focus of this work was to investigate substitution effects on the chemical bonding in compounds of AlB 2 -type and related structure types. Delocalization indices within the QTAIM approach and the topological analysis of the ELI functionals were used as tools to describe the bonding situation in digallides and diborides. Digallides of AlB 2 -type were found only within group I and II; for CaGa 2 (meta-stable phase), SrGa 2 , BaGa 2 , YGa 2 and LaGa 2 compounds. Within these compounds, QTAIM analysis showed similar trend as previously found in diborides. That is, along the period in the Periodic Table, metal-triel interactions increase at the expense of in-plane (triel-triel) ab interactions (Tr=triel). However, transition metal diborides adopt the AlB 2 -type up to group VI. To understand this difference, we simulated transition metal (TM) digallides and diborides up to group VI in the AlB 2 -type. Additionally, the puckered variants diborides ReB 2 and OsB 2 were also simulated in the AlB 2 -type. With filling of d shell, there is a delicate balance between increase of TM–Tr and decrease of in-plane (Tr–Tr) ab electron sharing. This balance is maintained as long as interlayer interactions in the c direction (Tr–Tr ) c and (TM–TM ) c are not relatively too high in comparison to in-plane electron sharing. In contrast to TM B 2 of AlB 2 -type, digallides in the same structure type build up strong interlayer interactions for early transition metal elements. Our results showed that within digallides, a relatively strong increase in interlayer electron sharing (Ga–Ga) c and (TM–TM ) c takes place. Such increase occurs already for ScGa 2 and TiGa 2 . On the other hand, diborides show a steady increase in electron sharing of TM –B and (TM–TM ) c , but not of (B–B) c . Therefore, it is reasonable to suggest that diborides will tend to adopt a 3D network composed of boron and transition metal atoms (ReB 2 and RuB 2 types). The additional high (Ga–Ga) c interlayer interactions indicate a tendency for digallides to form 3D networks composed only by gallium atoms, characteristic of CaGa 2 (CaIn 2 -type) and ScGa 2 (KHg 2 -type). The counterbalancing bonding effects of in-plane and out-of-plane interactions that give the chemical flexibility of the AlB 2 -type in diborides is thus disrupted in AlB 2 -type digallides by a further enhanced degree of interlayer interactions (Ga–Ga) c and (TM –TM ) c . This results in a smaller number of digallides than that of diborides in AlB 2 -type. The most conspicuous difference between diborides and digallides of AlB 2 -type is in the representation of the B – B and Ga – Ga bonds revealed by the ELI- D topology. Whereas AlB 2 -type diborides exhibit one ELI-D attractor at the B – B midpoint, AlB 2 -type digallides exhibit two ELI-D attractors symmetrically opposite around the Ga – Ga bond midpoint. We utilized the E 2 H 4 (E=triel, tetrel ) molecular series in the D 2h point group symmetry as model systems for solid state calculations. In particular, we addressed the appearance of ELI- D double maxima for Ga – Ga, by using orbital decomposition within the ELI framework. The ELI-D topology changes along the 13th group T r 2 H 4 series. Whereas B 2 H 4 and Al 2 H 4 exhibit one ELI-D attractor representing the Tr–Tr bond, Ga 2 H 4 and In 2 H 4 give rise to two ELI-D attractors. Partial ELI-D allows the orbital decomposition of the electron density. Partial ELI-q gives access to the decomposition of a two-particle property, which is given by the Fermi-hole curvature. We have found that the d-orbitals enable the formation of the two ELI-D attractors through pairing contributions. This has a net effect of lowering electron localizability at the Ga – Ga bond midpoint. Namely, the different ELI-D topology of Ga – Ga and B – B bonds stems from the contributions of d-orbitals to orbital pairing. We have also investigated the bonding situation in transition metal diborides of ReB 2 -type (MnB 2 , TcB 2 , ReB 2) and RuB 2 -type (OsB 2 , RuB 2). One can consider these two structure types as an extension of the trend found in TM B 2 of AlB 2 -type: an increase in TM –B interactions and an enhanced three-center bonding. The change in the structure type results in a puckered layer of boron atoms with electrons equally shared between B – B and TM –B. However, TM –B bonds exhibit a high three-center character. The ELI-D/QTAIM intersection technique also revealed a high participation of TM in the B – B bonding basin population. Moreover, ELI-D topology in the ReB 2 -type also discloses a seemingly important Re 3 three-center interaction along the flat layer of Re atoms. Such basin is absent in MnB 2 , which coincides with the fact that MnB 2 was only observed in the AlB 2 -type. In this regard, we concluded that the 3D network consists not only of covalent B – B bonds, but also of TM –B bonds.

Role-based approaches gain more and more interest for modeling and implementing variable software systems. Role models clearly separate static behavior represented by players and dynamic behavior modeled as roles which can be dynamically bound and unbound to players at run time. To support the execution of role-based systems, a dynamic binding mechanism is required. Especially, since instances of the same player type can play different roles in a single context, the binding mechanism is required to operate at instance level. In this paper, we introduce a mechanism called dynamic instance binding for implementing a runtime for role-based systems. It maintains a look-up table that allows the run-time system to determine and invoke the currently active role binding at instance level. We explain dynamic instance binding mechanism in detail and demonstrate that it is flexible enough to support both adaptation and evolution of software systems at run time.

No description available.

Mixed association of calix[4]resorcinarene with ethyl sulfonate groups on the lower rim and dimethylaminomethyl groups on the upper rim (CR) and cationic surfactant 4-aza-1-hexadecyl-azoniabicyclo[2.2.2]octane bromide (DABCO-16) is studied by methods of tensiometry, conductometry, potentiometry and NMR spectroscopy at fixed CR concentration and varied surfactant concentration. Beyond ca. 0.4 mM of DABCO-16, mixed aggregates enriched by CR are proved to be formed due to electrostatic forces, while beyond ca. 5 mM, aggregates enriched by surfactant occur due to the hydrophobic effect. Spectrophotometry monitoring of the solubilization of a hydrophobic dye, Orange OT, demonstrated that only the second type of mixed aggregate enriched by DABCO-16 is capable of binding the organic probe, while the mixed system where the surfactant is a minor component shows no binding capacity towards Orange OT. This finding can be used for the design of nanocontainers with controllable binding/release properties. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Transitive reflexive Sätze des Deutschen lassen sich unter den Begriff des Mediums fassen. Genauso wie entsprechende Konstruktionen in anderen indoeuropäischen Sprachen sind sie auch im Deutschen mehrdeutig und erlauben eine reflexive, mediale, antikausative und inherent reflexive Interpretation. Nach einem Überblick über die für die folgende Diskussion wesentlichen syntaktischen und semantischen Eigenschaften transitiver reflexiver Sätze wird anhand der Medialkonstruktion gezeigt, daß weder lexikalische noch syntaktische Ansätze in der Lage sind, eine korrekte und einheitliche Analyse der Medialkonstruktion im speziellen und von transitiven reflexiven Sätzen im allgemeinen zu bieten. Deshalb wird für einen neuen, dritten Ansatz argumentiert: a) alle transitiven reflexiven Sätze sind syntaktisch einheitlich zu analysieren; b) vermeintliche syntaktische Unterschiede bzgl. Koordination, Fokus und Voranstellung des (Argument- und Nichtargument-) Reflexivums lassen sich semantisch ableiten; c) (schwache) Reflexivpronomen sind bzgl. ihrer morphosyntaktischen Merkmale maximal unterspezifiziert; d) im Deutschen muß zwischen strukturellen und obliquen Kasusformen unterschieden werden. (c) und (d) erlauben eine einheitliche Analyse der Mehrdeutigkeit des Reflexivpronomens in transitiven reflexiven Sätzen im Rahmen einer entsprechend modifizierten Bindungstheorie. Die in dieser Arbeit entwickelte Theorie wird abschließend auf weitere Eigenschaften der sog. Medialkonstruktion angewandt. / Crosslinguistically, transitive reflexive sentences in German can be subsumed under the notion of middle voice. Like corresponding constructions in Indo-European languages they are also ambiguous in German and yield a reflexive, middle, anticausative, and inherent reflexive interpretation. First, we give a detailed survey of the syntactic and semantic properties of transitive reflexive sentences that will be relevant in the following discussion. Second, we illustrate by means of the middle construction that lexical and syntactic theories fail to formulate a correct and unified analysis of middle formation in particular and transitive reflexive sentences in general. Therefore, we develop a different and (so far new) approach: a) all kinds of transitive reflexive sentences do not differ in syntax; b) the differences concerning coordination, focus, and fronting of the argument and non-argument reflexive are derived in semantics; c) the morphosyntactic features of (weak) reflexive pronouns are maximally underspecified d) German distinguishes between between structural and oblique case forms. (c) and (d) permit a uniform derivation of all four interpretations of the reflexive pronoun in transitive reflexive sentences. This analysis is based on a corresponding modification of the binding theory. Finally, we apply the theory developed in this book to further propertiies of the so-called middle construction.

This work focused on the further characterisation of Idhp and of the Krebs cycle enzymes citrate synthase 1 (Cit1p) and malate dehydrogenase 1 (Mdh1p) both of which have been identified as RNA-binding proteins without known RNA recognition motifs. Besides analysing their effects on mitochondrial translation and their organisation in protein complexes the work focused on the characterisation of the RNA-binding properties of recombinant Cit1p and Mdh1p: · Cit1p and Mdh1p play no essential role in mitochondrial protein synthesis. · Idhp is in a complex of molecular weight larger than the cytochrome c oxidase (250 kDa). · Cit1p and Mdh1p are in mitochondrial complexes smaller than 250 kDa. · 1000-fold molar excess of tRNA referring to COX2 leader RNA did not inhibit the RNA-binding of Cit1p and Mdh1p. · Cit1p and Mdh1p bind mitochondrial mRNAs (sense and antisense). The influence of cofactors and substrates on RNA-binding was analysed in order to reveal a possible link between the enzymatic function and the property of RNA-binding: · Acetyl-CoA and ATP inhibited the RNA-binding of Cit1p and Mdh1p at a concentration of 5 mM.