Influence of cladding on robustness of multi-storey buildings

In this dissertation the influence of a precast concrete cladding system on structural robustness of a multi-storey steel-composite building is studied. The analysis follows the well-established framework developed at Imperial College London for the appraisal of robustness of multi-storey buildings. For this scope a simplified nonlinear model of a typical precast concrete façade-system is developed. Particular attention is given to the connection system between structural frame and panel, recognised as the driving component of the nonlinear behaviour of the façade-system. Only connections involved in the gravity load path are evaluated (bearing connections). Together with standard connection, a newly proposed system (Slotted Bearing Connection) is designed to achieve a more ductile behaviour of the panel-connection system. A parametric study involving the dimensions of panel-connection components is developed to search for an optimal configuration of the bearing connection. From the appraisal of structural robustness of the panelised frame it is found that the standard connection systems may reduce the robustness of a multi-storey frame due to a poor ductile behaviour while the newly proposed connection is able to guarantee an enhanced response to the panelised multi-storey frame thanks to a higher ductility.

Atropisomeric xanthines: Synthesis, stereodynamics and absolute configuration

During the thesis period a new class of atropisomeric xanthine derivatives has been studied. We decided to focus our attention on these purine bases because of their various biological activities, that could play an important role in the discovery of new bioactive atropisomers. The synthesized compounds bear an Aryl-N chiral axis in position 1 of the xanthine scaffold, around which the rotation is prevented by the presence of bulky ortho substituents. Through a retro synthetic analysis we synthesized three atropisomeric structures bearing in position 1 of the purine scaffold respectively an o-tolyl, o-nitrophenyl and a 1-naphthyl group. The conformational studies by DFT simulations showed that the interconversion energy barrier between the two available skewed conformations is higher enough to obtain thermally stable atropisomers. After the separation of the atropisomers, the experimental energy of interconversion was investigated by means of kinetic studies following the thermal racemization process using an enantioselective HPLC column. The absolute configuration of each atropisomer was assigned by experimental ECD analysis and TD-DFT simulations of the ECD spectra.

Synthesis and dynamic study of atropisomeric compounds containing boron-carbon bond

In this thesis we studied the stereodynamic behavior of 1,2-azaborines variously substituted on boron (7a, 7b, 13). Depending on the hindrance of the asymmetric aryl substituent the resulting conformations could be stereolabile or configurationally stable. Through dynamic NMR and lineshape simulation, the energy rotational barriers of the different conformers are obtained. When the barrier is higher than 22-23 kcal/mol stable atropisomers that are fisically separable could be obtained (case of compound 13) and the free activation energy barrier is determinable by kinetic analysis. Absolute configuration of two atropisomers were assigned by comparison between computational calculations and experimental ECD. Isosteric compound 21 is then synthesized in order to compare the rotational barrier around B-Caryl with the one around Cnaphth-Caryl bond.

Dithienopyrrole-based materials: development of new polymeric derivatives

The possibility to control molar mass and termination of the growing chain is fundamental to create well-defined, reproducible materials. For this reason, in order to apply polydithienopyrrole (PDTP) as organic conjugated polymer, the possibility of controlled polymerization needs to be verified. Another aspect that is still not completely explored is bound to the optical activity of the PDTP, which bearing appropriate substituents may adopt a helical conformation. The configuration of the helix, built up from achiral co-monomers, can be established in an enantiopure way by using only a small percentage of the chiral monomer co-polymerized with achiral co-monomer. The effect, called “sergeants and soldiers effect”, is expressed by the nonlinear increase of the chiral response vs the ratio of the chiral co-monomer used for the polymerization. To date, this effect is still not completely explored for PDTP. In this framework the project will investigate, firstly, the possibility to obtain a controlled polymerization of PDTP. Then, monomers with different side chains and organometallic functions will be screened for a CTCP-type polymerization. Also a Lewis-acid based cationic polymerization will be performed. Moreover the chemical derivatization of dithienopyrrole DTP is explored: the research is going to concern also block copolymers, built up by DTP and monomers of different nature. The research will be extended also to the investigation of optically active derivates of PDTP, using a chiral monomer for the synthesis. The possibility to develop a supramolecular distribution of the polymeric chains, together with the “sergeants and soldiers effect” will be checked investigating a series of polymers with increasing amounts of chiral monomer.

Wind analysis of the Messina Strait Bridge design project proposal with stabilizing cables

A new study on suspension bridges has been prompted by the big disaster of the Tacoma Narrow Bridge at half its design speed. The aerodynamic instability of long-span bridges has been studied using wind tunnel tests. As a result of improved aerodynamic performance from the geometrical configuration of the bridge deck, the aerodynamic criteria for suspension and cable-stayed bridges have become well established in recent years, thereby allowing longer bridge spans to be developed. Although the Messina Strait Bridge has yet to be constructed, we are looking forward to evaluating the impact of different deck cross-sections on both aerodynamic stability and cost reduction. To further improve the aerodynamic characteristics of long-span suspension bridges, an optimized multi-box bridge deck model with two side decks for traffic lanes, two middle railway decks, and three gaps separating them has been proposed aerodynamic performance has been experimentally verified. 1:80 scale wind tunnel tests have been conducted. According to the current MIDAS Model, the first torsional and the first vertical frequency ratios are 1.27787 and 1.36[1] respectively. It is the torsional/vertical frequency ratio, combined with the deck aerodynamic properties, that determines the wind response properties of the bridge for the most dangerous possible form of aeroelastic instability. The classic flutter is caused by the coupling of torsional and vertical modes. Stabilizing cables to the deck could be a solution to this classic flutter by reducing lateral displacement of the deck and increasing frequency ratios. Stabilizing cables will be installed on the deck in three different orientations: vertical, inclined, and horizontal, with diameters of 80 cm, 60 cm, and 40 cm in each orientation respectively. An overview of the research undertaken on this topic will be presented, as well as the most important findings.