Dynamic resolution of alpha-substituted dihydrocinnamic aldehydes. A new asymmetric synthesis of pharmaceutically important amine building blocks.

Crystallization-induced diastereoisomer transformation (CIDT) was successfully employed in the enantioselective synthesis of 2-alkyl-3-aryl-propan-1-amines. These products are seen as potentially useful building blocks in the field of asymmetric organic chemistry, notably for pharmaceutically relevant compounds. The procedure was based on a recently reported protocol for deracemization of dihydrocinnamic aldehydes in which enantiomerically enriched 1-(amino(phenyl)methyl)naphthalen-2-ol (Betti base) is employed as a resolving agent. Additionally, fenpropimorph, a biologically active substance which contains the 2-alkyl-3-aryl-propan-1-amine moiety was synthetized, as an attempt to assess the usefulness of the enantiomerically enriched amines.

Electromagnetic simulation and measurement of diffuse scattering from building walls

Il fenomeno dello scattering diffuso è stato oggetto di numerosi studi nell’arco degli ultimi anni, questo grazie alla sua rilevanza nell’ambito della propagazione elettromagnetica così come in molti altri campi di applicazione (remote sensing, ottica, fisica, etc.), ma la compresione completa di questo effetto è lungi dall’essere raggiunta. Infatti la complessità nello studio e nella caratterizzazione della diffusione deriva dalla miriade di casistiche ed effetti che si possono incontrare in un ambiente di propagazione reale, lasciando intuire la necessità di trattarne probabilisticamente il relativo contributo. Da qui nasce l’esigenza di avere applicazioni efficienti dal punto di vista ingegneristico che coniughino la definizione rigorosa del fenomeno e la conseguente semplificazione per fini pratici. In tale visione possiamo descrivere lo scattering diffuso come la sovrapposizione di tutti quegli effetti che si scostano dalle classiche leggi dell’ottica geometrica (riflessione, rifrazione e diffrazione) che generano contributi del campo anche in punti dello spazio e direzioni in cui teoricamente, per oggetti lisci ed omogenei, non dovrebbe esserci alcun apporto. Dunque l’effetto principale, nel caso di ambiente di propagazione reale, è la diversa distribuzione spaziale del campo rispetto al caso teorico di superficie liscia ed omogenea in congiunzione ad effetti di depolarizzazione e redistribuzione di energia nel bilancio di potenza. Perciò la complessità del fenomeno è evidente e l’obiettivo di tale elaborato è di proporre nuovi risultati che permettano di meglio descrivere lo scattering diffuso ed individuare altresì le tematiche sulle quali concentrare l’attenzione nei lavori futuri. In principio è stato quindi effettuato uno studio bibliografico così da identificare i modelli e le teorie esistenti individuando i punti sui quali riflettere maggiormente; nel contempo si sono analizzate le metodologie di caratterizzazione della permittività elettrica complessa dei materiali, questo per valutare la possibilità di ricavare i parametri da utilizzare nelle simulazioni utilizzando il medesimo setup di misura ideato per lo studio della diffusione. Successivamente si è realizzato un setup di simulazione grazie ad un software di calcolo elettromagnetico (basato sul metodo delle differenze finite nel dominio del tempo) grazie al quale è stato possibile analizzare la dispersione tridimensionale dovuta alle irregolarità del materiale. Infine è stata condotta una campagna di misure in camera anecoica con un banco sperimentale realizzato ad-hoc per effettuare una caratterizzazione del fenomeno di scattering in banda larga.

Pushover analysis of an existing reinforced concrete bridge:Jamboree Road Overcrossing in Irvine, California

The work for the present thesis started in California, during my semester as an exchange student overseas. California is known worldwide for its seismicity and its effort in the earthquake engineering research field. For this reason, I immediately found interesting the Structural Dynamics Professor, Maria Q. Feng's proposal, to work on a pushover analysis of the existing Jamboree Road Overcrossing bridge. Concrete is a popular building material in California, and for the most part, it serves its functions well. However, concrete is inherently brittle and performs poorly during earthquakes if not reinforced properly. The San Fernando Earthquake of 1971 dramatically demonstrated this characteristic. Shortly thereafter, code writers revised the design provisions for new concrete buildings so to provide adequate ductility to resist strong ground shaking. There remain, nonetheless, millions of square feet of non-ductile concrete buildings in California. The purpose of this work is to perform a Pushover Analysis and compare the results with those of a Nonlinear Time-History Analysis of an existing bridge, located in Southern California. The analyses have been executed through the software OpenSees, the Open System for Earthquake Engineering Simulation. The bridge Jamboree Road Overcrossing is classified as a Standard Ordinary Bridge. In fact, the JRO is a typical three-span continuous cast-in-place prestressed post-tension box-girder. The total length of the bridge is 366 ft., and the height of the two bents are respectively 26,41 ft. and 28,41 ft.. Both the Pushover Analysis and the Nonlinear Time-History Analysis require the use of a model that takes into account for the nonlinearities of the system. In fact, in order to execute nonlinear analyses of highway bridges it is essential to incorporate an accurate model of the material behavior. It has been observed that, after the occurrence of destructive earthquakes, one of the most damaged elements on highway bridges is a column. To evaluate the performance of bridge columns during seismic events an adequate model of the column must be incorporated. Part of the work of the present thesis is, in fact, dedicated to the modeling of bents. Different types of nonlinear element have been studied and modeled, with emphasis on the plasticity zone length determination and location. Furthermore, different models for concrete and steel materials have been considered, and the selection of the parameters that define the constitutive laws of the different materials have been accurate. The work is structured into four chapters, to follow a brief overview of the content. The first chapter introduces the concepts related to capacity design, as the actual philosophy of seismic design. Furthermore, nonlinear analyses both static, pushover, and dynamic, time-history, are presented. The final paragraph concludes with a short description on how to determine the seismic demand at a specific site, according to the latest design criteria in California. The second chapter deals with the formulation of force-based finite elements and the issues regarding the objectivity of the response in nonlinear field. Both concentrated and distributed plasticity elements are discussed into detail. The third chapter presents the existing structure, the software used OpenSees, and the modeling assumptions and issues. The creation of the nonlinear model represents a central part in this work. Nonlinear material constitutive laws, for concrete and reinforcing steel, are discussed into detail; as well as the different scenarios employed in the columns modeling. Finally, the results of the pushover analysis are presented in chapter four. Capacity curves are examined for the different model scenarios used, and failure modes of concrete and steel are discussed. Capacity curve is converted into capacity spectrum and intersected with the design spectrum. In the last paragraph, the results of nonlinear time-history analyses are compared to those of pushover analysis.

Investigation on laser shock peening capability by FE simulation

Laser shock peening is a technique similar to shot peening that imparts compressive residual stresses in materials for improving fatigue resistance. The ability to use a high energy laser pulse to generate shock waves, inducing a compressive residual stress field in metallic materials, has applications in multiple fields such as turbo-machinery, airframe structures, and medical appliances. The transient nature of the LSP phenomenon and the high rate of the laser's dynamic make real time in-situ measurement of laser/material interaction very challenging. For this reason and for the high cost of the experimental tests, reliable analytical methods for predicting detailed effects of LSP are needed to understand the potential of the process. Aim of this work has been the prediction of residual stress field after Laser Peening process by means of Finite Element Modeling. The work has been carried out in the Stress Methods department of Airbus Operations GmbH (Hamburg) and it includes investigation on compressive residual stresses induced by Laser Shock Peening, study on mesh sensitivity, optimization and tuning of the model by using physical and numerical parameters, validation of the model by comparing it with experimental results. The model has been realized with Abaqus/Explicit commercial software starting from considerations done on previous works. FE analyses are “Mesh Sensitive”: by increasing the number of elements and by decreasing their size, the software is able to probe even the details of the real phenomenon. However, these details, could be only an amplification of real phenomenon. For this reason it was necessary to optimize the mesh elements' size and number. A new model has been created with a more fine mesh in the trough thickness direction because it is the most involved in the process deformations. This increment of the global number of elements has been paid with an "in plane" size reduction of the elements far from the peened area in order to avoid too high computational costs. Efficiency and stability of the analyses has been improved by using bulk viscosity coefficients, a merely numerical parameter available in Abaqus/Explicit. A plastic rate sensitivity study has been also carried out and a new set of Johnson Cook's model coefficient has been chosen. These investigations led to a more controllable and reliable model, valid even for more complex geometries. Moreover the study about the material properties highlighted a gap of the model about the simulation of the surface conditions. Modeling of the ablative layer employed during the real process has been used to fill this gap. In the real process ablative layer is a super thin sheet of pure aluminum stuck on the masterpiece. In the simulation it has been simply reproduced as a 100µm layer made by a material with a yield point of 10MPa. All those new settings has been applied to a set of analyses made with different geometry models to verify the robustness of the model. The calibration of the model with the experimental results was based on stress and displacement measurements carried out on the surface and in depth as well. The good correlation between the simulation and experimental tests results proved this model to be reliable.

Influence of advanced load simulation models on fatigue design of jackets for offshore wind turbines.

Constant developments in the field of offshore wind energy have increased the range of water depths at which wind farms are planned to be installed. Therefore, in addition to monopile support structures suitable in shallow waters (up to 30 m), different types of support structures, able to withstand severe sea conditions at the greater water depths, have been developed. For water depths above 30 m, the jacket is one of the preferred support types. Jacket represents a lightweight support structure, which, in combination with complex nature of environmental loads, is prone to highly dynamic behavior. As a consequence, high stresses with great variability in time can be observed in all structural members. The highest concentration of stresses occurs in joints due to their nature (structural discontinuities) and due to the existence of notches along the welds present in the joints. This makes them the weakest elements of the jacket in terms of fatigue. In the numerical modeling of jackets for offshore wind turbines, a reduction of local stresses at the chord-brace joints, and consequently an optimization of the model, can be achieved by implementing joint flexibility in the chord-brace joints. Therefore, in this work, the influence of joint flexibility on the fatigue damage in chord-brace joints of a numerical jacket model, subjected to advanced load simulations, is studied.

Testing of subgrid scale (SGS) models for large-eddy simulation (LES) of turbulent channel flow

Sub-grid scale (SGS) models are required in order to model the influence of the unresolved small scales on the resolved scales in large-eddy simulations (LES), the flow at the smallest scales of turbulence. In the following work two SGS models are presented and deeply analyzed in terms of accuracy through several LESs with different spatial resolutions, i.e. grid spacings. The first part of this thesis focuses on the basic theory of turbulence, the governing equations of fluid dynamics and their adaptation to LES. Furthermore, two important SGS models are presented: one is the Dynamic eddy-viscosity model (DEVM), developed by \cite{germano1991dynamic}, while the other is the Explicit Algebraic SGS model (EASSM), by \cite{marstorp2009explicit}. In addition, some details about the implementation of the EASSM in a Pseudo-Spectral Navier-Stokes code \cite{chevalier2007simson} are presented. The performance of the two aforementioned models will be investigated in the following chapters, by means of LES of a channel flow, with friction Reynolds numbers $Re_\tau=590$ up to $Re_\tau=5200$, with relatively coarse resolutions. Data from each simulation will be compared to baseline DNS data. Results have shown that, in contrast to the DEVM, the EASSM has promising potentials for flow predictions at high friction Reynolds numbers: the higher the friction Reynolds number is the better the EASSM will behave and the worse the performances of the DEVM will be. The better performance of the EASSM is contributed to the ability to capture flow anisotropy at the small scales through a correct formulation for the SGS stresses. Moreover, a considerable reduction in the required computational resources can be achieved using the EASSM compared to DEVM. Therefore, the EASSM combines accuracy and computational efficiency, implying that it has a clear potential for industrial CFD usage.

An integrated system for building and running reproducible research

Our generation of computational scientists is living in an exciting time: not only do we get to pioneer important algorithms and computations, we also get to set standards on how computational research should be conducted and published. From Euclid’s reasoning and Galileo’s experiments, it took hundreds of years for the theoretical and experimental branches of science to develop standards for publication and peer review. Computational science, rightly regarded as the third branch, can walk the same road much faster. The success and credibility of science are anchored in the willingness of scientists to expose their ideas and results to independent testing and replication by other scientists. This requires the complete and open exchange of data, procedures and materials. The idea of a “replication by other scientists” in reference to computations is more commonly known as “reproducible research”. In this context the journal “EAI Endorsed Transactions on Performance & Modeling, Simulation, Experimentation and Complex Systems” had the exciting and original idea to make the scientist able to submit simultaneously the article and the computation materials (software, data, etc..) which has been used to produce the contents of the article. The goal of this procedure is to allow the scientific community to verify the content of the paper, reproducing it in the platform independently from the OS chosen, confirm or invalidate it and especially allow its reuse to reproduce new results. This procedure is therefore not helpful if there is no minimum methodological support. In fact, the raw data sets and the software are difficult to exploit without the logic that guided their use or their production. This led us to think that in addition to the data sets and the software, an additional element must be provided: the workflow that relies all of them.

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.

The influence of infill walls on seismic behavior of a historical building in Shanghai

Seismic assessment and seismic strengthening are the key issues need to be figured out during the process of protection and reusing of historical buildings. In this thesis the seismic behaviors of the hinged steel structure, a typical structure of historical buildings, i.e. hinged steel frames in Shanghai, China, were studied based on experimental investigations and theoretic analysis. How the non-structural members worked with the steel frames was analyzed thoroughly. Firstly, two 1/4 scale hinged steel frames were constructed based on the structural system of Bund 18, a historical building in Shanghai: M1 model without infill walls, M2 model with infill walls, and tested under the horizontal cyclic loads to investigate their seismic behavior. The Shaking Table Test and its results indicated that the seismic behavior of the hinged steel frames could be improved significantly with the help of non-structural members, i.e., surrounding elements outside the hinged steel frames and infilled walls. To specify, the columns are covered with bricks, they consist of I shape formed steel sections and steel plates, which are clenched together. The steel beams are connected to the steel column by steel angle, thus the structure should be considered as a hinged frame. And the infilled wall acted as a compression diagonal strut to withstand the horizontal load, therefore, the seismic capacity and stiffness of the hinged steel frames with infilled walls could be estimated by using the equivalent compression diagonal strut model. A SAP model has been constructed with the objective to perform a dynamic nonlinear analysis. The obtained results were compared with the results obtained from Shaking Table Test. The Test Results have validated that the influence of infill walls on seismic behavior can be estimated by using the equivalent diagonal strut model.

Modeling and validation of the thermal behavior of buildings for the development of demand response methods

The representation of the thermal behaviour of the building is achieved through a relatively simple dynamic model that takes into account the effects due to the thermal mass of the building components. The model of a intra-floor apartment has been built in the Matlab-Simulink environment and considers the heat transmission through the external envelope, wall and windows, the internal thermal masses, (i.e. furniture, internal wall and floor slabs) and the sun gain due to opaque and see-through surfaces of the external envelope. The simulations results for the entire year have been compared and the model validated, with the one obtained with the dynamic building simulation software Energyplus.