Planning and flexible operation of storage systems in power grids: from transmission to distribution networks

The first part of the thesis has been devoted to the transmission planning with high penetration of renewable energy sources. Both stationary and transportable battery energy storage (BES, BEST) systems have been considered in the planning model, so to obtain the optimal set of BES, BEST and transmission lines that minimizes the total cost in a power network. First, a coordinated expansion planning model with fixed transportation cost for BEST devices has been presented; then, the model has been extended to a planning formulation with a distance-dependent transportation cost for the BEST units, and its tractability has been proved through a case study based on a 190-bus test system. The second part of this thesis is then devoted to the analysis of planning and management of renewable energy communities (RECs). Initially, the planning of photovoltaic and BES systems in a REC with an incentive-based remuneration scheme according to the Italian regulatory framework has been analysed, and two planning models, according to a single-stage, or a multi-stage approach, have been proposed in order to provide the optimal set of BES and PV systems allowing to achieve the minimum energy procurement cost in a given REC. Further, the second part of this thesis is devoted to the study of the day-ahead scheduling of resources in renewable energy communities, by considering two types of REC. The first one, which we will refer to as “cooperative community”, allows direct energy transactions between members of the REC; the second type of REC considered, which we shall refer to as “incentive-based”, does not allow direct transactions between members but includes economic revenues for the community shared energy, according to the Italian regulation framework. Moreover, dispatchable renewable energy generation has been considered by including producers equipped with biogas power plants in the community.

Design and Performance Analysis of the Electrical Power System of a Petrochemical Facility

This thesis deals with the sizing and analysis of the electrical power system of a petrochemical plant. The activity was carried out in the framework of an electrical engineering internship. The sizing and electrical calculations, as well as the study of the dynamic behavior of network quantities, are accomplished by using the ETAP (Electrical Transient Analyzer Program) software. After determining the type and size of the loads, the calculation of power flows is carried out for all possible network layout and different power supply configurations. The network is normally operated in a double radial configuration. However, the sizing must be carried out taking into account the most critical configuration, i.e., the temporary one of single radial operation, and also considering the most unfavorable power supply conditions. The calculation of shortcircuit currents is then carried out and the appropriate circuit breakers are selected. Where necessary, capacitor banks are sized in order to keep power factor at the point of common coupling within the preset limits. The grounding system is sized by using the finite element method. For loads with the highest level of criticality, UPS are sized in order to ensure their operation even in the absence of the main power supply. The main faults that can occur in the plant are examined, determining the intervention times of the protections to ensure that, in case of failure on one component, the others can still properly operate. The report concludes with the dynamic and stability analysis of the power system during island operation, in order to ensure that the two gas turbines are able to support the load even during transient conditions.

De Novo Design of secondary structures: Synthesis and conformational studies

Chemists have long sought to extrapolate the power of biological catalysis and recognition to synthetic systems. These efforts have focused largely on low molecular weight catalysts and receptors; however, biological systems themselves rely almost exclusively on polymers, proteins and RNA, to perform complex chemical functions. Proteins and RNA are unique in their ability to adopt compact, well-ordered conformations, and specific folding provides precise spatial orientation of the functional groups that comprise the “active site”. These features suggest that identification of new polymer backbones with discrete and predictable folding propensities (“foldamers”) will provide a basis for design of molecular machines with unique capabilities. The foldamer approach complements current efforts to design unnatural properties into polypeptides and polynucleotides. The aim of this thesis is the synthesis and conformational studies of new classes of foldamers, using a peptidomimetic approach. Moreover their attitude to be utilized as ionophores, catalysts, and nanobiomaterials were analyzed in solution and in the solid state. This thesis is divided in thematically chapters that are reported below. It begins with a very general introduction (page 4) which is useful, but not strictly necessary, to the expert reader. It is worth mentioning that paragraph I.3 (page 22) is the starting point of this work and paragraph I.5 (page 32) isrequired to better understand the results of chapters 4 and 5. In chapter 1 (page 39) is reported the synthesis and conformational analysis of a novel class of foldamers containing (S)-β3-homophenylglycine [(S)-β3-hPhg] and D- 4-carboxy-oxazolidin-2-one (D-Oxd) residues in alternate order is reported. The experimental conformational analysis performed in solution by IR, 1HNMR, and CD spectroscopy unambiguously proved that these oligomers fold into ordered structures with increasing sequence length. Theoretical calculations employing ab initio MO theory suggest a helix with 11-membered hydrogenbonded rings as the preferred secondary structure type. The novel structures enrich the field of peptidic foldamers and might be useful in the mimicry of native peptides. In chapter 2 cyclo-(L-Ala-D-Oxd)3 and cyclo-(L-Ala-DOxd) 4 were prepared in the liquid phase with good overall yields and were utilized for bivalent ions chelation (Ca2+, Mg2+, Cu2+, Zn2+ and Hg2+); their chelation skill was analyzed with ESI-MS, CD and 1HNMR techniques and the best results were obtained with cyclo-(L-Ala-D-Oxd)3 and Mg2+ or Ca2+. Chapter 3 describes an application of oligopeptides as catalysts for aldol reactions. Paragraph 3.1 concerns the use of prolinamides as catalysts of the cross aldol addition of hydroxyacetone to aromatic aldeydes, whereas paragraphs 3.2 and 3.3 are about the catalyzed aldol addition of acetone to isatins. By means of DFT and AIM calculations, the steric and stereoelectronic effects that control the enantioselectivity in the cross-aldol addition of acetone to isatin catalysed by L-proline have been studied, also in the presence of small quantities of water. In chapter 4 is reported the synthesis and the analysis of a new fiber-like material, obtained from the selfaggregation of the dipeptide Boc-L-Phe-D-Oxd-OBn, which spontaneously forms uniform fibers consisting of parallel infinite linear chains arising from singleintermolecular N-H···O=C hydrogen bonds. This is the absolute borderline case of a parallel β-sheet structure. Longer oligomers of the same series with general formula Boc-(L-Phe-D-Oxd)n-OBn (where n = 2-5), are described in chapter 5. Their properties in solution and in the solid state were analyzed, in correlation with their attitude to form intramolecular hydrogen bond. In chapter 6 is reported the synthesis of imidazolidin-2- one-4-carboxylate and (tetrahydro)-pyrimidin-2-one-5- carboxylate, via an efficient modification of the Hofmann rearrangement. The reaction affords the desired compounds from protected asparagine or glutamine in good to high yield, using PhI(OAc)2 as source of iodine(III).

A Generic model for the design and analysis of production systems

This dissertation studies the process of operations systems design within the context of the manufacturing organization. Using the DRAMA (Design Routine for Adopting Modular Assembly) model as developed by a team from the IDOM Research Unit at Aston University as a starting point, the research employed empirically based fieldwork and a survey to investigate the process of production systems design and implementation within four UK manufacturing industries: electronics assembly, electrical engineering, mechanical engineering and carpet manufacturing. The intention was to validate the basic DRAMA model as a framework for research enquiry within the electronics industry, where the initial IDOM work was conducted, and then to test its generic applicability, further developing the model where appropriate, within the other industries selected. The thesis contains a review of production systems design theory and practice prior to presenting thirteen industrial case studies of production systems design from the four industry sectors. The results and analysis of the postal survey into production systems design are then presented. The strategic decisions of manufacturing and their relationship to production systems design, and the detailed process of production systems design and operation are then discussed. These analyses are used to develop the generic model of production systems design entitled DRAMA II (Decision Rules for Analysing Manufacturing Activities). The model contains three main constituent parts: the basic DRAMA model, the extended DRAMA II model showing the imperatives and relationships within the design process, and a benchmark generic approach for the design and analysis of each component in the design process. DRAMA II is primarily intended for use by researchers as an analytical framework of enquiry, but is also seen as having application for manufacturing practitioners.

A Framework supporting collaboration on the distributed design of integrated systems

The work described in this thesis aims to support the distributed design of integrated systems and considers specifically the need for collaborative interaction among designers. Particular emphasis was given to issues which were only marginally considered in previous approaches, such as the abstraction of the distribution of design automation resources over the network, the possibility of both synchronous and asynchronous interaction among designers and the support for extensible design data models. Such issues demand a rather complex software infrastructure, as possible solutions must encompass a wide range of software modules: from user interfaces to middleware to databases. To build such structure, several engineering techniques were employed and some original solutions were devised. The core of the proposed solution is based in the joint application of two homonymic technologies: CAD Frameworks and object-oriented frameworks. The former concept was coined in the late 80's within the electronic design automation community and comprehends a layered software environment which aims to support CAD tool developers, CAD administrators/integrators and designers. The latter, developed during the last decade by the software engineering community, is a software architecture model to build extensible and reusable object-oriented software subsystems. In this work, we proposed to create an object-oriented framework which includes extensible sets of design data primitives and design tool building blocks. Such object-oriented framework is included within a CAD Framework, where it plays important roles on typical CAD Framework services such as design data representation and management, versioning, user interfaces, design management and tool integration. The implemented CAD Framework - named Cave2 - followed the classical layered architecture presented by Barnes, Harrison, Newton and Spickelmier, but the possibilities granted by the use of the object-oriented framework foundations allowed a series of improvements which were not available in previous approaches: - object-oriented frameworks are extensible by design, thus this should be also true regarding the implemented sets of design data primitives and design tool building blocks. This means that both the design representation model and the software modules dealing with it can be upgraded or adapted to a particular design methodology, and that such extensions and adaptations will still inherit the architectural and functional aspects implemented in the object-oriented framework foundation; - the design semantics and the design visualization are both part of the object-oriented framework, but in clearly separated models. This allows for different visualization strategies for a given design data set, which gives collaborating parties the flexibility to choose individual visualization settings; - the control of the consistency between semantics and visualization - a particularly important issue in a design environment with multiple views of a single design - is also included in the foundations of the object-oriented framework. Such mechanism is generic enough to be also used by further extensions of the design data model, as it is based on the inversion of control between view and semantics. The view receives the user input and propagates such event to the semantic model, which evaluates if a state change is possible. If positive, it triggers the change of state of both semantics and view. Our approach took advantage of such inversion of control and included an layer between semantics and view to take into account the possibility of multi-view consistency; - to optimize the consistency control mechanism between views and semantics, we propose an event-based approach that captures each discrete interaction of a designer with his/her respective design views. The information about each interaction is encapsulated inside an event object, which may be propagated to the design semantics - and thus to other possible views - according to the consistency policy which is being used. Furthermore, the use of event pools allows for a late synchronization between view and semantics in case of unavailability of a network connection between them; - the use of proxy objects raised significantly the abstraction of the integration of design automation resources, as either remote or local tools and services are accessed through method calls in a local object. The connection to remote tools and services using a look-up protocol also abstracted completely the network location of such resources, allowing for resource addition and removal during runtime; - the implemented CAD Framework is completely based on Java technology, so it relies on the Java Virtual Machine as the layer which grants the independence between the CAD Framework and the operating system. All such improvements contributed to a higher abstraction on the distribution of design automation resources and also introduced a new paradigm for the remote interaction between designers. The resulting CAD Framework is able to support fine-grained collaboration based on events, so every single design update performed by a designer can be propagated to the rest of the design team regardless of their location in the distributed environment. This can increase the group awareness and allow a richer transfer of experiences among them, improving significantly the collaboration potential when compared to previously proposed file-based or record-based approaches. Three different case studies were conducted to validate the proposed approach, each one focusing one a subset of the contributions of this thesis. The first one uses the proxy-based resource distribution architecture to implement a prototyping platform using reconfigurable hardware modules. The second one extends the foundations of the implemented object-oriented framework to support interface-based design. Such extensions - design representation primitives and tool blocks - are used to implement a design entry tool named IBlaDe, which allows the collaborative creation of functional and structural models of integrated systems. The third case study regards the possibility of integration of multimedia metadata to the design data model. Such possibility is explored in the frame of an online educational and training platform.

The role of software tools in influencing creative problem solving in engineering design and education

Creativity is increasingly recognised as an essential component of engineering design. This paper describes an exploratory study into the nature and importance of creativity in engineering design problem solving in relation to the possible impact of software design tools. The first stage of the study involved an empirical investigation in the form of a case study of the use of standard CAD tool sets and the development of a systems engineering software support tool. It was found that there were several ways in which CAD influenced the creative process, including enhancing visualisation and communication, premature fixation, circumscribed thinking and bounded ideation. The tool development experience uncovered the difficulty in supporting creative processes from the developer's perspective. The issues were the necessity of making assumptions, achieving a balance between structure and flexibility, and the pitfalls of satisfying user wants and needs. The second part of the study involved the development of a model of the creative problem solving process in engineering design. This provided a possible explanation for why purpose designed engineering software tools might encourage an analytical problem solving approach and discourage a more creative approach.

Re-examination of the anion derivatives of isoflavones by radical fragmentation in negative electrospray ionization tandem mass spectrometry: experimental and computational studies

This paper reports theoretical and experimental studies of gas-phase fragmentation reactions of four naturally occurring isoflavones. The samples were analyzed in negative ion mode by direct infusion in ESI-QqQ, ESI-QqTOF and ESI-Orbitrap systems. The MS/MS and MS(n) spectra are in agreement with the fragmentation proposals and high-resolution analyses have confirmed the formulae for each ion observed. As expected, compounds with methoxyl aromatic substitution have showed a radical elimination of center dot CH(3) as the main fragmentation pathway. A second radical loss (center dot H) occurs as previously observed for compounds which exhibit a previous homolytic center dot CH(3) cleavage (radical anion) and involves radical resonance to stabilize the anion formed. However, in this study we suggest another mechanism for the formation of the main ions, on the basis of the enthalpies for each species. Compounds without methoxy substituent dissociate at the highest energies and exhibit the deprotonated molecule as the most intense ion. Finally, energy-resolved experiments were carried out to give more details about the gas-phase dissociation reaction of the isoflavones and the results are in agreement with the theoretical approaches. Copyright (C) 2011 John Wiley & Sons, Ltd.

No androcentric perspective in studies of one parent families. Relections and methodological implications

This paper presents a discussion on the process that led us to a progressively developing of a specific methodological approach for research on one parent families. This process has been systematized and built from the contributions of feminist epistemologies to the methodological design and participatory forms of work. From it derives a scientific and technical contribution, internationally unpublisheduntil now: Single Parenthood and family diversity Survey (EMODIF), which we propose as a not androcentric measuring tool of single parenthood, their profiles,experiences, expectations and realities. With this article we want to offer a systematization of the implications that has had our implementation of the feminist perspective in studies of one parent families.

Re-examination of the anion derivatives of isoflavones by radical fragmentation in negative electrospray ionization tandem mass spectrometry: experimental and computational studies

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Design, synthesis and biological evaluation of new aryl thiosemicarbazone as antichagasic candidates

The present work reports on the synthesis, biological assaying and docking studies of a series of 12 aryl thiosemicarbazones, which were planned to act over two main enzymes, cruzain and trypanothione reductase. These enzymes are used as targets of trypanocidal activity in Chagas disease control with a minimal mutagenic profile. Three p-nitroaromatic thiosemicarbazones showed high activity against Trypanosoma cruzi in in vitro assays (IC50 < 57 μM), and no mutagenic profile was observed in micronucleous tests. Although the in vitro inhibition test showed that 10-μM doses of eight compounds inhibited cruzain activity, no correlation was found between cruzain inhibition and trypanocidal activity. © 2013 Elsevier Masson SAS. All rights reserved.

Design and Development of Geographical Information System (GIS) Map for Nuclear Waste Streams

A nuclear waste stream is the complete flow of waste material from origin to treatment facility to final disposal. The objective of this study was to design and develop a Geographic Information Systems (GIS) module using Google Application Programming Interface (API) for better visualization of nuclear waste streams that will identify and display various nuclear waste stream parameters. A proper display of parameters would enable managers at Department of Energy waste sites to visualize information for proper planning of waste transport. The study also developed an algorithm using quadratic Bézier curve to make the map more understandable and usable. Microsoft Visual Studio 2012 and Microsoft SQL Server 2012 were used for the implementation of the project. The study has shown that the combination of several technologies can successfully provide dynamic mapping functionality. Future work should explore various Google Maps API functionalities to further enhance the visualization of nuclear waste streams.

Transition metal complexes of some N4-phenylsemicarbazones: crystal structures and spectral studies

The work embodied in this thesis was carried out by the author in the Department of Applied Chemistry, CUSAT, Kochi, during the period 2009-2012. The thesis is an introduction to our attempts to evaluate the coordination behavior of some compounds of our interest. The biological activities of semicarbazones and their metal complexes have been an active area of research during the past years because of their significant role in naturally occurring biological systems. Tridentate NNO and ONO semicarbazone systems formed from heterocyclic and aromatic carbonyl compounds and their transition metal complexes are wellauthenticated compounds in this field and their synthesis, crystal structures and spectral studies are well desirable. Hence, we decided to develop a research program aimed at the syntheses, crystal structures and spectral studies of new N4- phenylsemicarbazones derived from 2-formylpyridine and 3-ethoxysalicylaldehyde and their transition metal complexes and new transition metal complexes of 2- benzoylpyridine-N4-phenylsemicarbazone. In addition to various physicochemical methods of analysis, single crystal X-ray diffraction studies were also used for the characterization of the complexes.

Thermal activation, long-range ordering, and topological frustration of artificial spin ice

Frustrated systems, typically characterized by competing interactions that cannot all be simultaneously satisfied, are ubiquitous in nature and display many rich phenomena and novel physics. Artificial spin ices (ASIs), arrays of lithographically patterned Ising-like single-domain magnetic nanostructures, are highly tunable systems that have proven to be a novel method for studying the effects of frustration and associated properties. The strength and nature of the frustrated interactions between individual magnets are readily tuned by design and the exact microstate of the system can be determined by a variety of characterization techniques. Recently, thermal activation of ASI systems has been demonstrated, introducing the spontaneous reversal of individual magnets and allowing for new explorations of novel phase transitions and phenomena using these systems. In this work, we introduce a new, robust material with favorable magnetic properties for studying thermally active ASI and use it to investigate a variety of ASI geometries. We reproduce previously reported perfect ground-state ordering in the square geometry and present studies of the kagome lattice showing the highest yet degree of ordering observed in this fully frustrated system. We consider theoretical predictions of long-range order in ASI and use both our experimental studies and kinetic Monte Carlo simulations to evaluate these predictions. Next, we introduce controlled topological defects into our square ASI samples and observe a new, extended frustration effect of the system. When we introduce a dislocation into the lattice, we still see large domains of ground-state order, but, in every sample, a domain wall containing higher energy spin arrangements originates from the dislocation, resolving a discontinuity in the ground-state order parameter. Locally, the magnets are unfrustrated, but frustration of the lattice persists due to its topology. We demonstrate the first direct imaging of spin configurations resulting from topological frustration in any system and make predictions on how dislocations could affect properties in numerous materials systems.