Tailoring, synthesis and structure-property relationships of 2,3-thienoimide based molecular materials

Organic molecular semiconductors are subject of intense research for their crucial role as key components of new generation low cost, flexible, and large area electronic devices such as displays, thin-film transistors, solar cells, sensors and logic circuits. In particular, small molecular thienoimide (TI) based materials are emerging as novel multifunctional materials combining a good processability together to ambipolar or n-type charge transport and electroluminescence at the solid state, thus enabling the fabrication of integrated devices like organic field effect transistors (OFETs) and light emitting transistor (OLETs). Given this peculiar combination of characteristics, they also constitute the ideal substrates for fundamental studies on the structure-property relationships in multifunctional molecular systems. In this scenario, this thesis work is focused on the synthesis of new thienoimide based materials with tunable optical, packing, morphology, charge transport and electroluminescence properties by following a fine molecular tailoring, thus optimizing their performances in device as well as investigating and enabling new applications. Investigation on their structure-property relationships has been carried out and in particular, the effect of different π-conjugated cores (heterocycles, length) and alkyl end chain (shape, length) changes have been studied, obtaining materials with enhanced electron transport capability end electroluminescence suitable for the realization of OFETs and single layer OLETs. Moreover, control on the polymorphic behaviour characterizing thienoimide materials has been reached by synthetic and post-synthetic methodologies, developing multifunctional materials from a single polymorphic compound. Finally, with the aim of synthesizing highly pure materials, simplifying the purification steps and avoiding organometallic residues, procedures based on direct arylation reactions replacing conventional cross-couplings have been investigated and applied to different classes of molecules, bearing thienoimidic core or ends, as well as thiophene and anthracene derivatives, validating this approach as a clean alternative for the synthesis of several molecular materials.

Modular extensions for modular (Logic) languages

We address the problem of developing mechanisms for easily implementing modular extensions to modular (logic) languages. By(language) extensions we refer to different groups of syntactic definitions and translation rules that extend a language. Our use of the concept of modularity in this context is twofold. We would like these extensions to be modular, in the sense above, i.e., we should be able to develop different extensions mostly separately. At the same time, the sources and targets for the extensions are modular languages, i.e., such extensions may take as input sepárate pieces of code and also produce sepárate pieces of code. Dealing with this double requirement involves interesting challenges to ensure that modularity is not broken: first, combinations of extensions (as if they were a single extensión) must be given a precise meaning. Also, the sepárate translation of múltiple sources (as if they were a single source) must be feasible. We present a detailed description of a code expansion-based framework that proposes novel solutions for these problems. We argüe that the approach, while implemented for Ciao, can be adapted for other Prolog-based systems and languages.

Determinacy analysis for logic programs using mode and type information

We propose an analysis for detecting procedures and goals that are deterministic (i.e. that produce at most one solution), or predicates whose clause tests are mutually exclusive (which implies that at most one of their clauses will succeed) even if they are not deterministic (because they cali other predicates that can produce more than one solution). Applications of such determinacy information include detecting programming errors, performing certain high-level program transformations for improving search efñciency, optimizing low level code generation and parallel execution, and estimating tighter upper bounds on the computational costs of goals and data sizes, which can be used for program debugging, resource consumption and granularity control, etc. We have implemented the analysis and integrated it in the CiaoPP system, which also infers automatically the mode and type information that our analysis takes as input. Experiments performed on this implementation show that the analysis is fairly accurate and efncient.

Combined static and dynamic assertion-based debugging of constraint logic programs

We propose a general framework for assertion-based debugging of constraint logic programs. Assertions are linguistic constructions for expressing properties of programs. We define several assertion schemas for writing (partial) specifications for constraint logic programs using quite general properties, including user-defined programs. The framework is aimed at detecting deviations of the program behavior (symptoms) with respect to the given assertions, either at compile-time (i.e., statically) or run-time (i.e., dynamically). We provide techniques for using information from global analysis both to detect at compile-time assertions which do not hold in at least one of the possible executions (i.e., static symptoms) and assertions which hold for all possible executions (i.e., statically proved assertions). We also provide program transformations which introduce tests in the program for checking at run-time those assertions whose status cannot be determined at compile-time. Both the static and the dynamic checking are provably safe in the sense that all errors flagged are definite violations of the pecifications. Finally, we report briefly on the currently implemented instances of the generic framework.

Simultaneous environmental and economic process synthesis of Isobutane Alkylation

This multidisciplinary study concerns the optimal design of processes with a view to both maximizing profit and minimizing environmental impacts. This can be achieved by a combination of traditional chemical process design methods, measurements of environmental impacts and advanced mathematical optimization techniques. More to the point, this paper presents a hybrid simulation-multiobjective optimization approach that at once optimizes the production cost and minimizes the associated environmental impacts of isobutane alkylation. This approach has also made it possible to obtain the flowsheet configurations and process variables that are needed to manufacture isooctane in a way that satisfies the above-stated double aim. The problem is formulated as a Generalized Disjunctive Programming problem and solved using state-of-the-art logic-based algorithms. It is shown, starting from existing alternatives for the process, that it is possible to systematically generate a superstructure that includes alternatives not previously considered. The optimal solution, in the form a Pareto curve, includes different structural alternatives from which the most suitable design can be selected. To evaluate the environmental impact, Life Cycle Assessment based on two different indicators is employed: Ecoindicator 99 and Global Warming Potential.

Isobutane Alkylation Process Synthesis by means of Hybrid Simulation-Multiobjective Optimization

Multiobjective Generalized Disjunctive Programming (MO-GDP) optimization has been used for the synthesis of an important industrial process, isobutane alkylation. The two objective functions to be simultaneously optimized are the environmental impact, determined by means of LCA (Life Cycle Assessment), and the economic potential of the process. The main reason for including the minimization of the environmental impact in the optimization process is the widespread environmental concern by the general public. For the resolution of the problem we employed a hybrid simulation- optimization methodology, i.e., the superstructure of the process was developed directly in a chemical process simulator connected to a state of the art optimizer. The model was formulated as a GDP and solved using a logic algorithm that avoids the reformulation as MINLP -Mixed Integer Non Linear Programming-. Our research gave us Pareto curves compounded by three different configurations where the LCA has been assessed by two different parameters: global warming potential and ecoindicator-99.

An approach to the general synthesis of a threshold element network.

Vita.

Results of the synthesis of optimal networks of AND and OR gates for four-variable switching functions by a branch-and-bound computer program /

Bibliography: p. 39 (2d group)

Ueber geschichtliche Analysis und Synthesis. Auf Veranlassung der Schubartschen Abhandlung über die Hauptrichtungen des menschlichen Geistes.

Mode of access: Internet.

Expert systems for fault tree synthesis

Hazard and operability (HAZOP) studies on chemical process plants are very time consuming, and often tedious, tasks. The requirement for HAZOP studies is that a team of experts systematically analyse every conceivable process deviation, identifying possible causes and any hazards that may result. The systematic nature of the task, and the fact that some team members may be unoccupied for much of the time, can lead to tedium, which in turn may lead to serious errors or omissions. An aid to HAZOP are fault trees, which present the system failure logic graphically such that the study team can readily assimilate their findings. Fault trees are also useful to the identification of design weaknesses, and may additionally be used to estimate the likelihood of hazardous events occurring. The one drawback of fault trees is that they are difficult to generate by hand. This is because of the sheer size and complexity of modern process plants. The work in this thesis proposed a computer-based method to aid the development of fault trees for chemical process plants. The aim is to produce concise, structured fault trees that are easy for analysts to understand. Standard plant input-output equation models for major process units are modified such that they include ancillary units and pipework. This results in a reduction in the nodes required to represent a plant. Control loops and protective systems are modelled as operators which act on process variables. This modelling maintains the functionality of loops, making fault tree generation easier and improving the structure of the fault trees produced. A method, called event ordering, is proposed which allows the magnitude of deviations of controlled or measured variables to be defined in terms of the control loops and protective systems with which they are associated.

A modular holistic approach to prosody modelling for Standard Yorùbá speech synthesis

This paper presents a novel prosody model in the context of computer text-to-speech synthesis applications for tone languages. We have demonstrated its applicability using the Standard Yorùbá (SY) language. Our approach is motivated by the theory that abstract and realised forms of various prosody dimensions should be modelled within a modular and unified framework [Coleman, J.S., 1994. Polysyllabic words in the YorkTalk synthesis system. In: Keating, P.A. (Ed.), Phonological Structure and Forms: Papers in Laboratory Phonology III, Cambridge University Press, Cambridge, pp. 293–324]. We have implemented this framework using the Relational Tree (R-Tree) technique. R-Tree is a sophisticated data structure for representing a multi-dimensional waveform in the form of a tree. The underlying assumption of this research is that it is possible to develop a practical prosody model by using appropriate computational tools and techniques which combine acoustic data with an encoding of the phonological and phonetic knowledge provided by experts. To implement the intonation dimension, fuzzy logic based rules were developed using speech data from native speakers of Yorùbá. The Fuzzy Decision Tree (FDT) and the Classification and Regression Tree (CART) techniques were tested in modelling the duration dimension. For practical reasons, we have selected the FDT for implementing the duration dimension of our prosody model. To establish the effectiveness of our prosody model, we have also developed a Stem-ML prosody model for SY. We have performed both quantitative and qualitative evaluations on our implemented prosody models. The results suggest that, although the R-Tree model does not predict the numerical speech prosody data as accurately as the Stem-ML model, it produces synthetic speech prosody with better intelligibility and naturalness. The R-Tree model is particularly suitable for speech prosody modelling for languages with limited language resources and expertise, e.g. African languages. Furthermore, the R-Tree model is easy to implement, interpret and analyse.

Intonation contour realisation for Standard Yorùbá text-to-speech synthesis:a fuzzy computational approach

This paper presents a novel intonation modelling approach and demonstrates its applicability using the Standard Yorùbá language. Our approach is motivated by the theory that abstract and realised forms of intonation and other dimensions of prosody should be modelled within a modular and unified framework. In our model, this framework is implemented using the Relational Tree (R-Tree) technique. The R-Tree is a sophisticated data structure for representing a multi-dimensional waveform in the form of a tree. Our R-Tree for an utterance is generated in two steps. First, the abstract structure of the waveform, called the Skeletal Tree (S-Tree), is generated using tone phonological rules for the target language. Second, the numerical values of the perceptually significant peaks and valleys on the S-Tree are computed using a fuzzy logic based model. The resulting points are then joined by applying interpolation techniques. The actual intonation contour is synthesised by Pitch Synchronous Overlap Technique (PSOLA) using the Praat software. We performed both quantitative and qualitative evaluations of our model. The preliminary results suggest that, although the model does not predict the numerical speech data as accurately as contemporary data-driven approaches, it produces synthetic speech with comparable intelligibility and naturalness. Furthermore, our model is easy to implement, interpret and adapt to other tone languages.

A computational model of intonation for yorùbá text-to-speech synthesis:design and analysis

In this paper we present the design and analysis of an intonation model for text-to-speech (TTS) synthesis applications using a combination of Relational Tree (RT) and Fuzzy Logic (FL) technologies. The model is demonstrated using the Standard Yorùbá (SY) language. In the proposed intonation model, phonological information extracted from text is converted into an RT. RT is a sophisticated data structure that represents the peaks and valleys as well as the spatial structure of a waveform symbolically in the form of trees. An initial approximation to the RT, called Skeletal Tree (ST), is first generated algorithmically. The exact numerical values of the peaks and valleys on the ST is then computed using FL. Quantitative analysis of the result gives RMSE of 0.56 and 0.71 for peak and valley respectively. Mean Opinion Scores (MOS) of 9.5 and 6.8, on a scale of 1 - -10, was obtained for intelligibility and naturalness respectively.

Synthesis Methods of Multiple-valued Structures of Language Systems

The basic construction concepts of many-valued intellectual systems, which are adequate to primal problems of person activity and using hybrid tools with many-valued of coding are considered. The many-valued intellectual systems being two-place, but simulating neuron processes of space toting which are different on a level of actions, inertial and threshold of properties of neurons diaphragms, and also modification of frequency of following of the transmitted messages are created. All enumerated properties and functions in point of fact are essential not only are discrete on time, but also many-valued.