Preparation and characterization of multifunctional bio-based polymers exhibiting enhanced properties

Driven by environmental reasons and the expected depletion of crude oil, bio-based polymers are currently undergoing a renaissance in the attempt to replace fossil-based ones. The present work aims at contributing in the development of the steps that start from biomass and move to new polymeric multifunctional materials. The study focuses on two bio-based building blocks (itaconic and vanillic acids) characterized by exploitable functionalities, i.e. a lateral double bond and a substituted aromatic ring respectively, able to confer interesting properties to the final polymers. The lateral double bond of dimethyl itaconate was functionalized via thia-Michael addition reaction obtaining a thermo-stable building block that can undergo polycondensation under classical conditions of reaction. The addition of a long lateral chain allows the polymer to express antimicrobial activity against Staphylococcus aureus making it attractive for packaging and targeting antimicrobial applications. Moreover, the architecture of the homopolymer was modified by means of copolymerization with dimethyl 2,5-furandicarboxylate thus improving the rigidity and obtaining a thermo-processable material. Potential applications as thermoset or thermoplastic material have been discussed. As concerns vanillic acid, the presence of aromatic rings on the polymer backbone imparts high thermal stability, but brittle behaviour in the homopolymer. Therefore, the architecture of the polyester was successfully tuned by means of copolymerization with a flexible bio-based comonomer, i.e. ω-pentadecalactone, providing processable random copolymers. An in depth investigation of water transport mechanism has been undertaken on the synthesized polyesters. Since the copolymers present a succession of aromatic and aliphatic units, as a consequence of the chemical structure water vapor permeability interposes between polyethylene and poly(ethylene terephthalate) proving that the copolyesters are suitable for packaging applications. Moving towards a sustainable model of development, novel sustainable synthetic pathways for the eco-design of new bio-based polymeric structures with high value functionalities and different potential applications have been successfully developed.

Multi-functional electrocatalysts for CO2 reduction reaction: towards the modulation of selectivity

The electrocatalytic reduction of CO2 (CO2RR) is a captivating strategy for the conversion of CO2 into fuels, to realize a carbon neutral circular economy. In the recent years, research has focused on the development of new materials and technology capable of capturing and converting CO2 into useful products. The main problem of CO2RR is given by its poor selectivity, which can lead to the formation of numerous reaction products, to the detriment of efficiencies. For this reason, the design of new electrocatalysts that selectively and efficiently reduce CO2 is a fundamental step for the future exploitation of this technology. Here we present a new class of electrocatalysts, designed with a modular approach, namely, deriving from the combination of different building blocks in a single nanostructure. With this approach it is possible to obtain materials with an innovative design and new functionalities, where the interconnections between the various components are essential to obtain a highly selective and efficient reduction of CO2, thus opening up new possibilities in the design of optimized electrocatalytic materials. By combining the unique physic-chemical properties of carbon nanostructures (CNS) with nanocrystalline metal oxides (MO), we were able to modulate the selectivity of CO2RR, with the production of formic acid and syngas at low overpotentials. The CNS have not only the task of stabilizing the MO nanoparticles, but the creation of an optimal interface between two nanostructures is able to improve the catalytic activity of the active phase of the material. While the presence of oxygen atoms in the MO creates defects that accelerate the reaction kinetics and stabilize certain reaction intermediates, selecting the reaction pathway. Finally, a part was dedicated to the study of the experimental parameters influencing the CO2RR, with the aim of improving the experimental setup in order to obtain commercial catalytic performances.

Radio frequency communication and fault detection for railway signalling

The continuous and swift progression of both wireless and wired communication technologies in today's world owes its success to the foundational systems established earlier. These systems serve as the building blocks that enable the enhancement of services to cater to evolving requirements. Studying the vulnerabilities of previously designed systems and their current usage leads to the development of new communication technologies replacing the old ones such as GSM-R in the railway field. The current industrial research has a specific focus on finding an appropriate telecommunication solution for railway communications that will replace the GSM-R standard which will be switched off in the next years. Various standardization organizations are currently exploring and designing a radiofrequency technology based standard solution to serve railway communications in the form of FRMCS (Future Railway Mobile Communication System) to substitute the current GSM-R. Bearing on this topic, the primary strategic objective of the research is to assess the feasibility to leverage on the current public network technologies such as LTE to cater to mission and safety critical communication for low density lines. The research aims to identify the constraints, define a service level agreement with telecom operators, and establish the necessary implementations to make the system as reliable as possible over an open and public network, while considering safety and cybersecurity aspects. The LTE infrastructure would be utilized to transmit the vital data for the communication of a railway system and to gather and transmit all the field measurements to the control room for maintenance purposes. Given the significance of maintenance activities in the railway sector, the ongoing research includes the implementation of a machine learning algorithm to detect railway equipment faults, reducing time and human analysis errors due to the large volume of measurements from the field.

Development of machine learning methods for multi-modal biomarkers detection and integration

In medicine, innovation depends on a better knowledge of the human body mechanism, which represents a complex system of multi-scale constituents. Unraveling the complexity underneath diseases proves to be challenging. A deep understanding of the inner workings comes with dealing with many heterogeneous information. Exploring the molecular status and the organization of genes, proteins, metabolites provides insights on what is driving a disease, from aggressiveness to curability. Molecular constituents, however, are only the building blocks of the human body and cannot currently tell the whole story of diseases. This is why nowadays attention is growing towards the contemporary exploitation of multi-scale information. Holistic methods are then drawing interest to address the problem of integrating heterogeneous data. The heterogeneity may derive from the diversity across data types and from the diversity within diseases. Here, four studies conducted data integration using customly designed workflows that implement novel methods and views to tackle the heterogeneous characterization of diseases. The first study devoted to determine shared gene regulatory signatures for onco-hematology and it showed partial co-regulation across blood-related diseases. The second study focused on Acute Myeloid Leukemia and refined the unsupervised integration of genomic alterations, which turned out to better resemble clinical practice. In the third study, network integration for artherosclerosis demonstrated, as a proof of concept, the impact of network intelligibility when it comes to model heterogeneous data, which showed to accelerate the identification of new potential pharmaceutical targets. Lastly, the fourth study introduced a new method to integrate multiple data types in a unique latent heterogeneous-representation that facilitated the selection of important data types to predict the tumour stage of invasive ductal carcinoma. The results of these four studies laid the groundwork to ease the detection of new biomarkers ultimately beneficial to medical practice and to the ever-growing field of Personalized Medicine.

Modelling the influence of diradical character and aggregation on conjugated molecular materials

Molecular materials are made by the assembly of specifically designed molecules to obtain bulk structures with desired solid-state properties, enabling the development of materials with tunable chemical and physical properties. These properties result from the interplay of intra-molecular constituents and weak intermolecular interactions. Thus, small changes in individual molecular and electronic structure can substantially change the properties of the material in bulk. The purpose of this dissertation is, thus, to discuss and to contribute to the structure-property relationships governing the electronic, optical and charge transport properties of organic molecular materials through theoretical and computational studies. In particular, the main focus is on the interplay of intra-molecular properties and inter-molecular interactions in organic molecular materials. In my three-years of research activity, I have focused on three major areas: 1) the investigation of isolated-molecule properties for the class of conjugated chromophores displaying diradical character which are building blocks for promising functional materials; 2) the determination of intra- and intermolecular parameters governing charge transport in molecular materials and, 3) the development and application of diabatization procedures for the analysis of exciton states in molecular aggregates. The properties of diradicaloids are extensively studied both regarding their ground state (diradical character, aromatic vs quinoidal structures, spin dynamics, etc.) and the low-lying singlet excited states including the elusive double-exciton state. The efficiency of charge transport, for specific classes of organic semiconductors (including diradicaloids), is investigated by combining the effects of intra-molecular reorganization energy, inter-molecular electronic coupling and crystal packing. Finally, protocols aimed at unravelling the nature of exciton states are introduced and applied to different molecular aggregates. The role of intermolecular interactions and charge transfer contributions in determining the exciton state character and in modulating the H- to J- aggregation is also highlighted.

Hidden Schrödinger symmetry in FLRW and Bianchi I minisuperspace models of cosmology and black holes Schwarzschild dynamics

A broad sector of literature focuses on the relationship between fluid dynamics and gravitational systems. This thesis presents results that suggest the existence of a new kind of fluid/gravity duality not based on the holographic principle. The goal is to provide tools that allow us to systematically unearth hidden symmetries for reduced models of cosmology. The focus is on the field space of these models, i.e. the superspace. In fact, conformal isometries of the supermetric leave geodesics in the field space unaltered; this leads to symmetries of the models. An innovative aspect is the use of the Eisenhart-Duval’s lift. Using this method, systems constrained by a potential can be treated as free ones. Moreover, charges explicitly dependent on time, i.e. dynamical, can be found. A detailed analysis is carried out on three basic models of homogenous cosmology: i) flat Friedmann-Lemaître-Robertson-Walker’s isotropic universe filled with a massless scalar field; ii) Schwarzschild’s black hole mechanics and its extension to vacuum (A)dS gravity; iii) Bianchi’s anisotropic type I universe with a massless scalar field. The results show the presence of a hidden Schrödinger’s symmetry which, being intrinsic to both Navier-Stokes’ and Schrödinger’s equations, indicates a correspondence between cosmology and hydrodynamics. Furthermore, the central extension of this algebra explicitly relates two concepts. The first is the number of particles coming from the fluid picture; while the second is the ratio between the IR and UV cutoffs that weighs how much a theory has of “classical” over “quantum”. This suggests a spacetime that emerges from an underlying world which is described by quantum building blocks. These quanta statistically conspire to appear as gravitational phenomena from a macroscopic point of view.

The concrete engineer's handbook, a reference book dealing with cement, plain and reinforced concrete, building construction, architecture, concrete blocks, mill building, fireproof houses, etc.,

Mode of access: Internet.

Mechanical properties of adobe blocks used in building construction in Huambo Province - Angola

Despite significant advances in building technologies with the use of conventional construction materials (as concrete and steel), which significantly have driven the construction industry, earth construction have demonstrated its importance and relevance, as well as it has matched in an efficient and eco-friendly manner the social housing concerns. The diversity of earth construction techniques allowed this material to adapt to different climatic, cultural and social contexts until the present time. However, in Angola, the construction with earth is still associated with population fringes of weak economic resources, for which, given the impossibility of being able to acquire modern construction materials (steel, cement, brick, among others), they resort to the use of available natural materials. Furthermore, the lack of scientific and technical knowledge justifies the negative appreciation of traditional building techniques, and the derogatory way how are considered the earth constructions in Angolan territory. Given the country's current development status, and taking into account the environmental requirements and the real socio-economic sustainability of Angola, it is considered that one of the viable and adequate options, could be the recovering and upgrading of the ancestral techniques of earth construction. The purpose of this research is to develop the technical and scientific knowledge in order to improve and optimize these construction solutions, responding to the real problems of housing quality as well as to the current social, economic and environmental sustainability requirements. In this paper, a description of the physical and mechanical characteristics of the adobes typically used in the construction of traditional houses in some localities of Huambo, province in Angola, is carried out. The methodology was based on mechanical in-situ testing in adobe blocks manufactured with traditional procedures: i) tensile strength evaluated with the bending test and compressive strength test on earth blocks specimens; and, ii) durability and erodibility test by Geelong method adopting the New Zealand standard (NZS) procedures (4297: 1998; 4297: 1998 and 4297: 1999). The results allow the characterization of the materials used in the construction of raw earth in the Huambo region, contributing to the development of knowledge of these sustainable and traditional housing constructive solutions with a strong presence in Angola [1, 2]. This study is part of a larger project in the area of Earth Construction [3], which aims to produce knowledge which can stimulate the use of environmental friendly construction materials and contribute to develop constructive solutions with improved performance, durability, comfort, safety and sustainability.

(FAB07_002) From the 'Curry to the 'Weal: Aboriginal town camps and compounds of the back-blocks

My involvement with Aboriginal people began in 1972 in my final year of architecture, when a small group of students were asked to advise on some Aboriginal building projects in Mt Isa and Cloncurry. This led to my Doctoral research and grew into the Aboriginal Environments Research Centre now well established at the university of Queensland. Although the personnel of this Centre have completed over 140 field trips in the last 20 years, it is a set of data collected largely from the first ten field trips in 1972-76 that will be presented in this paper.

HLT Hilotec: self-building manual for sustainable housing

The future of the construction industry will require changes at many levels. One is the ability of companies to adapt to new challenges, converting needs to opportunities and simultaneously contributing to the solving of social and environmental problems. In the coming decades we will see a change in attitude in the industry, with a strong tendency to adopt natural and recycled materials, as well as bet on green technology and social innovation oriented to emerging countries. On the other hand, emerging countries have a high demand for housing construction on a large scale, but the current techniques in the developed countries for building requires a large amount of natural resources and skilled labor. This contextualization brings sustainability problems for the construction sector in emerging countries, often with scarce natural resources and with the construction sector underdeveloped. Through a cooperative action between the construction company Mota-Engil Engineering and the University of Minho in Portugal, a construction technology was developed based on the use of Compressed Earth Blocks as part of a social concept for innovative small houses, favoring the adoption of local and natural materials and with the main premise of being dedicated to self-construction. The HiLoTec project - Development of a Sustainable Self-Construction System for Developing Countries was based on this idea. One of the several results of this project is this construction manual. To Mota-Engil the project was a platform for incubation of knowledge about earth construction and to obtain a constructive solution validated technically and scientifically, suitable to be implemented in the markets where it operates. For the University of Minho the project was an opportunity to strengthen skills in research, laboratory and scientific development, through the development of engineering studies, architecture and sustainability, as well as supporting the doctoral scholarships and dissemination of scientific publications. May the knowledge of this project be of benefit, in the future, for the welfare of those who build a HiLoTec house.

Characterization of dry-stack interlocking compressed earth blocks

Earth has been a traditional building material to construct houses in Africa. One of the most common techniques is the use of sun dried or kiln fired adobe bricks with mud mortar. Fired bricks are the main cause for deforestation in countries like Malawi. Although this technique is low-cost, the bricks vary largely in shape, strength and durability. This leads to weak houses which suffer considerable damage during floods and seismic events. One solution is the use of dry-stack masonry with stabilized interlocking compressed earth blocks (ICEB). This technology has the potential of substituting the current bricks by a more sustainable kind of block. This study was made in the context of the HiLoTec project, which focuses on houses in rural areas of developing countries. For this study, Malawi was chosen for a case study. This paper presents the experimental results of tests made with dry-stack ICEBs. Soil samples from Malawi were taken and studied. Since the experimental campaign could not be carried out in Malawi, a homogenization process of Portuguese soil was made to produce ICEBs at the University of Minho, Portugal. Then, the compression and tensile strength of the materials was determined via small cylinder samples. Subsequently, the compression and flexural strength of units were determined. Finally, tests to determine the compressive strength of both prisms and masonry wallets and to determine the initial shear strength of the dry interfaces were carried out. This work provides valuable data for low-cost eco-efficient housing

Comportamento térmico de blocos de terra comprimida ativados alcalinamente

Dissertação de mestrado integrado em Engenharia Civil

Building Grounded Abstractions for Artificial Intelligence Programming

Most Artificial Intelligence (AI) work can be characterized as either ``high-level'' (e.g., logical, symbolic) or ``low-level'' (e.g., connectionist networks, behavior-based robotics). Each approach suffers from particular drawbacks. High-level AI uses abstractions that often have no relation to the way real, biological brains work. Low-level AI, on the other hand, tends to lack the powerful abstractions that are needed to express complex structures and relationships. I have tried to combine the best features of both approaches, by building a set of programming abstractions defined in terms of simple, biologically plausible components. At the ``ground level'', I define a primitive, perceptron-like computational unit. I then show how more abstract computational units may be implemented in terms of the primitive units, and show the utility of the abstract units in sample networks. The new units make it possible to build networks using concepts such as long-term memories, short-term memories, and frames. As a demonstration of these abstractions, I have implemented a simulator for ``creatures'' controlled by a network of abstract units. The creatures exist in a simple 2D world, and exhibit behaviors such as catching mobile prey and sorting colored blocks into matching boxes. This program demonstrates that it is possible to build systems that can interact effectively with a dynamic physical environment, yet use symbolic representations to control aspects of their behavior.

Multifunctional polyether architectures : versatile materials for surface attachment and functionalization

Chapter 1 of this thesis comprises a review of polyether polyamines, i.e., combinations of polyether scaffolds with polymers bearing multiple amino moieties. Focus is laid on controlled or living polymerization methods. Furthermore, fields in which the combination of cationic, complexing, and pH-sensitive properties of the polyamines and biocompatibility and water-solubility of polyethers promise enormous potential are presented. Applications include stimuli-responsive polymers with a lower critical solution temperature (LCST) and/or the ability to gel, preparation of shell cross-linked (SCL) micelles, gene transfection, and surface functionalization.rnIn Chapter 2, multiaminofunctional polyethers relying on the class of glycidyl amine comonomers for anionic ring-opening polymerization (AROP) are presented. In Chapter 2.1, N,N-diethyl glycidyl amine (DEGA) is introduced for copolymerization with ethylene oxide (EO). Copolymer microstructure is assessed using online 1H NMR kinetics, 13C NMR triad sequence analysis, and differential scanning calorimetry (DSC). The concurrent copolymerization of EO and DEGA is found to result in macromolecules with a gradient structure. The LCSTs of the resulting copolymers can be tailored by adjusting DEGA fraction or pH value of the environment. Quaternization of the amino moieties by methylation results in polyelectrolytes. Block copolymers are used for PEGylated gold nanoparticle formation. Chapter 2.2 deals with a glycidyl amine monomer with a removable protecting group at the amino moiety, for liberation of primary amines at the polyether backbone, which is N,N-diallyl glycidyl amine (DAGA). Its allyl groups are able to withstand the harsh basic conditions of AROP, but can be cleaved homogeneously after polymerization. Gradient as well as block copolymers poly(ethylene glycol)-PDAGA (PEG-PDAGA) are obtained. They are analyzed regarding their microstructure, LCST behavior, and cleavage of the protecting groups. rnChapter 3 describes applications of multi(amino)functional polyethers for functionalization of inorganic surfaces. In Chapter 3.1, they are combined with an acetal-protected catechol initiator, leading to well-defined PEG and heteromultifunctional PEG analogues. After deprotection, multifunctional PEG ligands capable of attaching to a variety of metal oxide surfaces are obtained. In a cooperative project with the Department of Inorganic and Analytical Chemistry, JGU Mainz, their potential is demonstrated on MnO nanoparticles, which are promising candidates as T1 contrast agents in magnetic resonance imaging. The MnO nanoparticles are solubilized in aqueous solution upon ligand exchange. In Chapter 3.2, a concept for passivation and functionalization of glass surfaces towards gold nanorods is developed. Quaternized mPEG-b-PqDEGA diblock copolymers are attached to negatively charged glass surfaces via the cationic PqDEGA blocks. The PEG blocks are able to suppress gold nanorod adsorption on the glass in the flow cell, analyzed by dark field microscopy.rnChapter 4 highlights a straightforward approach to poly(ethylene glycol) macrocycles. Starting from commercially available bishydroxy-PEG, cyclic polymers are available by perallylation and ring-closing metathesis in presence of Grubbs’ catalyst. Purification of cyclic PEG is carried out using α-cyclodextrin. This cyclic sugar derivative forms inclusion complexes with remaining unreacted linear PEG in aqueous solution. Simple filtration leads to pure macrocycles, as evidenced by SEC and MALDI-ToF mass spectrometry. Cyclic polymers from biocompatible precursors are interesting materials regarding their increased blood circulation time compared to their linear counterparts.rnIn the Appendix, A.1, a study of the temperature-dependent water-solubility of polyether copolymers is presented. Macroscopic cloud points, determined by turbidimetry, are compared with microscopic aggregation phenomena, monitored by continuous wave electron paramagnetic resonance (CW EPR) spectroscopy in presence of the amphiphilic spin probe and model drug (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO). These thermoresponsive polymers are promising candidates for molecular transport applications. The same techniques are applied in Chapter A.2 to explore the pH-dependence of the cloud points of PEG-PDEGA copolymers in further detail. It is shown that the introduction of amino moieties at the PEG backbone allows for precise manipulation of complex phase transition modes. In Chapter A.3, multi-hydroxyfunctional polysilanes are presented. They are obtained via copolymerization of the acetal-protected dichloro(isopropylidene glyceryl propyl ether)methylsilane monomer. The hydroxyl groups are liberated through acidic work-up, yielding versatile access to new multifunctional polysilanes.

Durabilidad de los bloques de tierra comprimida : Evaluación y recomendaciones para la normalización de los ensayos de erosión y absorción

La presente tesis continúa una línea de investigación iniciada en el 2006, centrada en el estudio de nuevas soluciones constructivas que toman la tierra cruda como base. Se pretende la difusión de los resultados obtenidos con el fin de fomentar estas técnicas constructivas, como por ejemplo, los sistemas de eco-construcción. El empleo de tierra cruda como sistema constructivo presenta grandes ventajas; entre ellas, un bajo impacto medioambiental, la capacidad de integración en el paisaje y un menor consumo energético. Con el fin de superar los inconvenientes que presenta el empleo de la tierra como elemento constructivo y afianzar su valor como posible material para la edificación, se estudian las propiedades de durabilidad de la misma y se dan pautas para una posible normativa futura. Se ha llevado a cabo un análisis exhaustivo de las normativas internacionales, estudiando los ensayos propuestos por los diferentes Organismos Internacionales de Normalización para caracterizar la durabilidad de los materiales de tierra. Ante la gran diversidad y heterogeneidad de las especificaciones encontradas en los ensayos que se aplican para un mismo fin, se han desarrollado dispositivos lo suficientemente versátiles para la ejecución de los ensayos propuestos. El conjunto de ensayos desarrollados en esta tesis, ha permitido elaborar una guía de recomendaciones para ensayos aplicados a materiales de tierra cruda. Además, se han estudiado las diferencias de comportamiento de los bloques de tierra comprimidos (BTC) fabricados en España, evaluando su viabilidad como material de construcción. Esta tesis ayuda a consolidar el papel de la tierra cruda en el panorama de edificación actual, solventando las dudas de los técnicos en cuanto a la durabilidad frente al agua y ausencia de normativa. Por tanto, las conclusiones sobre ensayos de durabilidad en materiales de tierra y las mejoras propuestas en algunos ensayos, sirven de referencia para la determinación de la durabilidad en los materiales basados en tierra cruda. De igual manera, es también un objetivo de la tesis que los resultados obtenidos aporten una visión general del estado normativo de los materiales a base de tierra cruda e información útil a aportar para la elaboración de documentos reconocidos sobre tierra en nuestro país, concretamente, apoyando la labor de normalización llevada a cabo en el subcomité de AENOR. This thesis continues a research line begun in 2006, focused on the study of new building solutions based on unbaked earth. With the aim to promote these construction techniques, it seeks the diffusion of the result obtained, for example eco-building systems. The use of unbaked earth as building system has great advantages such as low environmental impact, integrate ability into the landscape and lower energy consumption. In order to overcome the disadvantages of the use of earth as a building element and consolidate its value as possible building material, it is studied the properties of its durability and it is given guidelines for possible future standard. It has carried out an exhaustive analysis of international standards, studying the tests proposed by several International Organizations of Standards in order to characterize the durability of earth materials. Because of the great diversity and heterogeneity of the specifications found in the tests that are applied for the same purpose, we have developed devices versatile enough for the implementation of the proposed tests. The set of developed tests in this thesis has allowed developing a recommendation guideline for tests applied to unbaked earth materials. In addition, we have studied the differences of behavior of compressed earth blocks (CEB) manufactured in Spain, evaluating its viability as building material. This thesis helps to consolidate the role of unbaked earth in the scene of current building, solving the doubts of technicians about durability against rain and lack of standard. Therefore, the conclusions of durability tests in earth materials and the proposed improvements in some tests, serve as a reference for determining the durability of the materials based on raw earth. In the same way, it is also an objective of the thesis that the obtained results provide an overview of standards status of materials based on unbaked earth and useful information for the development documents recognized on earth in our country, supporting the standardization that is taking place at the subcommittee AENOR.