The combination of smart hydrogels and fibre optic sensor technology for analyte detection

The subject of investigation of the present research is the use of smart hydrogels with fibre optic sensor technology. The aim was to develop a costeffective sensor platform for the detection of water in hydrocarbon media, and of dissolved inorganic analytes, namely potassium, calcium and aluminium. The fibre optic sensors in this work depend upon the use of hydrogels to either entrap chemotropic agents or to respond to external environmental changes, by changing their inherent properties, such as refractive index (RI). A review of current fibre optic technology for sensing outlined that the main principles utilised are either the measurement of signal loss or a change in wavelength of the light transmitted through the system. The signal loss principle relies on changing the conditions required for total internal reflection to occur. Hydrogels are cross-linked polymer networks that swell but do not dissolve in aqueous environments. Smart hydrogels are synthetic materials that exhibit additional properties to those inherent in their structure. In order to control the non-inherent properties, the hydrogels were fabricated with the addition of chemotropic agents. For the detection of water, hydrogels of low refractive index were synthesized using fluorinated monomers. Sulfonated monomers were used for their extreme hydrophilicity as a means of water sensing through an RI change. To enhance the sensing capability of the hydrogel, chemotropic agents, such as pH indicators and cobalt salts, were used. The system comprises of the smart hydrogel coated onto an exposed section of the fibre optic core, connected to the interrogation system measuring the difference in the signal. Information obtained was analysed using a purpose designed software. The developed sensor platform showed that an increase in the target species caused an increase in the signal lost from the sensor system, allowing for a detection of the target species. The system has potential applications in areas such as clinical point of care, water detection in fuels and the detection of dissolved ions in the water industry.

Using overlay test to evaluate fracture properties of field-aged asphalt concrete

Field material testing provides firsthand information on pavement conditions which are most helpful in evaluating performance and identifying preventive maintenance or overlay strategies. High variability of field asphalt concrete due to construction raises the demand for accuracy of the test. Accordingly, the objective of this study is to propose a reliable and repeatable methodology to evaluate the fracture properties of field-aged asphalt concrete using the overlay test (OT). The OT is selected because of its efficiency and feasibility for asphalt field cores with diverse dimensions. The fracture properties refer to the Paris’ law parameters based on the pseudo J-integral (A and n) because of the sound physical significance of the pseudo J-integral with respect to characterizing the cracking process. In order to determine A and n, a two-step OT protocol is designed to characterize the undamaged and damaged behaviors of asphalt field cores. To ensure the accuracy of determined undamaged and fracture properties, a new analysis method is then developed for data processing, which combines the finite element simulations and mechanical analysis of viscoelastic force equilibrium and evolution of pseudo displacement work in the OT specimen. Finally, theoretical equations are derived to calculate A and n directly from the OT test data. The accuracy of the determined fracture properties is verified. The proposed methodology is applied to a total of 27 asphalt field cores obtained from a field project in Texas, including the control Hot Mix Asphalt (HMA) and two types of warm mix asphalt (WMA). The results demonstrate a high linear correlation between n and −log A for all the tested field cores. Investigations of the effect of field aging on the fracture properties confirm that n is a good indicator to quantify the cracking resistance of asphalt concrete. It is also indicated that summer climatic condition clearly accelerates the rate of aging. The impact of the WMA technologies on fracture properties of asphalt concrete is visualized by comparing the n-values. It shows that the Evotherm WMA technology slightly improves the cracking resistance, while the foaming WMA technology provides the comparable fracture properties with the HMA. After 15 months aging in the field, the cracking resistance does not exhibit significant difference between HMA and WMAs, which is confirmed by the observations of field distresses.

Development of Metal–Organic Frameworks for Catalysis : Designing Functional and Porous Crystals

Metal–organic frameworks, or MOFs, have emerged as a new class of porous materials made by linking metal and organic units. The easy preparation, structural and functional tunability, ultrahigh porosity, and enormous surface areas of MOFs have led to them becoming one of the fastest growing fields in chemistry. MOFs have potential applications in numerous areas such as clean energy, adsorption and separation processes, biomedicine, and sensing. One of the most promising areas of research with MOFs is heterogeneous catalysis. This thesis describes the design and synthesis of new, carboxylate-based MOFs for use as catalysts. These materials have been characterized using diffraction, spectroscopy, adsorption, and imaging techniques. The thesis has focused on preparing highly-stable MOFs for catalysis, using post-synthetic methods to modify the properties of these crystals, and applying a combination of characterization techniques to probe these complex materials. In the first part of this thesis, several new vanadium MOFs have been presented. The synthesis of MIL-88B(V), MIL-101(V), and MIL-47 were studied using ex situ techniques to gain insight into the synthesis–structure relationships. The properties of these materials have also been studied. In the second part, the use of MOFs as supports for metallic nanoparticles has been investigated. These materials, Pd@MIL-101–NH2(Cr) and Pd@MIL-88B–NH2(Cr), were used as catalysts for Suzuki–Miyaura and oxidation reactions, respectively. The effect of the base on the catalytic activity, crystallinity, porosity, and palladium distribution of Pd@MIL-101–NH2(Cr) was studied. In the final part, the introduction of transition-metal complexes into MOFs through different synthesis routes has been described. A ruthenium complex was grafted onto an aluminium MOF, MOF-253, and an iridium metallolinker was introduced into a zirconium MOF, UiO-68–2CH3. These materials were used as catalysts for alcohol oxidation and allylic alcohol isomerization, respectively.

Saccharomyces cerevisiae as a toxicological model to study synthetic cannabinoids and its pyrolysis products

Poster presented at the 7th European Academy of Forensic Science Conference. Prague, 6-11 September 2015

Evaluation of recycled carbon fibers as PLA reinforcement for additive manufacturing applications

The increased exploitation of carbon fiber reinforced polymers (CFRP) is inevitably bringing about an increase in production scraps and end-of-life components, resulting in a sharp increase in CFRP waste. Therefore, it is of paramount importance to find efficient ways to reintroduce waste into the manufacturing cycle. At present, several recycling methods for treating CFRPs are available, even if all of them still have to be optimized. The step after CFRP recycling, and also the key to build a solid and sustainable CFRP recycling market, is represented by the utilization of Re-CFs. The smartest way to utilize recovered carbon fibers is through the manufacturing of recycled CFRPs, that can be done by re-impregnating the recovered fibers with a new polymeric matrix. Fused Filament Fabrication (FFF) is one of the most widely used additive manufacturing (3D printing) techniques that fabricates parts with a polymeric filament deposition process that allows to produce parts adding material layer-by-layer, only where it is needed, saving energy, raw material cost, and waste. The filament can also contain fillers or reinforcements such as recycled short carbon fibers and this makes it perfectly compliant with the re-application of the shortened recycled CF. Therefore, in this thesis work recycled and virgin carbon fiber reinforced PLA filaments have been initially produced using 5% and 10% of CFs load. Properties and characteristics of the filaments have been determined conducting different analysis (TGA, DMA, DSC). Subsequently the 5%wt. Re-CFs filament has been used to 3D print specimens for mechanical characterization (DMA, tensile test and CTE), in order to evaluate properties of printed PLA composites containing Re-CFs and evaluate the feasibility of Re-CFs in 3D printing application.

Remote sensing the vertical profile of cloud droplet effective radius, thermodynamic phase, and temperature

Cloud-aerosol interaction is a key issue in the climate system, affecting the water cycle, the weather, and the total energy balance including the spatial and temporal distribution of latent heat release. Information on the vertical distribution of cloud droplet microphysics and thermodynamic phase as a function of temperature or height, can be correlated with details of the aerosol field to provide insight on how these particles are affecting cloud properties and their consequences to cloud lifetime, precipitation, water cycle, and general energy balance. Unfortunately, today's experimental methods still lack the observational tools that can characterize the true evolution of the cloud microphysical, spatial and temporal structure in the cloud droplet scale, and then link these characteristics to environmental factors and properties of the cloud condensation nuclei. Here we propose and demonstrate a new experimental approach (the cloud scanner instrument) that provides the microphysical information missed in current experiments and remote sensing options. Cloud scanner measurements can be performed from aircraft, ground, or satellite by scanning the side of the clouds from the base to the top, providing us with the unique opportunity of obtaining snapshots of the cloud droplet microphysical and thermodynamic states as a function of height and brightness temperature in clouds at several development stages. The brightness temperature profile of the cloud side can be directly associated with the thermodynamic phase of the droplets to provide information on the glaciation temperature as a function of different ambient conditions, aerosol concentration, and type. An aircraft prototype of the cloud scanner was built and flew in a field campaign in Brazil. The CLAIM-3D (3-Dimensional Cloud Aerosol Interaction Mission) satellite concept proposed here combines several techniques to simultaneously measure the vertical profile of cloud microphysics, thermodynamic phase, brightness temperature, and aerosol amount and type in the neighborhood of the clouds. The wide wavelength range, and the use of multi-angle polarization measurements proposed for this mission allow us to estimate the availability and characteristics of aerosol particles acting as cloud condensation nuclei, and their effects on the cloud microphysical structure. These results can provide unprecedented details on the response of cloud droplet microphysics to natural and anthropogenic aerosols in the size scale where the interaction really happens.

Care during freeze-drying of bovine pericardium tissue to be used as a biomaterial: A comparative study

Bovine pericardium (BP) tissue is widely used in the manufacture of bioprosthetics. The effects of freeze-drying on the BP tissue have been studied by some researchers in order to decrease their cytotoxicity due to preservation in formaldehyde solution, and to increase the lifetime of the product in storage. This study was undertaken in order to study the effect of freeze-drying in the structure of BP. To perform this study BP samples were freeze-dried in two different types of freeze-dryers available in our laboratory: a laboratory freeze-dryer, in which it was not possible to control parameters and a pilot freeze-dryer, wherein all parameters during freezing and drying were controlled. After freeze-drying processes, samples were analyzed by SEM, Raman spectroscopy, tensile strength, water uptake tests and TEM. In summary, it has been demonstrated that damages occur in collagen fibers by the loss of bulk water of collagen structure implicating in a drastic decreasing of BP mechanical properties due to its structural alterations. Moreover, it was proven that the collagen fibrils suffered breakage at some points, which can be attributed to the uncontrolled parameters during drying. (C) 2011 Elsevier Inc. All rights reserved.

Effect of fiber orientation in gelled poly (vinylience fluoride) electrospun membranes for Li-ion battery applications

Battery separators based on electrospun membranes of poly(vinylidene fluoride) (PVDF) have been prepared in order to study the effect of fiber alignment on the performance and characteristics of the membrane. The prepared membranes show an average fiber diameter of ~272 nm and a degree of porosity of ~87 %. The gel polymer electrolytes are prepared by soaking the membranes in the electrolyte solution. The alignment of the fibers improves the mechanical properties for the electrospun membranes. Further, the microstructure of the membrane also plays an important role in the ionic conductivity, being higher for the random electrospun membrane due to the lower tortuosity value. Independently of the microstructure, both membranes show good electrochemical stability up to 5.0 V versus Li/Li+. These results show that electrospun membranes based on PVDF are appropriate for battery separators in lithium-ion battery applications, the random membranes showing a better overall performance.

(Virtual) Agents for running electricity markets

This paper describes a multi-agent based simulation (MABS) framework to construct an artificial electric power market populated with learning agents. The artificial market, named TEMMAS (The Electricity Market Multi-Agent Simulator), explores the integration of two design constructs: (i) the specification of the environmental physical market properties and (ii) the specification of the decision-making (deliberative) and reactive agents. TEMMAS is materialized in an experimental setup involving distinct power generator companies that operate in the market and search for the trading strategies that best exploit their generating units' resources. The experimental results show a coherent market behavior that emerges from the overall simulated environment.

Linóleo como revestimento de piso: processos construtivos, execução e patologia

Dissertação para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização em Edificações

How to engage low category users through social media: The case of the make-up sector in Portugal

A Work Project, presented as part of the requirements for the Award of a Masters Degree in Management from the NOVA – School of Business and Economics

How to engage low category users through social media- The case of the make-up sector in Portugal

Purpose: This work project should be inevitably deemed as a practical approach to a marketing problem; “How to engage low category users through the social media – the case of the make-up sector in Portugal”. Design/methodology/approach: Online structured questionnaires and in-depth interviews were used. The questionnaire was answered by 110 women aged from 15 to 45 years old and the interviews were conducted with 14 women of the same age. The interviews provided key insights for the questionnaire formulation. Findings: Women are poorly informed on make-up properties and characteristics, feeling a genuine concern in regard to this subject. Lack of time, occasional usage and skin damage are the main barriers for make-up usage by low category users. Overcoming these aspects pass by demystifying the association of make-up with skin damage and emphasise the functional and emotional benefits of make-up. Further, brands need to create contents more consumer-oriented and ask directly to fans/followers suggestions and other insights. Resort to Portuguese “common” women for greater empathy in campaigns, promote online meetings between followers and make-up professionals on social media; and finally take advantage of the hybrid condition of Facebook, which incorporates multiple forms of content presentation, including videos, the most appealing format of make-up presentation for women. Research limitations/implications: Further studies addressing this topic, by using larger samples and study of specific make-up brands and campaign programs, over social media to reach a solid growth potential of make-up market evidences in Portugal. Originality/ value: Make-up brands are emphasising their interest in linking social media and marketing their promotional mix around social marketing.

Management of corn stalk waste as reinforcement for polypropylene injection moulded composites

The main objective of this study was the management of corn stalk waste as reinforcement for polypropylene (PP) injection moulded composites as an alternative to wood flour and fibers. In the first step, corn stalk waste was subjected to various treatments, and four different corn stalk derivatives (flour and fibers) able to be used as reinforcement of composite materials were prepared and characterized. These derivatives are corn stalk flour, thermo-mechanical, semi-chemical, and chemical fibers. They were characterized in terms of their yield, lignin content, Kappa number, fiber length/diameter ratio, fines, coarseness, viscosity, and the length at the break of a standard sheet of paper. Results showed that the corn stalk derivatives have different physico-chemical properties. In the second step, the prepared flour and fibers were explored as a reinforcing element for PP composites. Coupled and non-coupled PP composites were prepared and tested for tensile properties. For overall trend, with the addition of a coupling agent, tensile properties of composites significantly improved, as compared with non-coupled samples. In addition, a morphological study revealed the positive effect of the coupling agent on the interfacial bonding. The composites prepared with semichemical fiber gave better results in comparison with the rest of the corn stalk derivatives due to its chemical characteristics

Twitch and M-wave potentiation induced by intermittent maximal voluntary quadriceps contractions: Differences between direct quadriceps and femoral nerve stimulation.

Introduction: To investigate differences in twitch and M-wave potentiation in the quadriceps femoris when electrical stimulation is applied over the quadriceps muscle belly versus the femoral nerve trunk. Methods: M-waves and mechanical twitches were evoked using direct quadriceps muscle and femoral nerve stimulation between 48 successive isometric maximal voluntary contractions (MVC) from 10 young, healthy subjects. Potentiation was investigated by analyzing the changes in M-wave amplitude recorded from the vastus medialis (VM) and vastus lateralis (VL) muscles and in quadriceps peak twitch force. Results: Potentiation of twitch, VM M-wave, and VL M-wave were greater for femoral nerve than for direct quadriceps stimulation (P<0.05). Despite a 50% decrease in MVC force, the amplitude of the M-waves increased significantly during exercise. Conclusions: In addition to enhanced electrogenic Na(+) -K(+) pumping, other factors (such as synchronization in activation of muscle fibers and muscle architectural properties) might significantly influence the magnitude of M-wave enlargement. © 2013 Wiley Periodicals, Inc.

Consommation de cannabis : quels sont les risques ?

Abstract - Cannabis: what are the risks ? Cannabinoids from cannabis have a dual use and display often opposite pharmacological properties depending on the circumstances of use and the administered dose. Cannabinoids constitute mainly a recreative or addictive substance, but also a therapeutic drug. They can be either neurotoxic or neuroprotector, carcinogenic or an anti-cancer drug, hyperemetic or antiemetic, pro-inflammatory or anti-inflammatory... Improvement in in-door cultivation techniques and selection of high yield strains have resulted in a steadily increase of THC content. Cannabis is the most frequently prohibited drug used in Switzerland and Western countries. About half of teenagers have already experimented cannabis consumption. About 10% of cannabis users smoke it daily and can be considered as cannabis-dependant. About one third of these cannabis smokers are chronically intoxicated. THC, the main psychoactive drug interacts with the endocannnabinoid system which is made of cellular receptors, endogenous ligands and a complex intra-cellular biosynthetic, degradation and intra-cellular messengers machinery. The endocannabinoid system plays a major role in the fine tuning of the nervous system. It is thought to be important in memory, motor learning, and synaptic plasticity. At psychoactive dose, THC impairs psychomotor and neurocognitive performances. Learning and memory abilities are diminished. The risk to be responsible of a traffic car accident is slightly increased after administration of cannabis alone and strongly increased after combined use of alcohol and cannabis. With the exception of young children, cannabis intake does not lead to potentially fatal intoxication. However, cannabis exposure can act as trigger for cardiovascular accidents in rare vulnerable people. Young or vulnerable people are more at risk to develop a psychosis at adulthood and/or to become cannabis-dependant. Epidemiological studies have shown that the risk to develop a schizophrenia at adulthood is increased for cannabis smokers, especially for those who are early consumers. Likewise for the risk of depression and suicide attempt. Respiratory disease can be worsen after cannabis smoking. Pregnant and breast-feeding mothers should not take cannabis because THC gets into placenta and concentrates in breast milk. The most sensitive time-period to adverse side-effects of cannabis starts from foetus and extends to adolescence. The reason could be that the endocannabinoid system, the main target of THC, plays a major role in the setup of neuronal networks in the immature brain. The concomitant use of other psychoactive drugs such as alcohol, benzodiazepines or cocaine should be avoided because of possible mutual interactions. Furthermore, it has been demonstrated that a cross-sensitisation exists between most addictive drugs at the level of the brain reward system. Chronic use of cannabis leads to tolerance and withdrawals symptoms in case of cannabis intake interruption. Apart from the aforementioned unwanted side effects, cannabis displays useful and original medicinal properties which are currently under scientific evaluation. At the moment the benefit/risk ratio is not yet well assessed. Several minor phytocannabinoids or synthetic cannabinoids devoid of psychoactive properties could find their way in the modern pharmacopoeia (e.g. ajulemic acid). For therapeutic purposes, special cannabis varieties with unique cannabinoids composition (e.g. a high cannabidiol content) are preferred over those which are currently used for recreative smoking. The administration mode also differs in such a way that inhalation of carcinogenic pyrolytic compounds resulting from cannabis smoking is avoided. This can be achieved by inhaling cannabis vapors at low temperature with a vaporizer device. Résumé Les cannabinoïdes contenus dans la plante de cannabis ont un double usage et possèdent des propriétés opposées suivant les circonstances et les doses employées. Les cannabinoïdes, essentiellement drogue récréative ou d'abus pourraient, pour certains d'entre eux, devenir des médicaments. Selon les conditions d'utilisation, ils peuvent être neurotoxiques ou neuroprotecteurs, carcinogènes ou anticancéreux, hyper-émétiques ou antiémétiques, pro-inflammatoires ou anti-inflammatoires... Les techniques de culture sous serre indoor ainsi que la sélection de variétés de cannabis à fort potentiel de production ont conduit à un accroissement notable des taux de THC. Le cannabis est la drogue illégale la plus fréquemment consommée en Suisse et ailleurs dans le monde occidental. Environ la moitié des jeunes ont déjà expérimenté le cannabis. Environ 10 % des consommateurs le fument quotidiennement et en sont devenus dépendants. Un tiers de ces usagers peut être considéré comme chroniquement intoxiqué. Le THC, la principale substance psychoactive du cannabis, interagit avec le "système endocannabinoïde". Ce système est composé de récepteurs cellulaires, de ligands endogènes et d'un dispositif complexe de synthèse, de dégradation, de régulation et de messagers intra-cellulaires. Le système endocannabinoïde joue un rôle clé dans le réglage fin du système nerveux. Les endocannabinoïdes régulent la mémorisation, l'apprentissage moteur et la plasticité des liaisons nerveuses. À dose psychoactive, le THC réduit les performances psychomotrices et neurocognitives. Les facultés d'apprentissage et de mémorisation sont diminuées. Le risque d'être responsable d'un accident de circulation est augmenté après prise de cannabis, et ceci d'autant plus que de l'alcool aura été consommé parallèlement. À l'exception des jeunes enfants, la consommation de cannabis n'entraîne pas de risque potentiel d'intoxication mortelle. Toutefois, le cannabis pourrait agir comme facteur déclenchant d'accident cardiovasculaire chez de rares individus prédisposés. Les individus jeunes, et/ou vulnérables ont un risque significativement plus élevé de développer une psychose à l'âge adulte ou de devenir dépendant au cannabis. Des études épidémiologiques ont montré que le risque de développer une schizophrénie à l'âge adulte était augmenté pour les consommateurs de cannabis et ceci d'autant plus que l'âge de début de consommation était précoce. Il en va de même pour le risque de dépression. Les troubles respiratoires pourraient être exacerbés par la prise de cannabis. Les femmes enceintes et celles qui allaitent ne devraient pas consommer de cannabis car le THC traverse la barrière hémato-placentaire, en outre, il se concentre dans le lait maternel. La période de la vie la plus sensible aux effets néfastes du cannabis correspond à celle allant du foetus à l'adolescent. Le système endocannabinoïde sur lequel agit le THC serait en effet un acteur majeur orchestrant le développement des réseaux neuronaux dans le cerveau immature. La prise concomitante d'autres psychotropes comme l'alcool, les benzodiazépines ou la cocaïne conduit à des renforcements mutuels de leurs effets délétères. De plus, il a été montré l'existence d'une sensibilité croisée pour la majorité des psychotropes qui agissent sur le système de la récompense, le cannabis y compris, ce qui augmente ainsi le risque de pharmacodépendance. La prise régulière de doses élevées de cannabis entraîne l'apparition d'une tolérance et de symptômes de sevrage discrets à l'arrêt de la consommation. À part les effets négatifs mentionnés auparavant, le cannabis possède des propriétés médicales originales qui sont l'objet d'études attentives. Plusieurs cannabinoïdes mineurs naturels ou synthétiques, comme l'acide ajulémique, pourraient trouver un jour une place dans la pharmacopée. En usage thérapeutique, des variétés particulières de cannabis sont préférées, par exemple celles riches en cannabidiol non psychoactif. Le mode d'administration diffère de celui utilisé en mode récréatif. Par exemple, la vaporisation des cannabinoïdes à basse température est préférée à l'inhalation du "joint".