Application of NMR RDC’s, relaxation and self-diffusion for the study of dynamic processes of small molecules in solution

Spin-lattice Relaxation, self-Diffusion coefficients and Residual Dipolar Couplings (RDC’s) are the basis of well established Nuclear Magnetic Resonance techniques for the physicochemical study of small molecules (typically organic compounds and natural products with MW < 1000 Da), as they proved to be a powerful and complementary source of information about structural dynamic processes in solution. The work developed in this thesis consists in the application of the earlier-mentioned NMR techniques to explore, analyze and systematize patterns of the molecular dynamic behavior of selected small molecules in particular experimental conditions. Two systems were chosen to investigate molecular dynamic behavior by these techniques: the dynamics of ion-pair formation and ion interaction in ionic liquids (IL) and the dynamics of molecular reorientation when molecules are placed in oriented phases (alignment media). The application of NMR spin-lattice relaxation and self-diffusion measurements was applied to study the rotational and translational molecular dynamics of the IL: 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4]. The study of the cation-anion dynamics in neat and IL-water mixtures was systematically investigated by a combination of multinuclear NMR relaxation techniques with diffusion data (using by H1, C13 and F19 NMR spectroscopy). Spin-lattice relaxation time (T1), self-diffusion coefficients and nuclear Overhauser effect experiments were combined to determine the conditions that favor the formation of long lived [BMIM][BF4] ion-pairs in water. For this purpose and using the self-diffusion coefficients of cation and anion as a probe, different IL-water compositions were screened (from neat IL to infinite dilution) to find the conditions where both cation and anion present equal diffusion coefficients (8% water fraction at 25 ºC). This condition as well as the neat IL and the infinite dilution were then further studied by 13C NMR relaxation in order to determine correlation times (c) for the molecular reorientational motion using a mathematical iterative procedure and experimental data obtained in a temperature range between 273 and 353 K. The behavior of self-diffusion and relaxation data obtained in our experiments point at the combining parameters of molar fraction 8 % and temperature 298 K as the most favorable condition for the formation of long lived ion-pairs. When molecules are subjected to soft anisotropic motion by being placed in some special media, Residual Dipolar Couplings (RDCs), can be measured, because of the partial alignment induced by this media. RDCs are emerging as a powerful routine tool employed in conformational analysis, as it complements and even outperforms the approaches based on the classical NMR NOE or J3 couplings. In this work, three different alignment media have been characterized and evaluated in terms of integrity using 2H and 1H 1D-NMR spectroscopy, namely the stretched and compressed gel PMMA, and the lyotropic liquid crystals CpCl/n-hexanol/brine and cromolyn/water. The influence that different media and degrees of alignment have on the dynamic properties of several molecules was explored. Different sized sugars were used and their self-diffusion was determined as well as conformation features using RDCs. The results obtained indicate that no influence is felt by the small molecules diffusion and conformational features studied within the alignment degree range studied, which was the 3, 5 and 6 % CpCl/n-hexanol/brine for diffusion, and 5 and 7.5 % CpCl/n-hexanol/brine for conformation. It was also possible to determine that the small molecules diffusion verified in the alignment media presented close values to the ones observed in water, reinforcing the idea of no conditioning of molecular properties in such media.

Thermal performance of cool facades: evaluation by Infrared Thermography

High reflective paints (cool paints) are used on flat roofs to reduce heat gains from the incidence of solar radiation and thus improve the thermal comfort and energy efficiency of buildings, especially in summer periods. Given the application potential of these paints on vertical surfaces, a research study has been developed to evaluate the thermal performance of reflective paints on walls under real exposure conditions. Accordingly, different reflective paints have been applied as the final coating of an ETICS type solution, on the facades of a full scale experimental cell built at LNEC campus. For being applied in an ETICS system a paint has to fulfill several requirements, whether aesthetic or functional (such as the adhesion between the coating layers or the durability of the insulation), essential for its efficient performance. Since this construction coating system is subject to a prolonged sun exposure, various problems may arise, such as paint degradation or deterioration of the thermal insulation properties, particularly when dark colors are applied. To evaluate the thermal performance of the chosen paints, the method of non-destructive analysis by Infrared Thermography was used. Thermography allows knowing the temperature distribution of facades by measuring the radiation emitted by their surfaces. To complement the thermographic diagnosis, thermocouples were placed between the insulation and the paint system of the experimental cell. Additional laboratory tests allowed the characterization of the optical properties (reflectance and emittance) of the different reflective paints used in this study. The comparative analysis of the thermal performance of reflective and conventional paints revealed that the reflective paint allows a reduction of the facade surface temperature, reducing the risk of loss of insulating properties of the ETICS system and thus ensuring its longevity and functionality. The color of the paint used affects, naturally, the reflective ability of the surface and may have an important role in energy balance of the building. This paper also showed the potential of infrared thermography in the evaluation of the thermal performance of reflective paints.

Numerical prediction of diffusion and electric field-induced iron nanoparticle transport

Zero valent iron nanoparticles (nZVI) are considered very promising for the remediation of contaminated soils and groundwaters. However, an important issue related to their limited mobility remains unsolved. Direct current can be used to enhance the nanoparticles transport, based on the same principles of electrokinetic remediation. In this work, a generalized physicochemical model was developed and solved numerically to describe the nZVI transport through porous media under electric field, and with different electrolytes (with different ionic strengths). The model consists of the Nernst–Planck coupled system of equations, which accounts for the mass balance of ionic species in a fluid medium, when both the diffusion and electromigration of the ions are considered. The diffusion and electrophoretic transport of the negatively charged nZVI particles were also considered in the system. The contribution of electroosmotic flow to the overall mass transport was included in the model for all cases. The nZVI effective mobility values in the porous medium are very low (10−7–10−4 cm2 V−1 s−1), due to the counterbalance between the positive electroosmotic flow and the electrophoretic transport of the negatively charged nanoparticles. The higher the nZVI concentration is in the matrix, the higher the aggregation; therefore, low concentration of nZVI suspensions must be used for successful field application.

Correlation between microdilution, Etest, and disk diffusion methods for antifungal susceptibility testing of fluconazole against Candida sp. blood isolates

INTRODUCTION: Antifungal susceptibility testing assists in finding the appropriate treatment for fungal infections, which are increasingly common. However, such testing is not very widespread. There are several existing methods, and the correlation between such methods was evaluated in this study. METHODS: The susceptibility to fluconazole of 35 strains of Candida sp. isolated from blood cultures was evaluated by the following methods: microdilution, Etest, and disk diffusion. RESULTS: The correlation between the methods was around 90%. CONCLUSIONS: The disk diffusion test exhibited a good correlation and can be used in laboratory routines to detect strains of Candida sp. that are resistant to fluconazole.

The thermal effects on the methanol-to-olefins reaction: A modelling and experimental approach

With the projection of an increasing world population, hand-in-hand with a journey towards a bigger number of developed countries, further demand on basic chemical building blocks, as ethylene and propylene, has to be properly addressed in the next decades. The methanol-to-olefins (MTO) is an interesting reaction to produce those alkenes using coal, gas or alternative sources, like biomass, through syngas as a source for the production of methanol. This technology has been widely applied since 1985 and most of the processes are making use of zeolites as catalysts, particularly ZSM-5. Although its selectivity is not especially biased over light olefins, it resists to a quick deactivation by coke deposition, making it quite attractive when it comes to industrial environments; nevertheless, this is a highly exothermic reaction, which is hard to control and to anticipate problems, such as temperature runaways or hot-spots, inside the catalytic bed. The main focus of this project is to study those temperature effects, by addressing both experimental, where the catalytic performance and the temperature profiles are studied, and modelling fronts, which consists in a five step strategy to predict the weight fractions and activity. The mind-set of catalytic testing is present in all the developed assays. It was verified that the selectivity towards light olefins increases with temperature, although this also leads to a much faster catalyst deactivation. To oppose this effect, experiments were carried using a diluted bed, having been able to increase the catalyst lifetime between 32% and 47%. Additionally, experiments with three thermocouples placed inside the catalytic bed were performed, analysing the deactivation wave and the peaks of temperature throughout the bed. Regeneration was done between consecutive runs and it was concluded that this action can be a powerful means to increase the catalyst lifetime, maintaining a constant selectivity towards light olefins, by losing acid strength in a steam stabilised zeolitic structure. On the other hand, developments on the other approach lead to the construction of a raw basic model, able to predict weight fractions, that should be tuned to be a tool for deactivation and temperature profiles prediction.

Structural connectivity based on diffusion Kurtosis imaging

Structural connectivity models based on Diffusion Tensor Imaging (DTI) are strongly affected by the technique’s inability to resolve crossing fibres, either intra- or inter-hemispherical connections. Several models have been proposed to address this issue, including an algorithm aiming to resolve crossing fibres which is based on Diffusion Kurtosis Imaging (DKI). This technique is clinically feasible, even when multi-band acquisitions are not available, and compatible with multi-shell acquisition schemes. DKI is an extension of DTI enabling the estimation of diffusion tensor and diffusion kurtosis metrics. In this study we compare the performance of DKI and DTI in performing structural brain connectivity. Six healthy subjects were recruited, aged between 25 and 35 (three females). The MRI experiments were performed using a 3T Siemens Trio with a 32-channel head coil. The scans included a T1-weighted sequence (1mm3), and a DWI with b-values 0, 1000 and 2000 s:mm

Development of foam one-part geopolymers with enhanced thermal insulation performance and low carbon dioxide emissions

Buildings are responsible for more than 40% of the energy consumption and greenhouse gas emissions. Thus, increasing building energy efficiency is one the most cost-effective ways to reduce emissions. The use of thermal insulation materials could constitute the most effective way of reducing heat losses in buildings by minimising heat energy needs. These materials have a thermal conductivity factor, k (W/m.K) lower than 0.065 while other insulation materials such as aerated concrete can go up to 0.11. Current insulation materials are associated with negative impacts in terms of toxicity. Polystyrene, for example contains anti-oxidant additives and ignition retardants. In addition, its production involves the generation of benzene and chlorofluorocarbons. Polyurethane is obtained from isocyanates, which are widely known for their tragic association with the Bhopal disaster. Besides current insulation materials releases toxic fumes when subjected to fire. This paper presents experimental results on one-part geopolymers. It also includes global warming potential assessment and cost analysis. The results show that only the use of aluminium powder allows the production mixtures with a high compressive strength however its high cost means they are commercially useless when facing the competition of commercial cellular concrete. The results also show that one-part geopolymer mixtures based on 26%OPC +58.3%FA +8%CS +7.7%CH and 3.5% hydrogen peroxide constitute a promising cost efficient (67 euro/m3), thermal insulation solution for floor heating systems with low global warming potential of 443 KgCO2eq/m3.

Assessing the feasibility of impregnating phase change materials in lightweight aggregate for development of thermal energy storage systems

This paper assesses the feasibility of impregnation/encasement of phase change materials (PCMs) in lightweight aggregates (LWAs). An impregnation process was adopted to carry out the encasement study of two different PCMs in four different LWAs. The leakage of the impregnated/encased PCMs was studied when they were submitted to freeze/thawing and oven drying tests, separately. The results confirmed that, the impregnation/encasement method is effective with respect to the large thermal energy storage density, and can be suitable for applications were PCMs cannot be incorporated directly such as asphalt road pavements.

Mortars with incorporation of PCM based in different binders: mechanical and thermal behavior

Currently we are witnessing a huge concern of society with the parameters of comfort of the buildings and the energetic consumptions. It is known that there is a huge consumption of non-renewable sources of energy. Thus, it is urgent to develop and explore ways to take advantage of renewable sources of energy by improving the energy efficiency of buildings. The mortars with incorporation of phase change materials (PCM) have the ability to regulate the temperature inside buildings, contributing to the thermal comfort and reduction of the use of heating and cooling equipment, using only the energy supplied by the sun. However, the incorporation of phase change materials in mortars modifies its characteristics. The main purpose of this study was mechanical and thermal characterization of mortars with incorporation of PCM in mortars based in different binders. The binders studied were aerial lime, hydraulic lime, gypsum and cement. For each type of binder a reference composition (0% PCM) and a composition with incorporation of 40% of PCM were developed. It was possible to observe that the incorporation of PCM in mortars caused differences in properties such as workability, compressive strength, flexural strength and adhesion, however leads to an improvement of thermal behavior.

Contribution of portuguese vernacular building strategies to indoor thermal comfort and occupants’ perception

Solar passive strategies that have been developed in vernacular architecture from different regions are a response to specific climate effects. These strategies are usually simple, low-tech and have low potential environmental impact. For this reason, several studies highlight them as having potential to reduce the demands of non-renewable energy for buildings operation. In this paper, the climatic contrast between northern and southern parts of mainland Portugal is presented, namely the regions of Beira Alta and Alentejo. Additionally, it discusses the contribution of different climate-responsive strategies developed in vernacular architecture from both regions to assure thermal comfort conditions. In Beira Alta, the use of glazed balconies as a strategy to capture solar gains is usual, while in Alentejo the focus is on passive cooling strategies. To understand the effectiveness of these strategies, thermal performances and comfort conditions of two case studies were evaluated based on the adaptive comfort model. Field tests included measurement of hygrothermal parameters and surveys on occupants’ thermal sensation. From the results, it has been found that the case studies have shown a good thermal performance by passive means alone and that the occupants feel comfortable, except during winter where there is the need to use simple heating systems.

Thermal conditions affecting heat transfer in FDM/FFE: a contribution towards the numerical modelling of the process

The performance of parts produced by Free Form Extrusion (FFE), an increasingly popular additive manufacturing technique, depends mainly on their dimensional accuracy, surface quality and mechanical performance. These attributes are strongly influenced by the evolution of the filament temperature and deformation during deposition and solidification. Consequently, the availability of adequate process modelling software would offer a powerful tool to support efficient process set-up and optimisation. This work examines the contribution to the overall heat transfer of various thermal phenomena developing during the manufacturing sequence, including convection and radiation with the environment, conduction with support and between adjacent filaments, radiation between adjacent filaments and convection with entrapped air. The magnitude of the mechanical deformation is also studied. Once this exercise is completed, it is possible to select the material properties, process variables and thermal phenomena that should be taken in for effective numerical modelling of FFE.

Comparison of different numerical methods for the solution of the time-fractional reaction-diffusion equation with variable diffusion coefficient

In this work we perform a comparison of two different numerical schemes for the solution of the time-fractional diffusion equation with variable diffusion coefficient and a nonlinear source term. The two methods are the implicit numerical scheme presented in [M.L. Morgado, M. Rebelo, Numerical approximation of distributed order reaction- diffusion equations, Journal of Computational and Applied Mathematics 275 (2015) 216-227] that is adapted to our type of equation, and a colocation method where Chebyshev polynomials are used to reduce the fractional differential equation to a system of ordinary differential equations

Thermal characterization of polyhydroxyalkanoates and poly(lactic acid) blends obtained by injection molding

In this work we present the thermal characterization of the full scope of polyhydroxyalcanoate and poly(lactic acid) blends obtain by injection molding. Blends of polyhydroxyalcanoate and poly(lactic acid) (PHA/PLA) were prepared in different compositions ranging from 0–100% in steps of 10%. The blends were injection molded and then characterized by differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and wide angle X-ray diffraction (WAXD). The increment of PHA fraction increased the degree of crystallinity of the blend and the miscibility of the base polymers as verified by the Fox model. The WAXD analysis indicates that the presence of PHA hindered the PLA crystallization. The crystallization evolution trough PHA weight fraction (wf) shows a phase inversion around 50-60%. SEM analyses confirmed that the miscibility of PHA/PLA blends increased with the incorporation of PHA and became total for values of PHA higher that 50%.

Effect of the degree of porosity on the performance of poly(vinylidene fluoride-trifluoroethylene)/poly(ethylene oxide) blend membranes for lithium-ion battery separators

Porous polymer membranes based on poly(vinylidene fluoride-trifluoroethylene)/poly(ethylene oxide) copolymers, P(VDF-TrFE)/PEO, are prepared through the, from partial to total, elimination of PEO, leading to interconnected micropores in the polymer blends. Electrolyte uptake, thermal and mechanical properties depend on the amount of PEO present in the polymer blend. Further, the degree of crystallinity of PEO and the elastic modulus (E´) of the polymer blend decrease with increasing PEO removal. Electrical properties of the polymer blend membranes are influenced by the porosity and are dominated by diffusion. The temperature dependence of ionic conductivity follows the Arrhenius behavior. It is the highest for the membranes with a volume fraction of pores of 44% (i.e, 90% PEO removal), reaching a value of 0.54 mS.cm-1 at room temperature. Battery performance was determined by assembling Li/C-LiFePO4 swagelok cells. The polymer blends with 90% PEO removal exhibit rate (124 mAhg-1 at C/5 and 47 mAhg-1 at 2C) and cycling capabilities suitable for lithium ion battery applications.

Numerical modeling and assessment of the thermal environment in an industrial premise of automotive components

Dissertação de mestrado em Engenharia Industrial