Sensores de fibra ótica baseados em novos materiais flexíveis

Dissertação de mestrado integrado em Engenharia Eletrónica Industrial e de Computadores

Synthesis and characterization of novel 4H-pyran-4-ylidene indole-based heterocyclic systems for several optical applications

The development of organic materials displaying high two-photon absorption (TPA) has attracted much attention in recent years due to a variety of potential applications in photonics and optoelectronics, such as three-dimensional optical data storage, fluorescence imaging, two-photon microscopy, optical limiting, microfabrication, photodynamic therapy, upconverted lasing, etc. The most frequently employed structural motifs for TPA materials are donor–pi bridge–acceptor (D–pi–A) dipoles, donor–pi bridge–donor (D–pi–D) and acceptor–pi bridge-acceptor (A–pi–A) quadrupoles, octupoles, etc. In this work we present the synthesis and photophysical characterization of quadrupolar heterocyclic systems with potential applications in materials and biological sciences as TPA chromophores. Indole is a versatile building block for the synthesis of heterocyclic systems for several optoelectronic applications (chemosensors, nonlinear optical, OLEDs) due to its photophysical properties and donor electron ability and 4H-pyran-4-ylidene fragment is frequently used for the synthesis of red light-emitting materials. On the other hand, 2-(2,6-dimethyl-4H-pyran-4-ylidene)malononitrile (1) and 1,3-diethyl-dihydro-5-(2,6-dimethyl-4H-pyran-4-ylidene)-2-thiobarbituric (2) units are usually used as strong acceptor moieties for the preparation of π-conjugated systems of the push-pull type. These building blocks were prepared by Knoevenagel condensation of the corresponding ketone precursor with malononitrile or 1,3-diethyl-dihydro-2-thiobarbituric acid. The new quadrupolar 4H-pyran-4-ylidene fluorophores (3) derived from indole were prepared through condensation of 5-methyl-1H-indole-3-carbaldehyde with the acceptor precursors 1 and 2, in the presence of a catalytical amount of piperidine. The new compounds were characterized by the usual spectroscopic techniques (UV-vis., FT-IR and multinuclear NMR - 1H, 13C).

In-line rheo-optical microstructural characterization of complex polymer systems

Tese de Doutoramento em Ciência e Engenharia de Polímeros e Compósitos.

In-line rheo-optical characterization during small-scale polymer processing and compounding

As increasingly more sophisticated materials and products are being developed and times-to-market need to be minimized, it is important to make available fast response characterization tools using small amounts of sample, capable of conveying data on the relationships between rheological response, process-induced material structure and product characteristics. For this purpose, a single / twin-screw mini-extrusion system of modular construction, with well-controlled outputs in the range 30-300 g/h, was coupled to a in- house developed rheo-optical slit die able to measure shear viscosity and normal-stress differences, as well as performing rheo-optical experiments, namely small angle light scattering (SALS) and polarized optical microscopy (POM). In addition, the mini-extruder is equipped with ports that allow sample collection, and the extrudate can be further processed into products to be tested later. Here, we present the concept and experimental set-up [1, 2]. As a typical application, we report on the characterization of the processing of a polymer blend and of the properties of extruded sheets. The morphological evolution of a PS/PMMA industrial blend along the extruder, the flow-induced structures developed and the corresponding rheological characteristics are presented, together with the mechanical and structural characteristics of produced sheets. The application of this experimental tool to other material systems will also be discussed.

Enrollment time as a requirement for biometric hand recognition systems

Biometric systems are increasingly being used as a means for authentication to provide system security in modern technologies. The performance of a biometric system depends on the accuracy, the processing speed, the template size, and the time necessary for enrollment. While much research has focused on the first three factors, enrollment time has not received as much attention. In this work, we present the findings of our research focused upon studying user’s behavior when enrolling in a biometric system. Specifically, we collected information about the user’s availability for enrollment in respect to the hand recognition systems (e.g., hand geometry, palm geometry or any other requiring positioning the hand on an optical scanner). A sample of 19 participants, chosen randomly apart their age, gender, profession and nationality, were used as test subjects in an experiment to study the patience of users enrolling in a biometric hand recognition system.

Measuring end-to-end delay in real-time auralisation systems

One of the major challenges in the development of an immersive system is handling the delay between the tracking of the user’s head position and the updated projection of a 3D image or auralised sound, also called end-to-end delay. Excessive end-to-end delay can result in the general decrement of the “feeling of presence”, the occurrence of motion sickness and poor performance in perception-action tasks. These latencies must be known in order to provide insights on the technological (hardware/software optimization) or psychophysical (recalibration sessions) strategies to deal with them. Our goal was to develop a new measurement method of end-to-end delay that is both precise and easily replicated. We used a Head and Torso simulator (HATS) as an auditory signal sensor, a fast response photo-sensor to detect a visual stimulus response from a Motion Capture System, and a voltage input trigger as real-time event. The HATS was mounted in a turntable which allowed us to precisely change the 3D sound relative to the head position. When the virtual sound source was at 90º azimuth, the correspondent HRTF would set all the intensity values to zero, at the same time a trigger would register the real-time event of turning the HATS 90º azimuth. Furthermore, with the HATS turned 90º to the left, the motion capture marker visualization would fell exactly in the photo-sensor receptor. This method allowed us to precisely measure the delay from tracking to displaying. Moreover, our results show that the method of tracking, its tracking frequency, and the rendering of the sound reflections are the main predictors of end-to-end delay.

Thin films composed of gold nanoparticles dispersed in a dielectric matrix: the influence of the host matrix on the optical and mechanical responses

Gold nanoparticles were dispersed in two different dielectric matrices, TiO2 and Al2O3, using magnetron sputtering and a post-deposition annealing treatment. The main goal of the present work was to study how the two different host dielectric matrices, and the resulting microstructure evolution (including both the nanoparticles and the host matrix itself) promoted by thermal annealing, influenced the physical properties of the films. In particular, the structure and morphology of the nanocomposites were correlated with the optical response of the thin films, namely their localized surface plasmon resonance (LSPR) characteristics. Furthermore, and in order to scan the future application of the two thin film system in different types of sensors (namely biological ones), their functional behaviour (hardness and Young's modulus change) was also evaluated. Despite the similar Au concentrations in both matrices (~ 11 at.%), very different microstructural features were observed, which were found to depend strongly on the annealing temperature. The main structural differences included: (i) the early crystallization of the TiO2 host matrix, while the Al2O3 one remained amorphous up to 800 °C; (ii) different grain size evolution behaviours with the annealing temperature, namely an almost linear increase for the Au:TiO2 system (from 3 to 11 nm), and the approximately constant values observed in the Au:Al2O3 system (4–5 nm). The results from the nanoparticle size distributions were also found to be quite sensitive to the surrounding matrix, suggesting different mechanisms for the nanoparticle growth (particle migration and coalescence dominating in TiO2 and Ostwald ripening in Al2O3). These different clustering behaviours induced different transmittance-LSPR responses and a good mechanical stability, which opens the possibility for future use of these nanocomposite thin film systems in some envisaged applications (e.g. LSPR-biosensors).

Quantum field theory approach to the optical conductivity of strained and deformed graphene

The computation of the optical conductivity of strained and deformed graphene is discussed within the framework of quantum field theory in curved spaces. The analytical solutions of the Dirac equation in an arbitrary static background geometry for one dimensional periodic deformations are computed, together with the corresponding Dirac propagator. Analytical expressions are given for the optical conductivity of strained and deformed graphene associated with both intra and interbrand transitions. The special case of small deformations is discussed and the result compared to the prediction of the tight-binding model.

Dissolution enhancement of active pharmaceutical ingredients by therapeutic deep eutectic systems

A therapeutic deep eutectic system (THEDES) is here defined as a deep eutectic solvent (DES) having an active pharmaceutical ingredient (API) as one of the components. In this work, THEDESs are proposed as enhanced transporters and delivery vehicles for bioactive molecules. THEDESs based on choline chloride (ChCl) or menthol conjugated with three different APIs, namely acetylsalicylic acid (AA), benzoic acid (BA) and phenylacetic acid (PA), were synthesized and characterized for thermal behaviour, structural features, dissolution rate and antibacterial activity. Differential scanning calorimetry and polarized optical microscopy showed that ChCl:PA (1:1), ChCl:AA (1:1), menthol:AA (3:1), menthol:BA (3:1), menthol:PA (2:1) and menthol:PA (3:1) were liquid at room temperature. Dissolution studies in PBS led to increased dissolution rates for the APIs when in the form of THEDES, compared to the API alone. The increase in dissolution rate was particularly noticeable for menthol-based THEDES. Antibacterial activity was assessed using both Gram-positive and Gram-negative model organisms. The results show that all the THEDESs retain the antibacterial activity of the API. Overall, our results highlight the great potential of THEDES as dissolution enhancers in the development of novel and more effective drug delivery systems.

Optimization of magnetoelectric composites based on electroactive polymers for energy harvesting and sensor application

Tese de Doutoramento em Engenharia de Materiais.