Hyperspectral signal subspace estimation

Given an hyperspectral image, the determination of the number of endmembers and the subspace where they live without any prior knowledge is crucial to the success of hyperspectral image analysis. This paper introduces a new minimum mean squared error based approach to infer the signal subspace in hyperspectral imagery. The method, termed hyperspectral signal identification by minimum error (HySime), is eigendecomposition based and it does not depend on any tuning parameters. It first estimates the signal and noise correlation matrices and then selects the subset of eigenvalues that best represents the signal subspace in the least squared error sense. The effectiveness of the proposed method is illustrated using simulated data based on U.S.G.S. laboratory spectra and real hyperspectral data collected by the AVIRIS sensor over Cuprite, Nevada.

New fluorescent chemosensors based on bio-inspired ligands and macrocycles: from single molecules to nanoparticles

Dissertação apresentada para obtenção do grau de Doutor em Biotecnologia pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia. A presente dissertação foi preparada no âmbito do protocolo de acordo bilateral de educação avançada (ERASMUS) entre a Universidade de Vigo e a Universidade Nova de Lisboa

Parametric analog signal amplification applied to nanoscale cmos wireless digital transceivers

Thesis presented in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the subject of Electrical and Computer Engineering by the Universidade Nova de Lisboa,Faculdade de Ciências e Tecnologia

Sulphonamide-imprinted sol–gel materials as ionophores in potentiometric transduction

This work proposes different kind of solid-contact graphite-based electrodes for the selective determination of sulphonamides (SPHs) in pharmaceuticals, biological fluids and aquaculture waters. Sulfadiazine (SDZ) and sulfamethoxazole (SMX) were selected for this purpose for being the most representative compounds of this group. The template molecules were imprinted in sol–gel (ISG) and the resulting material was used as detecting element. This was made by employing it as either a sensing layer or an ionophore of PVC-based membranes and subsequent potentiometric transduction, a strategy never reported before. The corresponding non-imprinted sol–gel (NISG) membranes were used as blank. The effect of plasticizer and kind/charge of ionic lipophilic additive was also studied. The best performance in terms of slope, linearity ranges and signal reproducibility and repeatability was achieved by PVC membranes including a high dielectric constant plasticizer and 15 mg of ISG particles. The corresponding average slope was −51.4 and −52.4 mV/decade, linear responses were 9.0 × 10−6 and 1.7 × 10−5 M, and limits of detection were 0.74 and 1.3 μg/mL for SDZ and for SMX, respectively. Good selectivity with log Kpot < −0.3 was observed for carbonate, chloride, fluoride, hydrogenocarbonate, nitrate, nitrite, phosphate, cyanide, sulfate, borate, persulphate, citrate, tartrate, salicylate, tetracycline, ciprofloxacin, sulphamerazine, sulphatiazole, dopamine, glucose, galactose, cysteine and creatinine. The best sensors were successfully applied to the analysis of real samples with relative errors ranging from −6.8 to + 3.7%.

Photoelectron spectroscopy of nitrogen containing molecules of biological and industrial interest

A thesis submitted for the degree of Ph. D. in Physics

Myoelectric Signal Monitoring System

The Electromyography (EMG) is an important tool for gait analyzes and disorders diagnoses. Traditional methods involve equipment that can disturb the analyses, being gradually substituted by different approaches, like wearable and wireless systems. The cable replacement for autonomous systems demands for technologies capable of meeting the power constraints. This work presents the development of an EMG and kinematic data capture wireless module, designed taking into account power consumption issues. This module captures and converts the analog myoeletric signal to digital, synchronously with the capture of kinetic information. Both data are time multiplexed and sent to a PC via Bluetooth link. The work carried out comprised the development of the hardware, the firmware and a graphical interface running in an external PC. The hardware was developed using the PIC18F14K22, a low power family of microcontrollers. The link was established via Bluetooth, a protocol designed for low power communication. An application was also developed to recover and trace the signal to a Graphic User Interface (GUI), coordinating the message exchange with the firmware. Results were obtained which allowed validating the conceived system in static and with the subject performing short movements. Although it was not possible to perform the tests within more dynamic movements, it is shown that it is possible to capture, transmit and display the captured data as expected. Some suggestions to improve the system performance also were made.

Analysis of Natural and Artificial Phenomena Using Signal Processing and Fractional Calculus

In this paper we study several natural and man-made complex phenomena in the perspective of dynamical systems. For each class of phenomena, the system outputs are time-series records obtained in identical conditions. The time-series are viewed as manifestations of the system behavior and are processed for analyzing the system dynamics. First, we use the Fourier transform to process the data and we approximate the amplitude spectra by means of power law functions. We interpret the power law parameters as a phenomenological signature of the system dynamics. Second, we adopt the techniques of non-hierarchical clustering and multidimensional scaling to visualize hidden relationships between the complex phenomena. Third, we propose a vector field based analogy to interpret the patterns unveiled by the PL parameters.

Parallel programming in biomedical signal processing

Dissertação para obtenção do Grau de Mestre em Engenharia Biomédica

Algorithms for information extraction and signal annotation on long-term biosignals using clustering techniques

Dissertação para obtenção do Grau de Mestre em Engenharia Biomédica

Insight into the multicopper oxidases stability

Dissertation presented to obtain the PhD degree in Biochemistry

Low-Spin Heme b3 in the Catalytic Center of Nitric Oxide Reductase from Pseudomonas nautica

Biochemistry, 2011, 50 (20), pp 4251–4262 DOI: 10.1021/bi101605p

Signal transduction pathways involving the hypertension-related WNK1 and WNK4 protein kinases

Dissertação apresentada para obtenção do Grau de Doutor em Biologia, na especialidade de Genética Molecular, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

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.

Development of novel ionic liquids based on biological molecules

Ionic Liquids (ILs) belong to a class of compounds with unusual properties: very low vapour pressure; high chemical and thermal stability and the ability to dissolve a wide range of substances. A new field in research is evaluating the possibility to use natural chiral biomolecules for the preparation of chiral ionic liquids (CILs). This important challenge in synthetic chemistry can open new avenues of research in order to avoid some problems related with the intrinsic biodegradability and toxicity associated to conventional ILs. The research work developed aimed for the synthesis of CILs, their characterization and possible applications, based on biological moieties used either as chiral cations or anions, depending on the synthetic manipulation of the derivatives. Overall, a total of 28 organic salts, including CILs were synthesized: 9 based on L-cysteine derivatives, 12 based on L-proline, 3 based on nucleosides and 4 based on nucleotides. All these new CILs were completely characterized and their chemical and physical properties were evaluated. Some CILs based on L-cysteine have been applied for discrimination processes, including resolution of racemates and as a chiral catalyst for asymmetric Aldol condensation. L-proline derived CILs were also studied as chiral catalysts for Michael reaction. In parallel, the interactions of macrocyclic oligosugars called cyclodextrins (CDs) with several ILs were studied. It was possible to improve the solubility of CDs in water and serum. Additionally, fatty acids and steroids showed an increase in water solubility when ILs-CDs systems were used. The development of efficient and selective ILs-CDs systems is indispensable to expand the range of their applications in host-guest interactions, drug delivery systems or catalytic reactions. Novel salts derived from nucleobases were used in order to enhance the fluorescence in aqueous solution. Additionally, preliminary studies regarding ethyl lactate as an alternative solvent for asymmetric organocatalysis were performed.

Study of the electromyographic signal dynamic behavior in Amyotrophic Lateral Sclerosis (ALS)

Amyotrophic Lateral Sclerosis (ALS) is a neurodegenerative disease characterized by motor neurons degeneration, which reduces muscular force, being very difficult to diagnose. Mathematical methods are used in order to analyze the surface electromiographic signal’s dynamic behavior (Fractal Dimension (FD) and Multiscale Entropy (MSE)), evaluate different muscle group’s synchronization (Coherence and Phase Locking Factor (PLF)) and to evaluate the signal’s complexity (Lempel-Ziv (LZ) techniques and Detrended Fluctuation Analysis (DFA)). Surface electromiographic signal acquisitions were performed in upper limb muscles, being the analysis executed for instants of contraction for ipsilateral acquisitions for patients and control groups. Results from LZ, DFA and MSE analysis present capability to distinguish between the patient group and the control group, whereas coherence, PLF and FD algorithms present results very similar for both groups. LZ, DFA and MSE algorithms appear then to be a good measure of corticospinal pathways integrity. A classification algorithm was applied to the results in combination with extracted features from the surface electromiographic signal, with an accuracy percentage higher than 70% for 118 combinations for at least one classifier. The classification results demonstrate capability to distinguish members between patients and control groups. These results can demonstrate a major importance in the disease diagnose, once surface electromyography (sEMG) may be used as an auxiliary diagnose method.