Optimizing potentiometric ionophore and electrode design for environmental on-site control of antibiotic drugs: Application to sulfamethoxazole

Potentiometric sensors are typically unable to carry out on-site monitoring of environmental drug contaminants because of their high limits of detection (LODs). Designing a novel ligand material for the target analyte and managing the composition of the internal reference solution have been the strategies employed here to produce for the first time a potentiometric-based direct reading method for an environmental drug contaminant. This concept has been applied to sulfamethoxazole (SMX), one of the many antibiotics used in aquaculture practices that may occur in environmental waters. The novel ligand has been produced by imprinting SMX on the surface of graphitic carbon nanostructures (CN) < 500 nm. The imprinted carbon nanostructures (ICN) were dispersed in plasticizer and entrapped in a PVC matrix that included (or not) a small amount of a lipophilic additive. The membrane composition was optimized on solid-contact electrodes, allowing near-Nernstian responses down to 5.2 μg/mL and detecting 1.6 μg/mL. The membranes offered good selectivity against most of the ionic compounds in environmental water. The best membrane cocktail was applied on the smaller end of a 1000 μL micropipette tip made of polypropylene. The tip was then filled with inner reference solution containing SMX and chlorate (as interfering compound). The corresponding concentrations were studied for 1 × 10−5 to 1 × 10−10 and 1 × 10−3 to 1 × 10−8 mol/L. The best condition allowed the detection of 5.92 ng/L (or 2.3 × 10−8 mol/L) SMX for a sub-Nernstian slope of −40.3 mV/decade from 5.0 × 10−8 to 2.4 × 10−5 mol/L.

Electrochemical sensor for simultaneous determination of herbicide MCPA and its metabolite 4-chloro-2-methylphenol. Application to photodegradation environmental monitoring

The development and application of a polyaniline/carbon nanotube (CNT) cyclodextrin matrix (PANI-β-CD/MWCNT)-based electrochemical sensor for the quantitative determination of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) and its main transformation product 4-chloro-2-methylphenol in natural waters are described. A simple cyclic voltammetry-based electrochemical methodology, in phosphate buffer solution at pH 6.0, was used to develop a method to determine both MCPA and 4-chloro-2-methylphenol, without any previous extraction or derivatization steps. A linear concentration range (10 to 50 μmol L−1) and detection limits of 1.1 and 1.9 μmol L−1, respectively, were achieved using optimized cyclic voltammetric parameters. The proposed method was successfully applied to the determination of MCPA and 4-chloro-2-methylphenol in natural water samples with satisfactory recoveries (94 to 107 %) and in good agreement with the results obtained by an established high-performance liquid chromatography technique, no significant differences being found between the methods. Interferences from ionic species and other herbicides used for broad-leaf weed control were shown to be small. The newly developed methodology was also successfully applied to MCPA photodegradation environmental studies.

SHõWA: A Self-healing Framework for Web-based Applications

The complexity of systems is considered an obstacle to the progress of the IT industry. Autonomic computing is presented as the alternative to cope with the growing complexity. It is a holistic approach, in which the systems are able to configure, heal, optimize, and protect by themselves. Web-based applications are an example of systems where the complexity is high. The number of components, their interoperability, and workload variations are factors that may lead to performance failures or unavailability scenarios. The occurrence of these scenarios affects the revenue and reputation of businesses that rely on these types of applications. In this article, we present a self-healing framework for Web-based applications (SHõWA). SHõWA is composed by several modules, which monitor the application, analyze the data to detect and pinpoint anomalies, and execute recovery actions autonomously. The monitoring is done by a small aspect-oriented programming agent. This agent does not require changes to the application source code and includes adaptive and selective algorithms to regulate the level of monitoring. The anomalies are detected and pinpointed by means of statistical correlation. The data analysis detects changes in the server response time and analyzes if those changes are correlated with the workload or are due to a performance anomaly. In the presence of per- formance anomalies, the data analysis pinpoints the anomaly. Upon the pinpointing of anomalies, SHõWA executes a recovery procedure. We also present a study about the detection and localization of anomalies, the accuracy of the data analysis, and the performance impact induced by SHõWA. Two benchmarking applications, exercised through dynamic workloads, and different types of anomaly were considered in the study. The results reveal that (1) the capacity of SHõWA to detect and pinpoint anomalies while the number of end users affected is low; (2) SHõWA was able to detect anomalies without raising any false alarm; and (3) SHõWA does not induce a significant performance overhead (throughput was affected in less than 1%, and the response time delay was no more than 2 milliseconds).

Environmental Decision-making utilizing a Web GIS to Monitor Hazardous Industrial Emissions in the Valencian community of Spain

Dissertation submitted in partial fulfillment of the requirements for the Degree of Master of Science in Geospatial Technologies.

Estudo de vulnerabilidades em aplicações web e o seu reflexo em domínios Portugueses

Muito se tem falado sobre revolução tecnológica e do aparecimento constante de novas aplicações Web, com novas funcionalidades que visam facilitar o trabalho dos utilizadores. Mas será que estas aplicações garantem que os dados transmitidos são tratados e enviados por canais seguros (protocolos)? Que garantias é que o utilizador tem que mesmo que a aplicação utilize um canal, que prevê a privacidade e integridade de dados, esta não apresente alguma vulnerabilidade pondo em causa a informação sensível do utilizador? Software que não foi devidamente testado, aliado à falta de sensibilização por parte dos responsáveis pelo desenvolvimento de software para questões de segurança, levam ao aumento de vulnerabilidades e assim exponenciam o número de potenciais vítimas. Isto aliado ao efeito de desinibição que o sentimento de invisibilidade pode provocar, conduz ao facilitismo e consequentemente ao aumento do número de vítimas alvos de ataques informáticos. O utilizador, por vezes, não sabe muito bem do que se deve proteger, pois a confiança que depõem no software não pressupõem que os seus dados estejam em risco. Neste contexto foram recolhidos dados históricos relativos a vulnerabilidades nos protocolos SSL/TLS, para perceber o impacto que as mesmas apresentam e avaliar o grau de risco. Para além disso, foram avaliados um número significativo de domínios portugueses para perceber se os mesmos têm uma vulnerabilidade específica do protocolo SSL/TLS.

Web Processing Services for Forestry and Environmental Applications

Dissertation submitted in partial fulfillment of the requirements for the Degree of Master of Science in Geospatial Technologies.

Dynamic adaptation of interaction models for stateful web services

Dissertação para obtenção do Grau de Mestre em Engenharia Informática

Ionic liquids as catalysts of lignocellulosic biomass processing

The present work is devoted to study the pre-treatment of lignocellulosic biomass, especially wheat straw, by the application of the acidic ionic liquid (IL) such as 1-butyl-3-methylimidazolium hydrogen sulphate. The ability of this IL to hydrolysis and conversion of biomass was scrutinised. The pre-treatment with hydrogen sulphate-based IL allowed to obtain a liquor rich in hemicellulosic sugars, furans and organic acids, and a solid fraction mainly constituted by cellulose and lignin. Quantitative and qualitative analyses of the produced liquors were made by capillary electrophoresis and high-performance liquid chromatography. Pre-treatment conditions were set to produce xylose or furfural. Specific range of temperatures from 70 to 175 °C and residence times from 20.0 to 163.3 min were studied by fixing parameters such as biomass/IL ratio (10 % (w/w)) and water content (1.25 % (w/w)) in the pre-treatment process. Statistical modelling was applied to maximise the xylose and furfural concentrations. For the purpose of reaction condition comparison the severity factor for studied ionic liquid was proposed and applied in this work. Optimum conditions for xylose production were identified to be at 125 °C and 82.1 min, at which 16.7 % (w/w) xylose yield was attained. Furfural was preferably formed at higher pre-treatment temperatures and longer reaction time (161 °C and 104.5 min) reaching 30.7 % (w/w) maximum yield. The influence of water content on the optimum xylose formation was also studied. Pre-treatments with 5 and 10 % (w/w) water content were performed and an increase of 100 % and 140 % of xylose yield was observed, respectively, while the conversion into furfural maintained unchanged.

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.

Design and characterization of novel biopolymeric structure using biocompatible ionic liquids

The main objective of this thesis was the development of polymeric structures from the dissolution of FucoPol, a bacterial exopolysaccharide (EPS), in a biocompatible ionic liquid, choline acetate. The FucoPol was produced by the bacteria Enterobacter A47 using glycerol as carbon source at controlled temperature and pH (30ºC and 7, respectively). At the end of 3 days it was produced 7 g/L of FucoPol. The net yield of Fucopol in glycerol (YP/S) was 0.22 g/g and the maximum productivity 2.37 g/L.d This polymer was characterized about its composition in sugars and acyl groups (by High-Performance Liquid Chromatography - HPLC), containing fucose (35 % mol), galactose (21 % mol), glucose (29 % mol), rhamnose (3% mol) and glucuronic acid (12% mol) as well as acetate (14.28 % mol), pyruvate (2.15 % mol) and succinate (1.80 % mol). Its content of water and ash was 15% p/p and 2% p/p, respectively, and the chemical bonds (determined by Infrared Spectroscopy - FT-IR) are consistent to the literature reports. However, due to limitations in Differential Scanning Calorimetry (DSC) equipment it was not possible to determine the glass transition temperature. In turn, the ionic liquid showed the typical behavior of a Newtonian fluid, glass transition temperature (determined by DSC) -98.03ºC and density 1.1031 g/cm3. The study of chemical bonds by FT-IR showed that amount of water (8.80%) influenced the visualization of the bands predicted to in view of their chemical structure. After the dissolution of the FucoPol in the ionic liquid at different temperatures (50, 60, 80 and 100 ° C) it was promoted the removal of this by the phase inversion method using deionized water as a solvent, followed by drying in an oven at 70 ° C. The mixtures before and after the phase inversion method were characterized through the studies mentioned above. In order to explore possible application field’s biocompatibility assays and collage on balsa wood tests were performed. It was found that the process of washing with water by the phase inversion method was not totally effective in removing the biocompatible ionic liquid, since all FucoPol – IL mixtures still contained ionic liquid in their composition as can be seen by the DSC results and FT-IR. In addition, washing the mixtures with water significantly altered the composition of FucoPol. However, these mixtures, that developed a viscous behavior typical of a non-Newtonian fluid (shear-thinning), have the potential to be applied in the biomedical field as well as biological glues.

Development and modulation of magnetic responsive supported ionic liquid membranes

The work presented in this thesis aims at developing a new separation process based on the application of supported magnetic ionic liquid membranes, SMILMs, using magnetic ionic liquids, MILs. MILs have attracted growing interest due to their ability to change their physicochemical characteristics when exposed to variable magnetic field conditions. The magnetic responsive behavior of MILs is thus expected to contribute for the development of more efficient separation processes, such as supported liquid membranes, where MILs may be used as a selective carrier. Driven by the MILs behavior, these membranes are expected to switch reversibly their permeability and selectivity by in situ and non-invasive adjustment of the conditions (e.g. intensity, direction vector and uniformity) of an external applied magnetic field. The development of these magnetic responsive membrane processes were anticipated by studies, performed along the first stage of this PhD work, aiming at getting a deep knowledge on the influence of magnetic field on MILs properties. The influence of the magnetic field on the molecular dynamics and structural rearrangement of MILs ionic network was assessed through a 1H-NMR technique. Through the 1H-NMR relaxometry analysis it was possible to estimate the self-diffusion profiles of two different model MILs, [Aliquat][FeCl4] and [P66614][FeCl4]. A comparative analysis was established between the behavior of magnetic and non-magnetic ionic liquids, MILs and ILs, to facilitate the perception of the magnetic field impact on MILs properties. In contrast to ILs, MILs show a specific relaxation mechanism, characterized by the magnetic dependence of their self-diffusion coefficients. MILs self-diffusion coefficients increased in the presence of magnetic field whereas ILs self-diffusion was not affected. In order to understand the reasons underlying the magnetic dependence of MILs self-diffusion, studies were performed to investigate the influence of the magnetic field on MILs’ viscosity. It was observed that the MIL´s viscosity decreases with the increase of the magnetic field, explaining the increase of MILs self-diffusion according to the modified Stokes- Einstein equation. Different gas and liquid transport studies were therefore performed aiming to determine the influence of the magnetic behavior of MILs on solute transport through SMILMs. Gas permeation studies were performed using pure CO2 andN2 gas streams and air, using a series of phosphonium cation based MILs, containing different paramagnetic anions. Transport studies were conducted in the presence and absence of magnetic field at a maximum intensity of 1.5T. The results revealed that gas permeability increased in the presence of the magnetic field, however, without affecting the membrane selectivity. The increase of gas permeability through SMILMs was related to the decrease of the MILs viscosity under magnetic field conditions.(...)

Promoção da autonomia dos alunos na aprendizagem de programação para a WEB

Relatório de estágio de mestrado em Ensino de Informática

Reverse engineering of web applications

The MAP-i Doctoral Program of the Universities of Minho, Aveiro and Porto

Automatic eye blink detection using consumer web cameras

This research aims to advance blinking detection in the context of work activity. Rather than patients having to attend a clinic, blinking videos can be acquired in a work environment, and further automatically analyzed. Therefore, this paper presents a methodology to perform the automatic detection of eye blink using consumer videos acquired with low-cost web cameras. This methodology includes the detection of the face and eyes of the recorded person, and then it analyzes the low-level features of the eye region to create a quantitative vector. Finally, this vector is classified into one of the two categories considered —open and closed eyes— by using machine learning algorithms. The effectiveness of the proposed methodology was demonstrated since it provides unbiased results with classification errors under 5%

An investigation into system security requirements and implementation in an Application Service Provider (ASP) environment

Although the ASP model has been around for over a decade, it has not achieved the expected high level of market uptake. This research project examines the past and present state of ASP adoption and identifies security as a primary factor influencing the uptake of the model. The early chapters of this document examine the ASP model and ASP security in particular. Specifically, the literature and technology review chapter analyses ASP literature, security technologies and best practices with respect to system security in general. Based on this investigation, a prototype to illustrate the range and types of technologies that encompass a security framework was developed and is described in detail. The latter chapters of this document evaluate the practical implementation of system security in an ASP environment. Finally, this document outlines the research outputs, including the conclusions drawn and recommendations with respect to system security in an ASP environment. The primary research output is the recommendation that by following best practices with respect to security, an ASP application can provide the same level of security one would expect from any other n-tier client-server application. In addition, a security evaluation matrix, which could be used to evaluate not only the security of ASP applications but the security of any n-tier application, was developed by the author. This thesis shows that perceptions with regard to fears of inadequate security of ASP solutions and solution data are misguided. Finally, based on the research conducted, the author recommends that ASP solutions should be developed and deployed on tried, tested and trusted infrastructure. Existing Application Programming Interfaces (APIs) should be used where possible and security best practices should be adhered to where feasible.