MnFe2O4@CNT-N as novel electrochemical nanosensor for determination of caffeine, acetaminophen and ascorbic acid

For the first time, a glassy carbon electrode (GCE) modified with novel N-doped carbon nanotubes (CNT-N) functionalized with MnFe2O4 nanoparticles (MnFe2O4@CNT-N) has been prepared and applied for the electrochemical determination of caffeine (CF), acetaminophen (AC) and ascorbic acid (AA). The electrochemical behaviour of CF, AC and AA on the bare GCE, CNT-N/GCE and MnFe2O4@CNT-N/GCE were carefully investigated using cyclic voltammetry (CV) and square-wave voltammetry (SWV). Compared to bare GCE and CNT-N modified electrode, the MnFe2O4@CNT-N modified electrode can remarkably improve the electrocatalytic activity towards the oxidation of CF, AC and AA with an increase in the anodic peak currents of 52%, 50% and 55%, respectively. Also, the SWV anodic peaks of these molecules could be distinguished from each other at the MnFe2O4@CNT-N modified electrode with enhanced oxidation currents. The linear response ranges for the square wave voltammetric determination of CF, AC and AA were 1.0 × 10−6 to 1.1 × 10−3 mol dm−3, 1.0 × 10−6 to 1.0 × 10−3 mol dm−3 and 2.0 × 10−6 to 1.0 × 10−4 mol dm−3 with detection limit (S/N = 3) of 0.83 × 10−6, 0.83 × 10−6 and 1.8 × 10−6 mol dm−3, respectively. The sensitivity values at the MnFe2O4@CNT-N/GCE for the individual determination of AC, AA and CF and in the presence of the other molecules showed that the quantification of AA and CF show no interferences from the other molecules; however, AA and CF interfered in the determination of AC, with the latter molecule showing the strongest interference. Nevertheless, the obtained results show that MnFe2O4@CNT-N composite material acted as an efficient electrochemical sensor towards the selected biomolecules.

O tratamento jurídico e contabilístico das reservas nas cooperativas

Este estudo pretende aferir a relevância das reservas na estrutura financeira da cooperativa e compará-las com a relevância das reservas numa sociedade comercial, de idêntica estrutura financeira. Para o efeito, depois de uma reflexão sobre o tratamento jurídico e contabilístico das reservas nas cooperativas, procede-se a um estudo empírico, tendo por referência a Cooperativa dos Pedreiros. Tendo em conta um conjunto de vertentes construídas a partir do enquadramento jurídico e contabilístico – constituição e utilização das reservas, as suas finalidades (quer durante a vida das cooperativas quer no momento da dissolução e liquidação do seu património), as funções das reservas, e o seu enquadramento contabilístico, – realizou-se uma entrevista em profundidade e procedeu-se à análise dos Estatutos da Cooperativa dos Pedreiros, com vista a analisar tais vertentes na atividade desenvolvida pela mesma e refletida nos relatórios de contas dos anos 2010, 2011, 2012, 2013 e 2014. Os resultados do estudo confirmam que as reservas nas cooperativas têm um regime jurídico diferente face ao das sociedades comerciais, nomeadamente quanto ao destino da reserva legal, que nas cooperativas se circunscreve à cobertura de perdas, bem como a sua irrepartibilidade entre os cooperadores. Tal diferença é, igualmente, visível quando se estabeleceu o paralelismo entre o regime das reservas na cooperativa e na sociedade comercial. Constata-se que as reservas apresentam maior importância na estrutura financeira da cooperativa do que na sociedade comercial. Por fim, refira-se que o caráter pioneiro deste estudo empírico poderá contribuir para uma futura alteração ao normativo jurídico português aplicável às cooperativas quanto a aspetos particulares do seu regime, destacando-se a importância da contínua dotação das reservas irrepartíveis, nomeadamente da reserva legal.

A informação contabilística no processo de tomada de decisão de microempresas

A globalização, o desenvolvimento económico e o aumento da competitividade, possibilitaram um acréscimo do número de microempresas, originado o aumento do peso que estas detêm na economia. Estas absorvem a maioria da mão-de-obra do setor privado e criam parte significativa da riqueza de um país, no entanto, apresentam elevados índices de dissolução e liquidação, pondo em causa o desenvolvimento sustentável das economias onde estão sediadas. A informação contabilística é essencial em qualquer tipo de organização. Para as microempresas a utilização da informação contabilística no processo de tomada de decisão determina a diferença entre sucesso e o insucesso do empreendimento, no entanto, este tipo de informação continua a ser menosprezado pela gerência das microempresas. É assim importante estudar os fatores que limitam a utilização da informação contabilística no processo de tomada de decisão de microempresas e investigar a sua relação com os fatores de insucesso deste tipo de entidades. Nesta investigação para se atingirem os objetivos propostos considera-se adequado a adoção de uma metodologia de natureza quantitativa, assente num inquérito dirigido aos Contabilistas Certificados. Através da investigação demonstrou-se a importância que a informação contabilística detém no processo de tomada de decisão das microempresas Portuguesas. Constatou-se que os gerentes limitam a utilização deste tipo de informação, uma vez que não têm capacidade para interpretar a informação contabilística, nem reconhecem os benefícios inerentes à sua utilização nas decisões empresariais. Confirmou-se ainda que existe uma relação positiva entre os fatores de insucesso e os fatores que limitam a utilização da informação contabilística no processo de tomada de decisão de microempresas.

Pre-treatment of different types of lignocellulosic biomass using ionic liquids

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau Mestre em Biotecnologia

Deeper insights into SRB-driven biocorrosion mechanisms

Dissertação para obtenção do Grau de Doutor em Química Sustentável

Durability to marine environment of innovative products for consolidation and chromatic reintegration of historical renders

9th International Masonry Conference 2014, 7-9 July, Universidade do Minho, Guimarães

Design and characterization of Chitin- Glucan polymeric structures for wound dressing materials

The main objective of this work was the development of polymeric structures, gel and films, generated from the dissolution of the Chitin-Glucan Complex (CGC) in biocompatible ionic liquids for biomedical applications. Similar as chitin, CGC is only soluble in some special solvents which are toxic and corrosive. Due to this fact and the urgent development of biomedical applications, the need to use biocompatible ionic liquids to dissolve the CGC is indispensable. For the dissolution of CGC, the biocompatible ionic liquid used was Choline acetate. Two different CGC’s, KiOnutrime from KitoZyme and biologically produced CGC from Faculdade de Ciencias e Tecnologia (FCT) - Universidade Nova de Lisboa, were characterized in order to develop biocompatible wound dressing materials. The similar result is shown in term of the ratio of chitin:glucan, which is 1:1.72 for CGC-FCT and 1:1.69 for CGC-Commercial. For the analysis of metal element content, water and inorganic salts content and protein content, both polymers showed some discrepancies, where the content in CGC-FCT is always higher compared to the commercial one. The different characterization results between CGC-FCT and CGC-Commercial could be addressed to differences in the purification method, and the difference of its original strain yeast, whereas CGC-FCT is derived from P.pastoris and the commercial CGC is from A.niger. This work also investigated the effect of biopolymers, temperature dissolution, non-solvent composition on the characteristics of generated polymeric structure with biocompatible ionic liquid. The films were prepared by casting a polymer mixture, immersion in a non-solvent, followed by drying at ambient temperature. Three different non-solvents were tested in phase inversion method, i.e. water, methanol, and glycerol. The results indicate that the composition of non-solvent in the coagulation bath has great influence in generated polymeric structure. Water was found to be the best coagulant for producing a CGC polymeric film structure. The characterizations that have been done include the analysis of viscosity and viscoelasticity measurement, as well as sugar composition in the membrane and total sugar that was released during the phase inversion method. The rheology test showed that both polymer mixtures exhibit a non- Newtonian shear thinning behaviour. Where the viscosity and viscoelasticity test reveal that CGCFCT mixture has a typical behaviour of a viscous solution with entangled polymer chains and CGCCommercial mixture has true gel behaviour. The experimental results show us that the generated CGC solution from choline acetate could be used to develop both polymeric film structure and gel. The generated structures are thermally stable at 100° C, and are hydrophilic. The produced films have dense structure and mechanical stabilities against puncture up to 60 kPa.

Fiber functionalization for biomedical applications

Deep-eutectic solvents (DES) are considered novel renewable and biodegradable solvents, with a cheap and easy synthesis, without waste production. Later it was discovered a new subclass of DES that even can be biocompatible, since their synthesis uses primary metabolites such as amino acids, organic acids and sugars, from organisms. This subclass was named natural deep-eutectic solvents (NADES). Due to their properties it was tried to study the interaction between these solvents and biopolymers, in order to produce functionalized fibers for biomedical applications. In this way, fibers were produced by using the electrospinning technique. However, it was first necessary to study some physical properties of NADES, as well as the influence of water in their properties. It has been concluded that the water has a high influence on NADES properties, which can be seen on the results obtained from the rheology and viscosity studies. The fluid dynamics had changed, as well as the viscosity. Afterwards, it was tested the viability of using a starch blend. First it was tested the dissolution of these biopolymers into NADES, in order to study the viability of their application in electrospinning. However the results obtained were not satisfactory, since the starch polymers studied did not presented any dissolution in any NADES, or even in organic solvents. In this way it was changed the approach, and it was used other biocompatible polymers. Poly(ethylene oxide), poly(vinyl alcohol) and gelatin were the others biopolymers tested for the electrospinning, with NADES. All polymers show good results, since it was possible to obtain fibers. However for gelatin it was used only eutectic mixtures, containing active pharmaceutical ingredients (API’s), instead of NADES. For this case it was used mandelic acid (antimicrobial properties), choline chloride, ibuprofen (anti-inflammatory properties) and menthol (analgesic properties). The polymers and the produced fibers were characterized by scanning electron microscope (SEM), Transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR). With the help of these techniques it was possible to conclude that it was possible to encapsulate NADES within the fibers. Rheology it was also study for poly(ethylene oxide) and poly(vinyl alcohol), in a way to understand the influence of polymer concentration, on the electrospinning technique. For the gelatin, among the characterization techniques, it was also performed cytotoxicity and drug release studies. The gelatin membranes did not show any toxicity for the cells, since their viability was maintained. Regarding the controlled release profile experiment no conclusion could be drawn from the experiments, due to the rapid and complete dissolution of the gelatin in the buffer solution. However it was possible to quantify the mixture of choline chloride with mandelic acid, allowing thus to complete, and confirm, the information already obtained for the others characterization technique.

Da responsabilidade civil por abandono afetivo

This study, in the Family Law area, aims to examine the civil liability for emotional distance from a multidisciplinary perspective. The work and reflection made thereunder tend to corroborate the cognizance that self-representation, sociability and the ability of future adults to define their life’s projects, depend, to a large extent, on the emotional stability and maturity that has been assured to them, as children, by the material and emotional care that has been provided to them by both parents. It is therefore crucial to tend to the feelings of loss and to the potential lack of self-esteem that the affective rupture with either parents may cause. Thus, we promote an analysis of the sustainability, under Portuguese law, of the imposition of compensatory measures, independent from other injunctions foreseen in civil and guardianship law, upon the dissolution of family ties in result of a guilty injury of parental obligations, which have caused serious and evident injuries to the children.

Contrato de abertura de crédito bancário

La recherche que nous avons mené à bien avait pour but, dans un premier temps de comprendre la notion de contrat, ses caractéristiques, fonctions et les garanties qui en peuvent être fournies. Nous invoquerons le contenu du contrat, c'est à dire, les effets de celui-ci en essayant de montrer les droits et obligations auxquels les parties seront liées. Bien qu'étant un contrat assez requérant dans la pratique bancaire, celui-ci n'a pas encore attiré l'attention du législateur de façon à établir un régime qui pourrait lui être appliqué au lieu de s'appuyer sur d'autres contrats lui étant similaires. Nous proposons l'analyse de la cessation du contrat, en se concentrant sur les moyens de la dissolution, survenue suite à la conclusion de l'accord comme la plainte, l'abrogation, l'expiration et la résolution du contrat, en laissant de côté la dissolution du contrat pour des raisons survenues avant la conclusion du contrat, comme la nullité et l'annulation.

Evaluation of mechanical soft-abrasive blasting and chemical cleaning methods on alkyd-paint graffiti made on carbonate stones

In the context of this dissertation several studies were developed resulting in submission and publication “Evaluation of mechanical soft-abrasive blasting and chemical cleaning methods on alkyd-paint graffiti made on calcareous stones” to Journal of Cultural Heritage. (http://dx.doi.org/10.101 /j.culher.2014.10.004)

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.

Contrato de abertura de crédito bancário

La recherche que nous avons mené à bien avait pour but, dans un premier temps de comprendre la notion de contrat, ses caractéristiques, fonctions et les garanties qui en peuvent être fournies. Nous invoquerons le contenu du contrat, c'est à dire, les effets de celui-ci en essayant de montrer les droits et obligations auxquels les parties seront liées. Bien qu'étant un contrat assez requérant dans la pratique bancaire, celui-ci n'a pas encore attiré l'attention du législateur de façon à établir un régime qui pourrait lui être appliqué au lieu de s'appuyer sur d'autres contrats lui étant similaires. Nous proposons l'analyse de la cessation du contrat, en se concentrant sur les moyens de la dissolution, survenue suite à la conclusion de l'accord comme la plainte, l'abrogation, l'expiration et la résolution du contrat, en laissant de côté la dissolution du contrat pour des raisons survenues avant la conclusion du contrat, comme la nullité et l'annulation.

Respiratory characteristics of Hoplostenum littorale (Siluriformes, Callichthyidae)

Hematological parameters, intraerythrocytic phosphates, hemoglobin, and whole blood Bohr effect of the South American armored catfish Hoplostenum littorale were studied during different seasons of the year. In addition, the degree of dependence on air breathing was determined for this species. The hematological parameters presented seasonal variations, which were not correlated to oxygen, temperature, and water level oscillations. Five anodic hemoglobin fractions were detected in starch gel electrophoresis. In addition to ATP, GTP and Fe-GTP being detected, 2,3-DPG was also detected in red blood cells of H. littorale. The latter is an intraerythrocytic phosphate characteristic to red blood cells of mammalians. The increased production of 2,3-DPG could be associated with decreasing Hb-O2 affinity and both features could be related to environmental temperature increase. Whole blood Bohr effect was influenced by water temperature. This study confirms H. littorale to be continuous and not obligate air breather, under all dissolved oxygen level conditions.

Micro- and mesoporous structures as drug delivery carriers for salicylic acid

The potential of salicylic acid (SA) encapsulated in porous materials as drug delivery carriers for cancer treatment was studied. Different porous structures, the microporous zeolite NaY, and the mesoporous SBA-15 and MCM-41 were used as hosts for the anti-inflammatory drug. Characterization with different techniques (FTIR, UV/vis, TGA, 1H NMR, and 13C CPMAS NMR) demonstrated the successful loading of SA into the porous hosts. The mesoporous structures showed to be very efficient to encapsulate the SA molecule. The obtained drug delivery systems (DDS) accommodated 0.74 mmol (341 mg/gZEO) in NaY and 1.07 mmol (493 mg/gZEO) to 1.23 mmol (566 mg/gZEO) for SBA-15 and MCM-41, respectively. Interactions between SA molecules and pore structures were identified. A fast and unrestricted liberation of SA at 10 min of the dissolution assay was achieved with 29.3, 46.6, and 50.1 µg/mL of SA from NaY, SBA-15, and MCM-41, respectively, in the in vitro drug release studies (PBS buffer pH 7.4, 37 °C). Kinetic modeling was used to determine the release patterns of the DDS. The porous structures and DDS were evaluated on Hs578T and MDA-MB-468 breast cancer cell lines viability. The porous structures are nontoxic to cancer cells. Cell viability reduction was only observed after the release of SA from MCM- 41 followed by SBA-15 in both breast cancer cell lines.