Development and application of NMR techniques to study water-in-CO2 microemulsions

Self-assembly is a phenomenon that occurs frequently throughout the universe. In this work, two self-assembling systems were studied: the formation of reverse micelles in isooctane and in supercritical CO2 (scCO2), and the formation of gels in organic solvents. The goal was the physicochemical study of these systems and the development of an NMR methodology to study them. In this work, AOT was used as a model molecule both to comprehensively study a widely researched system water/AOT/isooctane at different water concentrations and to assess its aggregation in supercritical carbon dioxide at different pressures. In order to do so an NMR methodology was devised, in which it was possible to accurately determine hydrodynamic radius of the micelle (in agreement with DLS measurements) using diffusion ordered spectroscopy (DOSY), the micellar stability and its dynamics. This was mostly assessed by 1H NMR relaxation studies, which allowed to determine correlation times and size of correlating water molecules, which are in agreement with the size of the shell that interacts with the micellar layer. The encapsulation of differently-sized carbohydrates was also studied and allowed to understand the dynamics and stability of the aggregates in such conditions. A W/CO2 microemulsion was prepared using AOT and water in scCO2, with ethanol as cosurfactant. The behaviour of the components of the system at different pressures was assessed and it is likely that above 130 bar reverse microemulsions were achieved. The homogeneity of the system was also determined by NMR. The formation of the gel network by two small molecular organogelators in toluene-d8 was studied by DOSY. A methodology using One-shot DOSY to perform the spectra was designed and applied with success. This yielded an understanding about the role of the solvent and gelator in the aggregation process, as an estimation of the time of gelation.

Aedes aegypti eggs oviposited on water surface collected from field ovitraps in Nova Iguaçu City, Brazil

ABSTRACT INTRODUCTION: Aedes aegypti eggs can be collected from the water surface. METHODS: Aedes aegypti oviposition from 97 field ovitraps was studied. RESULTS: Of the 16,016 eggs collected, 11,439 were obtained from paddles in ovitraps and 4,577 from water. Further, 89 (91.8%) traps contained eggs on water and 22 (22.7%) traps contained eggs only on water. CONCLUSIONS: In field traps, Aedes aegypti females usually oviposit some eggs on water surface suggesting that they might also oviposit on water of some natural breeding, and this possibility needs to be investigated. Eggs oviposited on water need to be considered for collecting trap data.

Valorization of grape pomace through hot compressed water extraction/hydrolysis

The world energy consumption is expected to increase strongly in coming years, because of the emerging economies. Biomass is the only renewable carbon resource that is abundant enough to be used as a source of energy Grape pomace is one of the most abundant agro-industrial residues in the world, being a good biomass resource. The aim of this work is the valorization of grape pomace from white grapes (WWGP) and from red grapes (RWGP), through the extraction of phenolic compounds with antioxidant activity, as well as through the extraction/hydrolysis of carbohydrates, using subcritical water, or hot compressed water (HCW). The main focus of this work is the optimization of the process for WWGP, while for RWGP only one set of parameters were tested. The temperatures used were 170, 190 and 210 °C for WWGP, and 180 °C for RWGP. The water flow rates were 5 and 10 mL/min, and the pressure was always kept at 100 bar. Before performing HCW assays, both residues were characterized, revealing that WWGP is very rich in free sugars (around 40%) essentially glucose and fructose, while RWGP has higher contents of structural sugars, lignin, lipids and protein. For WWGP the best results were achieved at 210 °C and 10 mL/min: higher yield in water soluble compounds (69 wt.%), phenolics extraction (26.2 mg/g) and carbohydrates recovery (49.3 wt.% relative to the existing 57.8%). For RWGP the conditions were not optimized (180 °C and 5 mL/min), and the values of the yield in water soluble compounds (25 wt.%), phenolics extraction (19.5 mg/g) and carbohydrates recovery (11.4 wt.% relative to the existing 33.5%) were much lower. The antioxidant activity of the HCW extracts from each assay was determined, the best result being obtained for WWGP, namely for extracts obtained at 210 °C (EC50=20.8 μg/mL; EC50 = half maximum effective concentration; EC50 = 22.1 μg/mL for RWGP, at 180 ºC).

Assessment of schistosomiasis in the semi-arid Northeast region of Brazil: the São Francisco River large-scale water transposition project

Abstract: INTRODUCTION Risk of schistosomiasis expansion to semi-arid northeastern Brazil under the influence of the Integration Project of the São Francisco River (IPSFR) was assessed. METHODS: Stool examinations of schoolchildren, epidemiological investigation, and survey of the local host snail Biomphalaria straminea were performed in five IPSFR municipalities. RESULTS Six of 4,770 examined schoolchildren were egg-positive for Schistosoma mansoni. Biomphalaria straminea was widespread, but not naturally infected with S. mansoni. Snails experimentally exposed to two laboratory S. mansoni strains yielded infection indices of 1-4.5%. CONCLUSIONS: There is evidence of active schistosomiasis transmission in the area; thus, intensive surveillance actions are required.

Secondary transmission of cryptosporidiosis associated with well water consumption: two case studies

Abstract: Cryptosporidiosis is a very prominent disease in the field of public health, and usually causes diarrhea. We describe two immunocompetent patients who presented with chronic diarrhea that was ultimately found to be caused by continuous exposure to well water contaminated with the microbial cysts (oocysts) of the Cryptosporidium spp parasite. We describe the patients' histories and possible explanations for their prolonged symptoms.

Production and characterization of electrospun composite fibers: confinement of thermosensitive microgels

Materials engineering focuses on the assembly of materials´ properties to design new products with the best performance. By using sub-micrometer size materials in the production of composites, it is possible to obtain objects with properties that none of their compounds show individually. Once three-dimensional materials can be easily customized to obtain desired properties, much interest has been paid to nanostructured poly-mers in order to build biocompatible devices. Over the past years, the thermosensitive microgels have become more common in the framework of bio-materials with potential applicability in therapy and/or diagnostics. In addition, high aspect ratio biopolymers fibers have been produced using the cost-effective method called electrospinning. Taking advantage of both microgels and electrospun fibers, surfaces with enhanced functionalities can be obtained and, therefore employed in a wide range of applications. This dissertation reports on the confinement of stimuli-responsive microgels through the colloidal electro-spinning process. The process mainly depends on the composition, properties and patterning of the precur-sor materials within the polymer jet. Microgels as well as the electrospun non-woven mats were investigated to correlate the starting materials with the final morphology of the composite fibers. PNIPAAm and PNIPAAm/Chitosan thermosensitive microgels with different compositions were obtained via surfactant free emulsion polymerization (SFEP) and characterized in terms of chemical structure, morphology, thermal sta-bility, swelling properties and thermosensitivity. Finally, the colloidal electrospinning method was carried out from spinning solutions composed of the stable microgel dispersions (up to a concentration of about 35 wt. % microgels) and a polymer solution of PEO/water/ethanol mixture acting as fiber template solution. The confinement of microgels was confirmed by Scanning Electron Microscopy (SEM). The electrospinning process was statistically analysed providing the optimum set of parameters aimed to minimize the fiber diameter, which give rise to electrospun nanofibers of PNIPAAm microgels/PEO with a mean fiber diameter of 63 ± 25 nm.

A discriminação em função da idade no direito do trabalho

In this thesis, we will treat the discrimination based on age, more specifically of older workers. In recent years, there was an increasing interest on the part of doctrine and jurisprudence on this subject. In fact, in a world in which you live a real economic crisis, older workers tend to have difficulties finding jobs or are targets of the discrimination based on age, at the time of hiring or during the contract. Thus, we will focus on discrimination. We will examine, first, the difference between direct and indirect discrimination, taking into account the importance of the burden of proof, then we will study the figures of positive action measures. Then, treat the legislative framework of the discrimination based on age, that is, in relation to the Labor Code and the Directive 2000/78/EC of November 27, 2000. Eventually, we will determine the cases in which they may accept the discrimination based on age. In fact, these differences in treatment based on age are justified, but must be aimed at a legitimate objective with appropriate and necessary means.

Consumer satisfaction with water, wastewater and waste services in Portugal

While the concept of consumer satisfaction is a central topic in modern marketing theory and practice, citizens' satisfaction with public services, and especially water and waste services, is a eld that still remains empirically rather unexplored. The following study aims to contribute to this area by analysing the determinants of user satisfaction in the water, wastewater and waste sector in Portugal, using a unique survey of 1070 consumers undertaken by the Portuguese Water and Waste Regulator ERSAR. I perform an analysis of the relation between overall service satisfaction and attributespeci c service satisfaction with an ordered logit model. I then explore if subjective consumer satisfaction can be re ected by ERSAR's technical performance indicators. The results suggest that overall consumer satisfaction is driven by consumer's satisfaction with speci c service aspects but unrelated to socioeconomic and demographic characteristics. Furthermore, I show that there is no monotonic association between ERSAR's technical performance indicators and consumers' levels of satisfaction.

Determination of fat soluble vitamins from amazonian fresh-water fishes. I. HPLC analysis of tambaqui, pirarucu and cuiu-cuiu livers .

It was found that fish livers from the Amazon have considerable amounts of vitamins A, D and E compared with the values of the standartized cod-liver oil. Tambaqui liver oil has high concentration of vitamin A1(retinol) and vitamin A2 (degidroretinol) whereas the liver oils of pirarucu and cuiu-cuiu have preferently the vitamin A2. The contents of the vitamins D and E observed in the liver oils of tambaqui and cuiu-cuiu was extremely high.

The effect of deforestation on the water cycle in the amazon basin: an attempt reformulate the problem

If widespread deforestation in Amazon results in reduced evaporative water flux, then either a decrease in evaporation is compensated locally by reduced rainfall,or else changed moisture balance expresses itself downwind in the yet undisturbed forest. The question of where rain will occur is crucial. It is suggested that the appearance of clouds and the occurrence of rainout is governed primarily by the interplay of local meteorologic and physical geography parameters with the atmospheric stability structure except for a few well-defined periods when rain is dominated by large scale atmospheric instability. This means that the study of these phenomena (local heat balances,studies on cloud formation mechanism, vertical atmospheric stability, etc.) must be made on the scale of the cloud size, a few tens of kilometers at most.

O princípio da confidencialidade na mediação em matéria civil e comercial

The purpose of the following study is to analyze the relevance of the principle of confidentiality concerning mediation on civil and commercial matters developed in Portugal. We will, essentially, try to determine just how pivotal is this principle and how it affects the effectiveness of that method of alternative dispute resolution. We believe it is fundamental to understand the true extent of this principle and its goals, emphasizing the protection given to those who decide to resort to mediation and its impact on this process. For this dissertation, we have based our analysis on the interpretation of the set rules assembled by Law nr 29/2013, April 19th, while combining it with data gathered from other laws and regulations that had also addressed mediation. Furthermore, given the fact that this subject has been regulated by Directive 2008/52/EC, we deem pertinent to include references to other European mediation regulations, namely from Germany, Spain and France. With this study, we have established that, even though the Portuguese mediation law is based on a European Directive, we have determined a more restrictive regulation for the principle of confidentiality. We have concluded that the rules regarding this principle try to preserve, above all, the trust and honesty established during the course of the mediation, while restricting the possibility of using the information disclosed during these sessions on other cases. Additionally, we believe confidentiality is such a distinctive and relevant feature that its legal framework leads us to deem it as a true obstacle to the parties’ private autonomy and their power to determine how the mediation should be carried out.

Chlorite Dismutase from perchlorate reducing bacteria. A potential biocatalyst to eliminate chlorinated species from polluted water resources and industrial wastes

Magnetospirillum (M.) sp. strain Lusitani, a perchlorate reducing bacteria (PRB), was previously isolated from a wastewater treatment plant and phylogenetic analysis was performed to classify the isolate. The DNA sequence of the genes responsible for perchlorate reduction and chlorite dismutation was determined and a model was designed based on the physiological roles of the proteins involved in the pcr-cld regulon. Chlorite dismutase (Cld) was purified from Magnetospirillum sp. strain Lusitani cells grown in anaerobiosis in the presence of perchlorate. The protein was purified up to electrophoretic grade using HPLC techniques as a 140 kDa homopentamer comprising five ~28 kDa monomers. Steady-state kinetic studies showed that the enzyme follows a Michaelis-Menten model with optimal pH and temperature of 6.0 and 5°C, respectively. The average values for the kinetic constants KM and Vmax were respectively 0.56 mM and 10.2 U, which correspond to a specific activity of 35470 U/mg and a turnover number of 16552 s-1. Cld from M. sp. strain Lusitani is inhibited by the product chloride, but not by dioxygen. Inhibition constants KiC= 460 mM and KiU= 480 mM indicated that sodium chloride is a weak mixed inhibitor of Cld, with a slightly stronger competitive character. The X-ray crystallography structure of M. sp. strain Lusitani Cld was solved at 3.0 Å resolution. In agreement with cofactor content biochemical analysis, the X-ray data showed that each Cld monomer harbors one heme b coordinated by a histidine residue (His188), hydrogen-bonded to a conserved glutamic acid residue (Glu238). The conserved neighboring arginine residue (Arg201) important for substrate positioning, was found in two different conformations in different monomers depending on the presence of the exogenous ligand thiocyanate. UV-Visible and CW-EPR spectroscopies were used to study the effect of redox agents, pH and exogenous ligands on the heme environment.

The Beglocal framework applied to B2C E-commerce

This case-study examined the use of the BeGloCal Framework applied to B2C E-commerce, for a fast moving consumer goods European manufacturing firm. It explains how the framework supported the team within the company to identify the right local market as to where to start the project, the problem for the company was to find the most appealing area to invest resources. By going through all the steps of the framework the findings led the company to London (Kensington and Chelsea). It shows how managers should act when they have to find a trade-off between standardization and adaptation.

A new credit monitoring framework for agents' networks

The purpose of this work is to develop a practicable approach for Telecom firms to manage the credit risk exposition to their commercial agents’ network. Particularly it will try to approach the problem of credit concession to clients’ from a corporation perspective and explore the particular scenario of agents that are part of the commercial chain of the corporation and therefore are not end-users. The agents’ network that served as a model for the presented study is composed by companies that, at the same time, are both clients and suppliers of the Telecommunication Company. In that sense the credit exposition analysis must took into consideration all financial fluxes, both inbound and outbound. The current strain on the Financial Sector in Portugal, and other peripheral European economies, combined with the high leverage situation of most companies, generates an environment prone to credit default risk. Due to these circumstances managing credit risk exposure is becoming increasingly a critical function for every company Financial Department. The approach designed in the current study combined two traditional risk monitoring tools: credit risk scoring and credit limitation policies. The objective was to design a new credit monitoring framework that is more flexible, uses both external and internal relationship history to assess risk and takes into consideration commercial objectives inside the agents’ network. Although not explored at length, the blueprint of a Credit Governance model was created for implementing the new credit monitoring framework inside the telecom firm. The Telecom Company that served as a model for the present work decided to implement the new Credit Monitoring framework after this was presented to its Executive Commission.