On the solubility of proteins as a function of pH: Mathematical development and application

Thermodynamic relations between the solubility of a protein and the solution pH are presented in this work. The hypotheses behind the development are that the protein chemical potential in liquid phase can be described by Henry`s law and that the solid-liquid equilibrium is established only between neutral molecules. The mathematical development results in an analytical expression of the solubility curve, as a function of the ionization equilibrium constants, the pH and the solubility at the isoelectric point. It is shown that the same equation can be obtained either by directly calculating the fraction of neutral protein molecules or by integrating the curve of the protein average charge. The methodology was successfully applied to the description of the solubility of porcine insulin as a function of pH at three different temperatures and of bovine beta-lactoglobulin at four different ionic strengths. (C) 2011 Elsevier B.V. All rights reserved.

KI effects on the reversible electrodeposition of silver on poly(ethylene oxide) for application in electrochromic devices

A new approach to electrochromics, based on the reversible coating-dissolution of an oxide from an inorganic electrochromic electrolyte consisting of a silver-amine complex in a polymer electrolyte (PEO), has proven successful. The reversible electrodeposition of silver onto indium-tin oxide coated glass (ITO) was investigated and the influence of HClO(4) and KI was evaluated. Several characteristics of the electrolyte Ag-PEO make it suitable for use in electrochromic reversible silver electrodeposition devices, such as visible absorption spectrum with an absorbance variation of 60%, an electrochromic efficiency of 5.2 cm(2) C(-1) and an ionic conductivity 4.4 x 10(-4) S cm(-1). The addition of perchloric acid improved the transparency of Ag-PEO, and potassium iodide (KI) was fundamental in setting up the process of reversible silver electrodeposition in the PEO polymeric matrix. A description of the electrochemical processes implied is presented. A number of approaches focusing on the improvement of system performance are tested. (C) 2009 Elsevier Ltd. All rights reserved.

Physical, physicochemical and chemical characterization of turf, sulphur mud and fango for cosmetic application

Focusing on the therapeutic and cosmetic potentials of the thermal water, several processes were developed to achieve a raw material known as fango which presents in its constitution water, clay and organic soil. This research work aimed at characterizing turf, sulphur mud and fango from Araxa, MG, Brazil, through physical, physicochemical, inorganic and organic assessments for cosmetic and topical product proposes. The characterization permitted the determination of relevant parameters to suggest the efficacy (presence, of ions) and safety (absence of toxic metals) of those raw materials for cosmetic and pharmaceutical utilization.

Gypsum solubility in seawater, and its application to bauxite residue amelioration

The solubilities and dissolution rates of three gypsum sources (analytical grade (AG), phosphogypsum (PG) and mined gypsum (MG)) with six MG size fractions ((mm) > 2.0, 1.0-2.0, 0.5-1.0, 0.25-0.5, 0.125-0.25, and < 0.125) were investigated in triple deionised water (TDI) and seawater to examine their suitability for bauxite residue amelioration. Gypsum solubility was greater in seawater (3.8 g L 1) than TDI (2.9 g L 1) due to the ionic strength effect, with dissolution in both TDI and seawater following first order kinetics. Dissolution rate constants varied with gypsum source (AR > PG > MG) due to reactivity and surface area differences, with 1:20 gypsum:solution suspensions reaching saturation within 15 s (AR) to 30 min (MG > 2.0). The ability of bauxite residue to adsorb Ca from solution was also examined. The quantity of the total solution Ca adsorbed was found to be small (5 %). These low rates of solution Ca adsorption combined with the comparatively rapid dissolution rates preclude the application of gypsum to the residue sand/seawater slurry as a method for residue amelioration. Instead, direct field application to the residue would ensure more efficient gypsum use. In addition, the formation of a sparingly soluble CaCO3 coating around the gypsum particles after mixing in a highly alkaline seawater/supernatant liquor (SNL) solution greatly reduced the rate of gypsum dissolution.

Cross-reactivity of Sydney funnel-web spider antivenom: neutralization of the in vitro toxicity of other Australian funnel-web (Atrax and Hadronyche) spider venoms

Australian funnel-web spiders are recognized as one of the most venomous spiders to humans world-wide. Funnel-web spider antivenom (FWS AV) reverses clinical effects of envenomation from the bite of Atrax robustus and a small number of related Hadronyche species. This study assessed the in vitro efficacy of FWS AV in neutralization of the effects of funnel-web spider venoms, collected from various locations along the eastern seaboard of Australia, in an isolated chick biventer cervicis nerve-muscle preparation. Venoms were separated by SDS-PAGE electrophoresis to compare protein composition and transblotted for Western blotting and incubation with FWS AV. SDS-PAGE of venoms revealed similar low and high molecular weight protein bands. Western blotting with FWS AV showed similar antivenom binding with protein bands in all the venoms tested. Male funnel-web spider venoms (7/7) and female venoms (5110) produced muscle contracture and fasciculation when applied to the nerve-muscle preparation. Venom effects were reversed by subsequent application of FWS AV or prevented by pretreatment of the preparation with antivenom. FWS AV appears to reverse the in vitro toxicity of a number of funnel-web spider venoms from the eastern seaboard of Australia. FWS AV should be effective in the treatment of envenomation from most, if not all, species of Australian funnel-web spiders. (C) 2001 Elsevier Science Ltd. All rights reserved.

A Divulgação de Informação sobre Responsabilidade Social nas paginas web dos Municípios Portugueses- Factores determinantes

Este estudo pretende conhecer o nível de divulgação de informação sobre responsabilidade social(RS) e analisar possíveis factores determinantes em 60 municípios portugueses. Assumindo que os municípios utilizam cada vez mais Internet como meio de comunicação com seus stakholders, a metodologia de estudo consistiu na analise de conteúdo dos websites e dos documentos disponíveis para download. com vista a determinar se para cada item de informação necessária é elaboração dos Índices de Divulgação de Informação, que permitissem medir o nível de divulgação de informação de cada município. Como forma de analisar a associação existente entre os índices de divulgação de informação criados e os potenciais factores determinantes, foram efectuados diversos testes ás hipóteses formuladas. Os resultados apontam para níveis de divulgação médios na maioria dos índices analisados. O Índice de Divulgação Total(IDT) apurado foi de 0,46. Para cada bloco de informação, o índice que apresentou um valor mais alto foi o da Informação Económica(IDE) com 0,66, seguindo-se o da Informação Social(IDS) com 0,61 e o Ambiental(IDA) com 0,36. O Índice de divulgação de informação genérica(IDG) sobre o RS foi o qeu apresentou valores mais reduzidos, 0,22. Foi efectuada uma analise univariada e bivariada que surgem vários factores como explicativos dos níveis de divulgação de informação. Da aplicação do Modelo de Regressão Linear Multiplica resulta que o IDG é influenciado pelo facto e o município implementar a Agenda 21 Local(A21L) e a pela percentagem de despesas ambientais nas despesas totais(DAMB);que apenas a elevada percentagem de despesas de licenciados(ESCOL)influência o IDE; e a localização do município(LOC, a A21L e a Carga Fiscal(FISC) tem influência no IDA e que a percentagem de habitantes com idade <19 anos e >65 anos(POPID) influencia negativamente o IDA; por ultimo e no que diz respeito ao Índice de Divulgação Total, a CARAT, a A21L, o possuir Certificação e a FISC influenciam positivamente o IDT, enquanto que a POPID influencia negativamente.

Modelo para avaliação da qualidade de conteúdos de sítios Web de Unidades de Saúde

Os sítios Web são a face das instituições, mas há evidências de frequentemente serem pouco cuidados, sobretudo ao nível dos seus conteúdos. Nesta tese apresentamos uma investigação que desenvolve um modelo de avaliação da qualidade dos conteúdos de sítios Web de unidades de saúde. A revisão bibliográfica, realizada neste trabalho, permitiu identificar as dimensões e atributos de avaliação da qualidade de conteúdos de sítios Web mais considerados pelos diversos autores dos trabalhos mais importantes da área, mas não um modelo que, a partir deles, fosse capaz de os avaliar objetivamente. Assim, levantou-se o problema de saber se todos os atributos têm a mesma importância. Atributos mais importantes devem dar maior contributo na avaliação pretendida e o modelo a ser considerado deve refletir isso, adicionalmente a ferramenta de avaliação deveria ser intuitiva e rápida na aplicação. Para determinar a importância de cada atributo aplicou-se o Método Delphi tendo sido necessário três rondas para encontrar consenso relativamente à importância dos atributos a que se seguiu a aplicação de um conjunto de modelos estatísticos de forma a determinar uma métrica consistente e que permitisse a comparação de pontuações entre sítios web. De acordo com as questões de investigação e os objetivos definidos foi possível encontrar um modelo que fornecesse uma medida objetiva, normalizada e consistente acerca da qualidade de conteúdos de sítios web de unidades de saúde

O ataque ao sítio web da Al-Jazeera

O ataque ao sítio web da Al-Jazeera, levado a cabo por hackers na primeira semana da Guerra do Iraque, terá constituído o primeiro sinal importante da assimilação da imprensa online pelo campo da guerra informática, apresentada desde há décadas como «guerra do futuro», mas mantendo um estatuto marginal no quadro dos conflitos militares entre estados. O acontecimento atravessa o terreno cientificamente minado do estudo da Internet, nomeadamente pela «retórica de substituição» que acompanhou o nascimento das principais tecnologias de comunicação e que regressou em força com a chegada do novo meio. Mas este e outros perigos não nos devem inibir de encarar de frente o significado do bloqueio do sítio web da Al-Jazeera, nas suas dimensões bélica, simbólica e política. É o que este artigo procura fazer, a partir da confrontação das teorizações já produzidas acerca das notícias online e da guerra informática com um conjunto de dados empíricos relevantes.

Synthesis, characterization and antiproliferative activity on cancer cell lines of new ionic liquids from ampicillin

Ionic Liquids (ILs) are ionic compounds that possess melting temperature below 100ºC and they have been a topic of great interest since the mid-1990s due to their unique properties. The range of IL uses has been broadened, due to a significant increase in the variety of physical, chemical and biological ILs properties. They are now used as Active Pharmaceutical Ingredients (APIs) and recent interests are focused on their application as innovative solutions in new medical treatment and delivery options.1 In this work, our principal objective was the synthesis and investigation of physicochemical and medical properties of ionic liquids (ILs) and organic salts from ampicillin. This approach is of huge interest in pharmaceutical industry as cation and anion composition of ILs and organic salts can greatly alter their desired properties, namely the melting temperature and even synergistic effects can be obtained.2,3 For the synthesis of these compounds we used a recently developed method proposed by Ohno et al.4 for the preparation of quaternary ammonium and phosphonium hydroxides, that were neutralized by ampicillin. After purification we obtained pure ILs and salts in good yields. These ILs shows good antimicrobial and antifungal activities. As it is well known that some ionic liquids containing phosphonium and ammonium cation also shows anti-cancer activity1,5 we also decided to study these compounds against some cancer cell lines.

Metal deposition using Ionic liquids

There is an interest to create zinc/tin alloys to replace cadmium as a corrosion protective coating material. Existing aqueous electroplating systems for these alloys are commercially available but have several limitations. Dangerous and highly toxic complexing agents are uses e.g. cyanides. To overcome these problems, ionic liquids could provide a solution to obtain an alloy containing 20 to 30% of zinc. Ionic liquids (IL’s) often have wider electrochemical windows which allow the deposition of e.g. refractive metals that can not be deposited from aqueous solutions. In IL’s it is often not necessary to add complexing agents. The Zn/Sn alloy deposition from IL’s is therefore a promising application for the plating industry. Nevertheless, there are some issues with this alternative for aqueous systems. The degradation of the organic components, the control of the concentration of two metals and the risk of a two phase deposition instead of an alloy had to be overcome first. It is the main purpose of this thesis to obtain a Zn/Sn alloy with 20% zinc using IL’s as an electrolyte. First a separate study was performed on both the zinc and the tin deposition. Afterwards, an attempt to deposit a Zn/Sn alloy was made. An introduction to a study about the electrodeposition of refractive metals concludes this work. It initiated the research for oxygen-free IL’s to deposit molybdenum or tungsten. Several parameters (temperature, metal source and concentration, organic complexing agents,…) were optimized for both the zinc, tin and zinc/tin deposition. Experiments were performed both in a parallel plate cell and a Hull cell, so as to investigate the effect of current density as well. Ethaline200 was selected as electrolyte. As substrate, brass and iron were selected, while as anode a plate of the metal to deposit was chosen, tin for the alloy. The best efficiencies were always obtained on brass; however the iron substrate resulted in the best depositions. A concentration of 0.27M ZnCl2, 0.07M SnCl2 with 0.015M of K3-HEDTA as complexant resulted in a deposition containing the desired alloy with the amount of 20% zinc and 80% tin with good appearance. Refractory metals as molybdenum and tungsten cannot be electrodeposited from aqueous solutions without forming a co-deposition with Ni, Co or Fe. Here, IL’s could again provide a solution. A first requirement is the dissolution of a metal source. MoO3 could be suitable, however there are doubts about using oxides. Oxygen-free IL’s were sought for. A first attempt was the combination of ZnCl2 with chlormequat (CCC), which gave liquids below 150°C in molar ratios of 2 : 1 and 3 : 1. Unfortuna tely, MoO3 didn’t dissolve in these IL’s. Another route to design oxygen-free IL’s was the synthesis of quaternary ammonium salts. None of the methods used, proved viable as reaction time was long and resulted in very low yields. Therefore, no sufficient quantities were obtained to perform the possible electrochemical behavior of refractive metals.

Uma abordagem de alto nível para a verificação de conteúdos na web

A manutenção do conteúdo web pode ser uma tarefa difícil, especialmente se considerarmos websites em que muitos utilizadores têm permissões para alterar o seu conteúdo. Um exemplo deste tipo de websites são os wikis. Se por um lado permitem rápida disseminação de conhecimento, por outro lado implicam um grande esforço para verificar a qualidade do seu conteúdo. Nesta tese analisamos diferentes abordagens à modelação de websites, especialmente para a verificação de conteúdo, onde contribuímos com uma extensão à ferramenta VeriFLog para a tornar mais adequada à verificação de conteúdos em websites colaborativos.

Chlormequat selective electrodes: construction, evaluation and application at FIA systems

A flow injection analysis (FIA) system having a chlormequat selective electrode is proposed. Several electrodes with poly(vinyl chloride) based membranes were constructed for this purpose. Comparative characterization suggestedthe use of membrane with chlormequat tetraphenylborate and dibutylphthalate. On a single-line FIA set-up, operating with 1x10-2 mol L-1 ionic strength and 6.3 pH, calibration curves presented slopes of 53.6±0.4mV decade-1 within 5.0x10-6 and1.0x10-3 mol L-1, andsquaredcorrelation coefficients >0.9953. The detection limit was 2.2x10-6 mol L-1 and the repeatability equal to ±0.68mV (0.7%). A dual-channel FIA manifold was therefore constructed, enabling automatic attainment of previous ionic strength andpH conditions and thus eliminating sample preparation steps. Slopes of 45.5±0.2mV decade -1 along a concentration range of 8.0x10-6 to 1.0x10-3 mol L-1 with a repeatability ±0.4mV (0.69%) were obtained. Analyses of real samples were performed, and recovery gave results ranging from 96.6 to 101.1%.

Flow-injection potentiometric method for the routine determination of chloride: application to bread analysis

Bread is consumed worldwide by man, thus contributing to the regular ingestion of certain inorganic species such as chloride. It controls the blood pressure if associated to a sodium intake and may increase the incidence of stomach ulcer. Its routine control should thus be established by means of quick and low cost procedures. This work reports a double- channel flow injection analysis (FIA) system with a new chloride sensor for the analysis of bread. All solutions are prepared in water and necessary ionic strength adjustments are made on-line. The body of the indicating electrode is made from a silver needle of 0.8 mm i.d. with an external layer of silver chloride. These devices were constructed with different lengths. Electrodes of 1.0 to 3.0 cm presented better analytical performance. The calibration curves under optimum conditions displayed Nernstian behaviour, with average slopes of 56 mV decade-1, with sampling rates of 60 samples h-1. The method was applied to analyze several kinds of bread, namely pão de trigo, pão integral, pão de centeio, pão de mistura, broa de milho, pão sem sal, pão meio sal, pão-de-leite, and pão de água. The accuracy and precision of the potentiometric method were ascertained by comparison to a spectrophotometric method of continuous segmented flow. These methods were validated against ion-chromatography procedures.

Design and implementation of a behaviorally typed programming system for web services

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para a obtenção do Grau de Mestre em Engenharia Informática.