Sensitized terbium(iii) macrocyclic-phthalimide complexes as luminescent pH switches

Four new macrocyclic-phthalimide ligands were synthesised via the coupling of N-(3-bromopropyl)phthalimide either to cyclen (1,4,7,10- tetraazacyclododecane) itself or its carboxylate-functionalized analogues, and photophysical studies were carried out on their corresponding Tb(iii) complexes in aqueous media as a function of pH. Luminescence intensities of Tb·L^1a-Tb·L^3a were in 'switched off' mode under acidic conditions (pH < 4), and were activated on progression to basic conditions as the phthalimido functions therein were hydrolysed to their corresponding phthalamates Tb·L^1b-Tb·L^3b. Emission of phthalamate-based macrocyclic Tb(iii) complexes Tb·L ^1b-Tb·L^3b was in 'switched on' mode between pH 4 and 11, exhibiting high quantum yields (Φ) and long lifetimes (τ) of the order of milliseconds at pH ∼ 6. Tb(iii) emissions were found to decline with increasing number of chromophores. The values of Φ and τ were 46% and 2.4 ms respectively for Tb·L^1b at pH ∼ 6 when activated. This is the best pH-dependent sensor based on a Tb(iii) complex reported to date, benefiting from the macrocyclic architecture of the ligand. © 2013 The Royal Society of Chemistry.

Chloride transport and the resulting corrosion of steel bars in alkali activated slag concretes

As the relative performance of alkali activated slag (AAS) concretes in comparison to Portland cement (PC) counterparts for chloride transport and resulting corrosion of steel bars is not clear, an investigation was carried out and the results are reported in this paper. The effect of alkali concentration and modulus of sodium silicate solution used in AAS was studied. Chloride transport and corrosion properties were assessed with the help of electrical resistivity, non-steady state chloride diffusivity, onset of corrosion, rate of corrosion and pore solution chemistry. It was found that: (i) although chloride content at surface was higher for the AAS concretes, they had lower chloride diffusivity than PC concrete; (ii) pore structure, ionic exchange and interaction effect of hydrates strongly influenced the chloride transport in the AAS concretes; (iii) steel corrosion resistance of the AAS concretes was comparable to that of PC concrete under intermittent chloride ponding regime, with the exception of 6% Na2O and Ms of 1.5; (iv) the corrosion behaviour of the AAS concretes was significantly influenced by ionic exchange, carbonation and sulphide concentration; (v) the increase of alkali concentration of the activator generally increased the resistance of AAS concretes to chloride transport and reduced its resulting corrosion, and a value of 1.5 was found to be an optimum modulus for the activator for improving the chloride transport and the corrosion resistance.

Chloride induced corrosion of steel bars in alkali activated slag concretes

The studies on chloride induced corrosion of steel bars in alkali activated slag (AAS) concretes are scarcely reported in the past. In order to make this issue clearer and compare the corrosion performance of AAS with Portland cement (PC) counterpart, an investigation was carried out and the results are reported in this paper. Corrosion properties were assessed with the help of rate of corrosion, electrical resistivity and pore solution chemistry. It was found that: (i) steel corrosion resistance of the AAS concretes was comparable or in some cases even worse than that of Portland cement (PC) concrete under intermittent chloride ponding regime; (ii) the corrosion behaviour of the AAS concretes was significantly influenced by ionic exchange, carbonation and sulphide concentration; (iii) the increase of alkali concentration of the activator generally reduced chloride resulting corrosion, and a value of 1.5 was found to be an optimum modulus for the activator for improving the corrosion resistance.

Effect of high pressure processing in combination with Weissella viridescens as a protective culture against Listeria monocytogenes in ready-to-eat salads of different pH

This study explored the effect of HPP (400 MPa/1 min) and a Weissella viridescens protective culture, alone or in conjunction, against Listeria monocytogenes in ready-to-eat (RTE) salads with different pH values (4.32 and 5.59) during storage at 4 and 12 °C. HPP was able to reduce the counts of the pathogen after treatment achieving approximately a 4.0 and 1.5 log CFU/g reduction in the low and higher pH RTE salad, respectively. However, L. monocytogenes was able to recover and grow during subsequent storage. W. viridescens grew in both RTE salads at both storage temperatures, with HPP resulting in only a small immediate reduction of W. viridescens ranging from 0.50 to 1.2 log CFU/g depending on the pH of the RTE salad. For the lower pH RTE salad, the protective culture was able to gradually reduce the L. monocytogenes counts during storage whereas for the higher pH RTE salad in some cases it delayed growth significantly or exerted a bacteriostatic effect. exerted a bacteriostatic effect. The results revealed that the increased storage temperature led to an increase in the inactivation/inhibition of L. monocytogenes in the presence of W. viridescens. The combination of HPP and W. viridescens is a promising strategy to control L. monocytogenes and can increase safety even when a break in the chill chain occurs.

Comorbidity in severe asthma requiring systemic corticosteroid therapy: cross-sectional data from the Optimum Patient Care Research Database and the British Thoracic Difficult Asthma Registry

Objective: To determine the prevalence of systemic corticosteroid-induced morbidity in severe asthma.
Design: Cross-sectional observational study.Setting The primary care Optimum Patient Care Research Database and the British Thoracic Society Difficult Asthma Registry.
Participants: Optimum Patient Care Research Database (7195 subjects in three age- and gender-matched groups)—severe asthma (Global Initiative for Asthma (GINA) treatment step 5 with four or more prescriptions/year of oral corticosteroids, n=808), mild/moderate asthma (GINA treatment step 2/3, n=3975) and non-asthma controls (n=2412). 770 subjects with severe asthma from the British Thoracic Society Difficult Asthma Registry (442 receiving daily oral corticosteroids to maintain disease control).
Main outcome measures: Prevalence rates of morbidities associated with systemic steroid exposure were evaluated and reported separately for each group.
Results: 748/808 (93%) subjects with severe asthma had one or more condition linked to systemic corticosteroid exposure (mild/moderate asthma 3109/3975 (78%), non-asthma controls 1548/2412 (64%); p<0.001 for severe asthma versus non-asthma controls). Compared with mild/moderate asthma, morbidity rates for severe asthma were significantly higher for conditions associated with systemic steroid exposure (type II diabetes 10% vs 7%, OR=1.46 (95% CI 1.11 to 1.91), p<0.01; osteoporosis 16% vs 4%, OR=5.23, (95% CI 3.97 to 6.89), p<0.001; dyspeptic disorders (including gastric/duodenal ulceration) 65% vs 34%, OR=3.99, (95% CI 3.37 to 4.72), p<0.001; cataracts 9% vs 5%, OR=1.89, (95% CI 1.39 to 2.56), p<0.001). In the British Thoracic Society Difficult Asthma Registry similar prevalence rates were found, although, additionally, high rates of osteopenia (35%) and obstructive sleep apnoea (11%) were identified.

Conclusions: Oral corticosteroid-related adverse events are common in severe asthma. New treatments which reduce exposure to oral corticosteroids may reduce the prevalence of these conditions and this should be considered in cost-effectiveness analyses of these new treatments.

An optimized reverse-phase high performance liquid chromatographic method for evaluating percutaneous absorption of glucosamine hydrochloride

A relatively simple, selective, precise and accurate high performance liquid chromatography (HPLC) method based on a reaction of phenylisothiocyanate (PITC) with glucosamine (GL) in alkaline media was developed and validated to determine glucosamine hydrochloride permeating through human skin in vitro. It is usually problematic to develop an accurate assay for chemicals traversing skin because the excellent barrier properties of the tissue ensure that only low amounts of the material pass through the membrane and skin components may leach out of the tissue to interfere with the analysis. In addition, in the case of glucosamine hydrochloride, chemical instability adds further complexity to assay development. The assay, utilising the PITC-GL reaction was refined by optimizing the reaction temperature, reaction time and PITC concentration. The reaction produces a phenylthiocarbamyl-glucosamine (PTC-GL) adduct which was separated on a reverse-phase (RP) column packed with 5 microm ODS (C18) Hypersil particles using a diode array detector (DAD) at 245 nm. The mobile phase was methanol-water-glacial acetic acid (10:89.96:0.04 v/v/v, pH 3.5) delivered to the column at 1 ml min-1 and the column temperature was maintained at 30 degrees C. Galactosamine hydrochloride (Gal-HCl) was used as an internal standard. Using a saturated aqueous solution of glucosamine hydrochloride, in vitro permeation studies were performed at 32+/-1 degrees C over 48 h using human epidermal membranes prepared by a heat separation method and mounted in Franz-type diffusion cells with a diffusional area 2.15+/-0.1 cm2. The optimum derivatisation reaction conditions for reaction temperature, reaction time and PITC concentration were found to be 80 degrees C, 30 min and 1% v/v, respectively. PTC-Gal and GL adducts eluted at 8.9 and 9.7 min, respectively. The detector response was found to be linear in the concentration range 0-1000 microg ml-1. The assay was robust with intra- and inter-day precisions (described as a percentage of relative standard deviation, %R.S.D.) <12. Intra- and inter-day accuracy (as a percentage of the relative error, %RE) was <or=-5.60 and <or=-8.00, respectively. Using this assay, it was found that GL-HCl permeates through human skin with a flux 1.497+/-0.42 microg cm-2 h-1, a permeability coefficient of 5.66+/-1.6x10(-6) cm h-1 and with a lag time of 10.9+/-4.6 h.

Mercury (II) removal from aqueous solutions by microporous materials

O Mercúrio é um dos metais pesados mais tóxicos existentes no meio ambiente, é persistente e caracteriza-se por bioamplificar e bioacumular ao longo da cadeia trófica. A poluição com mercúrio é um problema à escala global devido à combinação de emissões naturais e emissões antropogénicas, o que obriga a políticas ambientais mais restritivas sobre a descarga de metais pesados. Consequentemente o desenvolvimento de novos e eficientes materiais e de novas tecnologias para remover mercúrio de efluentes é necessário e urgente. Neste contexto, alguns materiais microporosos provenientes de duas famílias, titanossilicatos e zirconossilicatos, foram investigados com o objectivo de avaliar a sua capacidade para remover iões Hg2+ de soluções aquosas. De um modo geral, quase todos os materiais estudados apresentaram elevadas percentagens de remoção, confirmando que são bons permutadores iónicos e que têm capacidade para serem utilizados como agentes descontaminantes. O titanossilicato ETS-4 foi o material mais estudado devido à sua elevada eficiência de remoção (>98%), aliada à pequena quantidade de massa necessária para atingir essa elevada percentagem de remoção. Com apenas 4 mg⋅dm-3 de ETS-4 foi possível tratar uma solução com uma concentração igual ao valor máximo admissível para descargas de efluentes em cursos de água (50 μg⋅dm-3) e obter água com qualidade para consumo humano (<1.0 μg⋅dm-3), de acordo com a legislação Portuguesa (DL 236/98). Tal como para outros adsorbentes, a capacidade de remoção de Hg2+ do ETS- 4 depende de várias condições experimentais, tais como o tempo de contacto, a massa, a concentração inicial de mercúrio, o pH e a temperatura. Do ponto de vista industrial as condições óptimas para a aplicação do ETS-4 são bastante atractivas, uma vez que não requerem grandes quantidades de material e o tratamento da solução pode ser feito à temperatura ambiente. A aplicação do ETS-4 torna-se ainda mais interessante no caso de efluentes hospitalares, de processos de electro-deposição com níquel, metalúrgica, extracção de minérios, especialmente ouro, e indústrias de fabrico de cloro e soda cáustica, uma vez que estes efluentes apresentam valores de pH semelhantes ao valor de pH óptimo para a aplicação do ETS-4. A cinética do processo de troca iónica é bem descrita pelo modelo Nernst-Planck, enquanto que os dados de equilíbrio são bem ajustados pelas isotérmicas de Langmuir e de Freundlich. Os parâmetros termodinâmicos, ΔG° and ΔH° indicam que a remoção de Hg2+ pelo ETS-4 é um processo espontâneo e exotérmico. A elevada eficiência do ETS-4 é confirmada pelos valores da capacidade de remoção de outros materiais para os iões Hg2+, descritos na literatura. A utilização de coluna de ETS-4 preparada no nosso laboratório, para a remoção em contínuo de Hg2+ confirma que este material apresenta um grande potencial para ser utilizado no tratamento de águas. ABSTRACT: Mercury is one of the most toxic heavy metals, exhibiting a persistent character in the environment and biota as well as bioamplification and bioaccumulation along the food chain. Natural inputs combined with the global anthropogenic sources make mercury pollution a planetary-scale problem, and strict environmental policies on metal discharges have been enforced. The development of efficient new materials and clean-up technologies for removing mercury from effluents is, thus, timely. In this context, in my study, several microporous materials from two families, titanosilicates and zirconosilicates were investigated in order to assess their Hg2+ sorption capacity and removal efficiency, under different operating conditions. In general, almost all microporous materials studied exhibited high removal efficiencies, confirming that they are good ion exchangers and have potential to be used as Hg2+ decontaminant agents. Titanosilicate ETS-4 was the material most studied here, by its highest removal efficiency (>98%) and lowest mass necessary to attain it. Moreover, according with the Portuguese legislation (DL 236/98) it is possible to attain drinking water quality (i.e. [Hg2+]< 1.0 μg⋅dm-3) by treating a solution with a Hg2+ concentration equal to the maximum value admissible for effluents discharges into water bodies (50 μg⋅dm-3), using only 4 mg⋅dm-3 of ETS-4. Even in the presence of major freshwater cations, ETS-4 removal efficiency remains high. Like for other adsorbents, the sorption capacity of ETS-4 for Hg2+ ions is strongly dependent on the operating conditions, such as contact time, mass, initial Hg2+ concentration and solution pH and, to a lesser extent, temperature. The optimum operating conditions found for ETS-4 are very attractive from the industrial point of view because the application of ETS-4 for the treatment of wastewater and/or industrial effluents will not require larges amounts of adsorbent, neither energy supply for temperature adjustments becoming the removal process economically competitive. These conditions become even more interesting in the case of medical institutions liquid, nickel electroplating process, copper smelter, gold ore tailings and chlor-alkali effluents, since no significant pH adjustments to the effluent are necessary. The ion exchange kinetics of Hg2+ uptake is successfully described by the Nernst-Planck based model, while the ion exchange equilibrium is well fitted by both Langmuir and Freundlich isotherms. Moreover, the feasibility of the removal process was confirmed by the thermodynamic parameters (ΔG° and ΔH°) which indicate that the Hg2+ sorption by ETS-4 is spontaneous and exothermic. The higher efficiency of ETS-4 for Hg2+ ions is corroborate by the values reported in literature for the sorption capacity of other adsorbents for Hg2+ ions. The use of an ETS-4 fixed-bed ion exchange column, manufactured in our laboratory, in the continuous removal of Hg2+ ions from solutions confirms that this titanosilicate has potential to be used in industrial water treatment.

Temperature, pH, and conductivity control of the nutrient solution of an hydroponic greenhouse

One of the aspects of modern agriculture is characterised by a culture without soil (hydroponic cultures). These culture techniques are identified by possessing automatic control systems to control the nutrient solution. In first hydroponic cultures this control was accomplished by “on- off” analog controllers that applied a single control law implemented in hardware. Therefore, the changes of the control law resulted in the change of all interface electronics. In digital control implemented by micro-controllers the alteration of such control law is easily performed by changing only a computer program, leaving untouched all the interface hardware. In this way, the use and substitution of the control strategy is improved, as well, the use of advanced control strategies.

Sperm motility in Solea senegalensis: effect of temperature, salinity, pH and ovarian fluid

A análise da mobilidade seminal é uma ferramenta importante para reprodução em aquacultura. Esta é uma técnica in vitro que auxilia a estabulação, manutenção e selecção de lotes de reprodutores. A análise de mobilidade seminal pode tornar-se potencialmente uma ferramenta para o melhoramento das condições do ambiente de fertilização. A utilização do software CASA (Computer Assisted Sperm Analysis) revolucionou a descrição e quantificação específica da mobilidade seminal. A maioria da informação recolhida sobre mobilidade de sémen de peixes baseia-se em espécies de água doce, pelo que é crucial conhecer as condições óptimas de activação da mobilidade de espermatozóides para novas espécies de de água salgada de interesse em aquacultura tal como Solea senegalensis. A optimização das condições de fertilização desta espécie é particularmente importante já que os lotes de reprodutores em cativeiro podem desenvolver disfunções reprodutoras. Este trabalho teve como objectivo realizar a avaliação das condições óptimas de activação da mobilidade do sémen em S. senegalensis em termos de temperatura, salinidade e pH. O segundo objectivo foi realizar a avaliação da influência de fluido ovárico homólogo (S. senegalensis) e heterólogo (Epinephelus marginatus) na mobilidade seminal de S. senegalensis. Deste modo foram realizados dois conjuntos de experiências: 1) mobilidade de sémen de 7 machos analisado através do CASA em diferentes temperaturas, salinidades e pH, 2) mobilidade de sémen de 8 machos activados na presença de diferentes concentrações de fluido ovárico. Os parâmetros do CASA foram registados e posteriormente analisados através de médias e cluster analysis. Concluiu-se que temperaturas mais elevadas (20 ºC) e baixas salinidades (25 ‰ e 30 ‰) da solução de activação ocorre um melhoramento das características de mobilidade seminal, tal como a velocidade. A presença de fluido ovárico em baixas concentrações melhora as características da mobilidade seminal assim como a longevidade dos espermatozóides. O fluido ovárico é consequentemente um factor que estimula a mobilidade seminal que tem sido negligenciado em estudos anteriores. Este estudo demonstrou que durante a época de reprodução a temperatura da água (20 ºC) e a salinidade (25 ‰ e 30 ‰) no tanque são os principais factores que melhoram a activação da mobilidade do sémen, sendo consequentemente uma contribuição importante para compreender a dinâmica do processo de fertilização em S. senegalensis.

Instrumentação e controlo para regulação de pH em sistemas de cultivo de organismos aquáticos

A Ria Formosa é um tesouro ambiental sem paralelo, preservando uma fauna e flora únicas no mundo. A riqueza deste habitat é de enorme importância para a região, e extremamente apetecível para cientistas oriundos de todas as partes do globo, que aqui frequentemente se deslocam para conduzirem estudos científicos e experiências. O Centro de Ciências do Mar (CCMAR) da Universidade do Algarve (que inclui o Centro Experimental do Ramalhete) conduz estudos e experiências neste palco, estudos que são de inquestionável valor para o conhecimento e desenvolvimento científico. Um assunto que está a merecer a atenção da comunidade científica mundial nos últimos anos é a questão da acidificação dos oceanos. A diminuição gradual do pH das águas pode vir a ter graves repercussões nos ecossistemas marinhos, e o Centro Experimental do Ramalhete tem vindo a conduzir experiências com fauna e flora provenientes da Ria Formosa em águas com níveis de pH mais reduzido, condições que se prevê que os oceanos venham a ter no futuro. Os equipamentos de instrumentação e controlo a que o Centro tem acesso condicionam as experiências que ali são levadas a cabo pelos investigadores, pelo que o desenvolvimento de equipamentos adequados incorporando tecnologias apropriadas permitiria a realização de novas e melhores experiências no campo da biologia marinha. Ao nível do controlo existe uma lacuna no mercado, entre controladores para aquariofilia demasiado simples e controladores industriais demasiado dispendiosos e complexos. Esta dissertação pretende colmatar essa lacuna através do desenvolvimento de um protótipo de um sistema distribuído microcontrolado para aquisição de dados e controlo de pH que vá ao encontro das necessidades dos investigadores do Centro e que se pretende simples, modular, flexível, económico e expansível no futuro. O foco centra-se no desenvolvimento da instrumentação necessária para as medições de temperatura e pH, e depois no estudo de uma malha de controlo PID utilizando como base um modelo do sistema obtido através de resultados experimentais, para o controlo automático do pH.

Problems in the use of benzoic acid for estimating the internal pH of yeasts

Some yeasts have the peculiar ability to grow in the presence of weak acids at rather low pH. These conditions are predominant in preserved foods and beverages such as fruit concentrates, juices, wine, where these yeasts are responsible for spoilage. The main preservatives currently utilized by food industries are sorbic, propionic, benzoic acids and SO2. It is usually assumed that weak acids diffuse through the plasma membrane in the undissociated form. In the cytoplasm, where the pH is higher, dissociation occurs resulting in accumulation of the lipid-insoluble anion and internal acidification. This is probably a very general mechanism of preventing microbial growth in foods.

Measurement of pH: comparing methods across the Kuroshio Extension

Senior thesis written for Oceanography 445

pH Limitations in environmental geochemical monitoring

Senior thesis written for Oceanography 445

Electrospun pH-sensitive core–shell polymer nanocomposites fabricated using a tri-axial process

A modified tri-axial electrospinning process was developed for the generation of a new type of pH-sensitive polymer/lipid nanocomposite. The systems produced are able to promote both dissolution and permeation of a model poorly water-soluble drug. First, we show that it is possible to run a tri-axial process with only one of the three fluids being electrospinnable. Using an electrospinnable middle fluid of Eudragit S100 (ES100) with pure ethanol as the outer solvent and an unspinnable lecithin-diclofenac sodium (PL–DS) core solution, nanofibers with linear morphology and clear core/shell structures can be fabricated continuously and smoothly. X-ray diffraction proved that these nanofibers are structural nanocomposites with the drug present in an amorphous state. In vitro dissolution tests demonstrated that the formulations could preclude release in acidic conditions, and that the drug was released from the fibers in two successive steps at neutral pH. The first step is the dissolution of the shell ES100 and the conversion of the core PL–DS into sub-micron sized particles. This frees some DS into solution, and later the remaining DS is gradually released from the PL–DS particles through diffusion. Ex vivo permeation results showed that the composite nanofibers give a more than twofold uplift in the amount of DS passing through the colonic membrane as compared to pure DS; 74% of the transmitted drug was in the form of PL–DS particles. The new tri-axial electrospinning process developed in this work provides a platform to fabricate structural nanomaterials, and the core–shell polymer-PL nanocomposites we have produced have significant potential applications for oral colon-targeted drug delivery.