Sulphonamide-imprinted sol–gel materials as ionophores in potentiometric transduction

This work proposes different kind of solid-contact graphite-based electrodes for the selective determination of sulphonamides (SPHs) in pharmaceuticals, biological fluids and aquaculture waters. Sulfadiazine (SDZ) and sulfamethoxazole (SMX) were selected for this purpose for being the most representative compounds of this group. The template molecules were imprinted in sol–gel (ISG) and the resulting material was used as detecting element. This was made by employing it as either a sensing layer or an ionophore of PVC-based membranes and subsequent potentiometric transduction, a strategy never reported before. The corresponding non-imprinted sol–gel (NISG) membranes were used as blank. The effect of plasticizer and kind/charge of ionic lipophilic additive was also studied. The best performance in terms of slope, linearity ranges and signal reproducibility and repeatability was achieved by PVC membranes including a high dielectric constant plasticizer and 15 mg of ISG particles. The corresponding average slope was −51.4 and −52.4 mV/decade, linear responses were 9.0 × 10−6 and 1.7 × 10−5 M, and limits of detection were 0.74 and 1.3 μg/mL for SDZ and for SMX, respectively. Good selectivity with log Kpot < −0.3 was observed for carbonate, chloride, fluoride, hydrogenocarbonate, nitrate, nitrite, phosphate, cyanide, sulfate, borate, persulphate, citrate, tartrate, salicylate, tetracycline, ciprofloxacin, sulphamerazine, sulphatiazole, dopamine, glucose, galactose, cysteine and creatinine. The best sensors were successfully applied to the analysis of real samples with relative errors ranging from −6.8 to + 3.7%.

Sulfadiazine-selective determination in aquaculture environment: Selective potentiometric transduction by neutral or charged ionophores

Solid-contact sensors for the selective screening of sulfadiazine (SDZ) in aquaculture waters are reported. Sensor surfaces were made from PVC membranes doped with tetraphenylporphyrin-manganese(III) chloride, α-cyclodextrin, β-cyclodextrin, or γ-cyclodextrin ionophores that were dispersed in plasticizer. Some membranes also presented a positive or a negatively charged additive. Phorphyrin-based sensors relied on a charged carrier mechanism. They exhibited a near-Nernstian response with slopes of 52 mV decade−1 and detection limits of 3.91 × 10−5 mol L−1. The addition of cationic lipophilic compounds to the membrane originated Nernstian behaviours, with slopes ranging 59.7–62.0 mV decade−1 and wider linear ranges. Cyclodextrin-based sensors acted as neutral carriers. In general, sensors with positively charged additives showed an improved potentiometric performance when compared to those without additive. Some SDZ selective membranes displayed higher slopes and extended linear concentration ranges with an increasing amount of additive (always <100% ionophore). The sensors were independent from the pH of test solutions within 2–7. The sensors displayed fast response, always <15 s. In general, a good discriminating ability was found in real sample environment. The sensors were successfully applied to the fast screening of SDZ in real waters samples from aquaculture fish farms. The method offered the advantages of simplicity, accuracy, and automation feasibility. The sensing membrane may contribute to the development of small devices allowing in locus measurements of sulfadiazine or parent-drugs.

Trimethoprim-selective electrodes with molecularly imprinted polymers acting as ionophores and potentiometric transduction on graphite solid-contact

This work proposes a new biomimetic sensor material for trimethoprim. It is prepared by means of radical polymerization, having trimethylolpropane trimethacrylate as cross-linker, benzoyl peroxide as radicalar iniciator, chloroform as porogenic solvent, and methacrylic acid and 2-vinyl pyridine as monomers. Different percentages of sensor in a range between 1 and 6% were studied. Their behavior was compared to that obtained with ion-exchanger quaternary ammonium salt (additive tetrakis(p-chlorophenyl)borate or tetraphenylborate). The effect of an anionic additive in the sensing membrane was also tested. Trimethoprim sensors with 1% of imprinted particles from methacrylic acid monomers showed the best response in terms of slope (59.7 mV/decade) and detection limit (4.01 × 10− 7 mol/L). These electrodes displayed also a good selectivity towards nickel, manganese aluminium, ammonium, lead, potassium, sodium, iron, chromium, sulfadiazine, alanine, cysteine, tryptophan, valine and glycine. The sensors were not affected by pH changes from 2 to 6. They were successfully applied to the analysis of water from aquaculture.

Separating sequential equilibrium in a Bayesian international duopoly

We consider two Cournot firms, one located in the home country and the other in the foreign country, producing substitute goods for consumption in a third country. We suppose that neither the home government nor the foreign firm know the costs of the home firm, while the foreign firm cost is common knowledge. We determine the separating sequential equilibrium outputs.

Stackelberg duopoly with demand uncertainty

We consider a symmetric Stackelberg model in which there is asymmetric demand information owned by first and second movers. We analyse the advantages of leadership and flexibility, and prove that when the leading firm faces demand uncertainty, but the follower does not, the first mover does not necessarily have advantage over the second mover. Moreover, we show that the advantage of one firm over the other depends upon the demand fluctuation and also upon the degree of substitutability of the products.

Flexibility and leadership advantages in a model with uncertain demand

We consider a differentiated Stackelberg model with demand uncertainty only for the first mover. We study the advantages of flexibility over leadership as the degree of the differentiation of the goods changes.

Strategic trade policy and signaling costs with differentiated goods

We consider a trade policy model, where the costs of the home firm are private information but can be signaled through the output levels of the firm to a foreign competitor and a home policymaker. We compute the separating equilibrium and the Bayesian Nash equilibrium, and we compare the subsidies, firms’ expected profits and home government’s welfare in both equilibria, for different values of the own price effect parameter.

Cournot model with investments to change the market size

We present a new deterministic dynamical model on the market size of Cournot competitions, based on Nash equilibria of R&D investment strategies to increase the size of the market of the firms at every period of the game. We compute the unique Nash equilibrium for the second subgame and the profit functions for both firms. Adding uncertainty to the R&D investment strategies, we get a new stochastic dynamical model and we analyse the importance of the uncertainty to reverse the initial advantage of one firm with respect to the other.

Asymmetric dynamic price competition with uncertainty

We consider a dynamic setting-price duopoly model in which a dominant (leader) firm moves first and a subordinate (follower) firm moves second. We suppose that each firm has two different technologies, and uses one of them according to a certain probability distribution. The use of either one or the other technology affects the unitary production cost. We analyse the effect of the production costs uncertainty on the profits of the firms, for different values of the intercept demand parameters.

Cournot duopoly with competition in the R&D expenditures

We present a new R&D investment in a Cournot Duopoly model and we analyze the different possible types of Nash R&D investments. We observe that the new production costs region can be decomposed in three economical regions, depending on the Nash R&D investment, showing the relevance of the use of patents in new technologies.

As garantias financeiras e o seu controlo na atividade seguradora

Dissertação de Mestrado apresentado ao Instituto de Contabilidade e Administração do Porto para a obtenção do grau de Mestre em Contabilidade e Finanças, sob orientação do Professor Doutor Armindo Licínio da Silva Macedo

Ser intérprete em Portugal

Trabalho de Projeto apresentado ao Instituto de Contabilidade e Administração do Porto para a obtenção do grau de Mestre em Tradução e Interpretação Especializadas, sob orientação da Doutora Sara Cerqueira Pascoal