Ciprofloxacin-imprinted polymeric receptors as ionophores for potentiometric transduction

A 3D-mirror synthetic receptor for ciprofloxacin host–guest interactions and potentiometric transduction is presented. The host cavity was shaped on a polymeric surface assembled with methacrylic acid or 2-vinyl pyridine monomers by radical polymerization. Molecularly imprinted particles were dispersed in 2-nitrophenyl octyl ether and entrapped in a poly(vinyl chloride) matrix. The sensors exhibited a near-Nernstian response in steady state evaluations. Slopes and detection limits ranged from 26.8 to 50.0 mV decade−1 and 1.0 × 10−5 to 2.7 × 10−5 mol L−1, respectively. Good selectivity was observed for trimethoprim, enrofloxacin, tetracycline, cysteine, galactose, hydroxylamine, creatinine, ammonium chloride, sucrose, glucose, sulphamerazine and sulfadiazine. The sensors were successfully applied to the determination of ciprofloxacin concentrations in fish and in pharmaceuticals. The method presented offered the advantages of simplicity, accuracy, applicability to colored and turbid samples and automation feasibility, as well as confirming the use of molecularly imprinted polymers as ionophores for organic ion recognition in potentiometric transduction.

Molecularly-Imprinted Materials for Potentiometric Transduction: Application to the Antibiotic Enrofloxacin

Enrofloxacin (ENR) is an antimicrobial used both in humans and in food producing species. Its control is required in farmed species and their surroundings in order to reduce the prevalence of antibiotic resistant bacteria. Thus, a new biomimetic sensor enrofloxacin is presented. An artificial host was imprinted in specific polymers. These were dispersed in 2-nitrophenyloctyl ether and entrapped in a poly(vinyl chloride) matrix. The potentiometric sensors exhibited a near-Nernstian response. Slopes expressing mV/Δlog([ENR]/M) varied within 48–63. The detection limits ranged from 0.28 to 1.01 µg mL−1. Sensors were independent from the pH of test solutions within 4–7. Good selectivity was observed toward potassium, calcium, barium, magnesium, glycine, ascorbic acid, creatinine, norfloxacin, ciprofloxacin, and tetracycline. In flowing media, the biomimetic sensors presented good reproducibility (RSD of ± 0.7%), fast response, good sensitivity (47 mV/Δlog([ENR]/M), wide linear range (1.0 × 10−5–1.0 × 10−3 M), low detection limit (0.9 µg mL−1), and a stable baseline for a 5 × 10−2 M acetate buffer (pH 4.7) carrier. The sensors were used to analyze fish samples. The method offered the advantages of simplicity, accuracy, and automation feasibility. The sensing membrane may contribute to the development of small devices allowing in vivo measurements of enrofloxacin or parent-drugs.

Selective recognition in potentiometric transduction of amoxicillin by molecularly imprinted materials

The indiscriminate use of antibiotics in food-producing animals has received increasing attention as a contributory factor in the international emergence of antibiotic-resistant bacteria (Woodward in Pesticide, veterinary and other residues in food, CRC Press, Boca Raton, 2004). Numerous analytical methods for quantifying antibacterial residues in edible animal products have been developed over years (Woodward in Pesticide, veterinary and other residues in food, CRC Press, Boca Raton, 2004; Botsoglou and Fletouris in Handbook of food analysis, residues and other food component analysis, Marcel Dekker, Ghent, 2004). Being Amoxicillin (AMOX) one of those critical veterinary drugs, efforts have been made to develop simple and expeditious methods for its control in food samples. In literature, only one AMOX-selective electrode has been reported so far. In that work, phosphotungstate:amoxycillinium ion exchanger was used as electroactive material (Shoukry et al. in Electroanalysis 6:914–917, 1994). Designing new materials based on molecularly imprinted polymers (MIPs) which are complementary to the size and charge of AMOX could lead to very selective interactions, thus enhancing the selectivity of the sensing unit. AMOX-selective electrodes used imprinted polymers as electroactive materials having AMOX as target molecule to design a biomimetic imprinted cavity. Poly(vinyl chloride), sensors of methacrylic acid displayed Nernstian slopes (60.7 mV/decade) and low detection limits (2.9 × 10−5 mol/L). The potentiometric responses were not affected by pH within 4–5 and showed good selectivity. The electrodes were applied successfully to the analysis of real samples.

Hydrogeomechanics for rock engineering: coupling subsurface hydrogeomechanical assessement and hydrogeotechnical mapping on fracturated rock masses

The present work aims to achieve and further develop a hydrogeomechanical approach in Caldas da Cavaca hydromineral system rock mass (Aguiar da Beira, NW Portugal), and contribute to a better understanding of the hydrogeological conceptual site model. A collection of several data, namely geology, hydrogeology, rock and soil geotechnics, borehole hydraulics and hydrogeomechanics, was retrieved from three rock slopes (Lagoa, Amores and Cancela). To accomplish a comprehensive analysis and rock engineering conceptualisation of the site, a multi‐technical approach were used, such as, field and laboratory techniques, hydrogeotechnical mapping, hydrogeomechanical zoning and hydrogeomechanical scheme classifications and indexes. In addition, a hydrogeomechanical data analysis and assessment, such as Hydro‐Potential (HP)‐Value technique, JW Joint Water Reduction index, Hydraulic Classification (HC) System were applied on rock slopes. The hydrogeomechanical zone HGMZ 1 of Lagoa slope achieved higher hydraulic conductivities with poorer rock mass quality results, followed by the hydrogeomechanical zone HGMZ 2 of Lagoa slope, with poor to fair rock mass quality and lower hydraulic parameters. In addition, Amores slope had a fair to good rock mass quality and the lowest hydraulic conductivity. The hydrogeomechanical zone HGMZ 3 of Lagoa slope, and the hydrogeomechanical zones HGMZ 1 and HGMZ 2 of Cancela slope had a fair to poor rock mass quality but were completely dry. Geographical Information Systems (GIS) mapping technologies was used in overall hydrogeological and hydrogeomechanical data integration in order to improve the hydrogeological conceptual site model.

Taludes rochosos. Metodologias de inspecção e de avalialição de segurança. Caso de estudo das vertentes rochosas de S. Simão

A instabilização de taludes rochosos, com consequências mais ou menos gravosas, repete-se com frequência no território nacional. Os enquadramentos destes incidentes são diversos, sendo mais comum e mais visível a sua ocorrência em taludes adjacentes a vias de comunicação. No entanto, o fenómeno repete-se também em vertentes naturais, geralmente em alturas de pluviosidade mais prolongada e intensa. No presente trabalho reveem-se conceitos associados a maciços rochosos, nomeadamente as principais classificações geotécnicas e as diferentes tipologias de instabilidade em taludes rochosos. Desenvolve-se um caso de estudo de uma vertente localizada em S. Simão, concelho de Amarante. Percorrem-se as sucessivas fases de estudo, incluindo a realização da fotografia aérea com recurso a um veículo não tripulado, a geração de um modelo 3D de elevada precisão da vertente e a caracterização e a classificação dos diferentes afloramentos rochosos. Desenvolve-se uma metodologia de inspeção com a criação de dois conjuntos de fichas e propõe-se o agravamento da classificação das anomalias perante a simultaneidade de ocorrência de anomalias de idêntica gravidade e a hierarquização dos blocos potencialmente instáveis, de acordo com os respetivos níveis de gravidade (NGB). Recorre-se ao programa de modelação da queda de blocos, “Rocfall (4.0”, da “Rocscience”, a partir de trajetórias definidas no modelo 3D gerado e propõem-se soluções de reforço e de proteção da vertente.

Estudo e Projeto de Reabilitação dos Acessos aos Parques Eólicos da Iberwind

A Iberwind recebeu o aluno estagiário para a realização de um projeto de consultoria técnica focada nos acessos dos seus 31 parques eólicos presentes no território nacional. É apresentada a empresa, bem como todo o processo de construção e desenvolvimento de parques eólicos. O presente relatório de estágio foca-se, maioritariamente, na reabilitação de acessos a parques eólicos, debruçando-se sobre as especialidades de terraplenagens, drenagem e pavimentação, bem como as condicionantes geométricas. Verifica-se que com o passar dos anos, após a construção dos primeiros empreendimentos, começa a denotar-se a deterioração dos acessos aos mesmos. É, por isso, relevante e significativo o trabalho realizado no âmbito do estágio, por forma a avaliar as diversas necessidades de reabilitação e manutenção dos acessos a apresentar soluções globais. O levantamento de campo realizado cobriu todo o portefólio da empresa e documentou a totalidade das patologias relacionadas com as especialidades de pavimentação e drenagem. Executaram-se visitas a todos os parques, acompanhadas pelos operadores dos mesmos, e aliaram-se às mesmas entrevistas aos supervisores de zona com o intuito de aglomerar informação e contextualizar a problemática. Realizou-se uma proposta de reabilitação dos acessos em piores condições, o que levou à adjudicação da obra e acompanhamento de alguns trabalhos por parte do autor no presente ano. O trabalho realizado e detalhadamente documentado permitiu a criação de uma metodologia de inspeção e manutenção a ser implementada nos parques eólicos do grupo, de forma a reduzir custos e otimizar recursos a longo prazo. A metodologia consiste, de forma sintetizada, na inspecção periódica dos acessos de cada parque pelas equipas de campo e a definição das necessidades prioritárias de manutenção e reabilitação dos mesmos de maneira independente.