Development of paper-based color test-strip for drug detection in aquatic environment: Application to oxytetracycline

The wide use of antibiotics in aquaculture has led to the emergence of resistant microbial species. It should be avoided/minimized by controlling the amount of drug employed in fish farming. For this purpose, the present work proposes test-strip papers aiming at the detection/semi-quantitative determination of organic drugs by visual comparison of color changes, in a similar analytical procedure to that of pH monitoring by universal pH paper. This is done by establishing suitable chemical changes upon cellulose, attributing the paper the ability to react with the organic drug and to produce a color change. Quantitative data is also enabled by taking a picture and applying a suitable mathematical treatment to the color coordinates given by the HSL system used by windows. As proof of concept, this approach was applied to oxytetracycline (OXY), one of the antibiotics frequently used in aquaculture. A bottom-up modification of paper was established, starting by the reaction of the glucose moieties on the paper with 3-triethoxysilylpropylamine (APTES). The so-formed amine layer allowed binding to a metal ion by coordination chemistry, while the metal ion reacted after with the drug to produce a colored compound. The most suitable metals to carry out such modification were selected by bulk studies, and the several stages of the paper modification were optimized to produce an intense color change against the concentration of the drug. The paper strips were applied to the analysis of spiked environmental water, allowing a quantitative determination for OXY concentrations as low as 30 ng/mL. In general, this work provided a simple, method to screen and discriminate tetracycline drugs, in aquaculture, being a promising tool for local, quick and cheap monitoring of drugs.

RuSe Electrocatalysts and Single Wall Carbon Nanohorns Supports for the Oxygen Reduction Reaction

Selenium modified ruthenium electrocatalysts supported on carbon black were synthesized using NaBH4 reduction of the metal precursor. Prepared Ru/C electrocatalysts showed high dispersion and very small averaged particle size. These Ru/C electrocatalysts were subsequently modified with Se following two procedures: (a) preformed Ru/carbon catalyst was mixed with SeO2 in xylene and reduced in H2 and (b) Ru metal precursor was mixed with SeO2 followed by reduction with NaBH4. The XRD patterns indicate that a pyrite-type structure was obtained at higher annealing temperatures, regardless of the Ru:Se molar ratio used in the preparation step. A pyrite-type structure also emerged in samples that were not calcined; however, in this case, the pyrite-type structure was only prominent for samples with higher Ru:Se ratios. The characterization of the RuSe/C electrocatalysts suggested that the Se in noncalcined samples was present mainly as an amorphous skin. Preliminary study of activity toward oxygen reduction reaction (ORR) using electrocatalysts with a Ru:Se ratio of 1:0.7 indicated that annealing after modification with Se had a detrimental effect on their activity. This result could be related to the increased particle size of crystalline RuSe2 in heat-treated samples. Higher activity of not annealed RuSe/C catalysts could also be a result of the structure containing amorphous Se skin on the Ru crystal. The electrode obtained using not calcined RuSe showed a very promising performance with a slightly lower activity and higher overpotential in comparison with a commercial Pt/C electrode. Single wall carbon nanohorns (SWNH) were considered for application as ORR electrocatalysts' supports. The characterization of SWNH was carried out regarding their tolerance toward strong catalyzed corrosion conditions. Tests indicated that SWNH have a three times higher electrochemical surface area (ESA) loss than carbon black or Pt commercial electrodes.

Novel optical PVC probes for on-site detection/determination of fluoroquinolones in a solid/liquid interface: Application to the determination of Norfloxacin in aquaculture water

A novel optical disposable probe for screening fluoroquinolones in fish farming waters is presented, having Norfloxacin (NFX) as target compound. The colorimetric reaction takes place in the solid/liquid interface consisting of a plasticized PVC layer carrying the colorimetric reagent and the sample solution. NFX solutions dropped on top of this solid-sensory surface provided a colour change from light yellow to dark orange. Several metals were tested as colorimetric reagents and Fe(III) was selected. The main parameters affecting the obtained colour were assessed and optimised in both liquid and solid phases. The corresponding studies were conducted by visible spectrophotometry and digital image acquisition. The three coordinates of the HSL model system of the collected image (Hue, Saturation and Lightness) were obtained by simple image management (enabled in any computer). The analytical response of the optimised solid-state optical probe against concentration was tested for several mathematical transformations of the colour coordinates. Linear behaviour was observed for logarithm NFX concentration against Hue+Lightness. Under this condition, the sensor exhibited a limit of detection below 50 μM (corresponding to about 16 mg/mL). Visual inspection also enabled semi-quantitative information. The selectivity was ensured against drugs from other chemical groups than fluoroquinolones. Finally, similar procedure was used to prepare an array of sensors for NFX, consisting on different metal species. Cu(II), Mn(II) and aluminon were selected for this purpose. The sensor array was used to detect NFX in aquaculture water, without any prior sample manipulation.

Myoglobin-biomimetic electroactive materials made by surface molecular imprinting on silica beads and their use as ionophores in polymeric membranes for potentiometric transduction

Myoglobin (Mb) is among the cardiac biomarkers playing a major role in urgent diagnosis of cardiovascular diseases. Its monitoring in point-of-care is therefore fundamental. Pursuing this goal, a novel biomimetic ionophore for the potentiometric transduction of Mb is presented. It was synthesized by surface molecular imprinting (SMI) with the purpose of developing highly efficient sensor layers for near-stereochemical recognition of Mb. The template (Mb) was imprinted on a silane surface that was covalently attached to silica beads by means of self-assembled monolayers. First the silica was modified with an external layer of aldehyde groups. Then, Mb was attached by reaction with its amine groups (on the external surface) and subsequent formation of imine bonds. The vacant places surrounding Mb were filled by polymerization of the silane monomers 3-aminopropyltrimethoxysilane (APTMS) and propyltrimethoxysilane (PTMS). Finally, the template was removed by imine cleavage after treatment with oxalic acid. The results materials were finely dispersed in plasticized PVC selective membranes and used as ionophores in potentiometric transduction. The best analytical features were found in HEPES buffer of pH 4. Under this condition, the limits of detection were of 1.3 × 10−6 mol/L for a linear response after 8.0 × 10−7 mol/L with an anionic slope of −65.9 mV/decade. The imprinting effect was tested by preparing non-imprinted (NI) particles and employing these materials as ionophores. The resulting membranes showed no ability to detect Mb. Good selectivity was observed towards creatinine, sacarose, fructose, galactose, sodium glutamate, and alanine. The analytical application was conducted successfully and showed accurate and precise results.

Disposable solid state probe for optical screening of chlorpromazine

We are presenting a simple, low-cost and rapid solid-state optical probe for screening chlorpromazine (CPZ) in aquacultures. The method exploits the colourimetric reaction between CPZ and Fe(III) ion that occurs at a solid/liquid interface, the solid layer consisting of ferric iron entrapped in a layer of plasticized PVC. If solutions containing CPZ are dropped onto such a layer, a colour change occurs from light yellow to dark pink or even light blue, depending on the concentration of CPZ. Visual inspection enables the concentration of CPZ to be estimated. The resulting colouration was also monitored by digital image collection for a more accurate quantification. The three coordinates of the hue, saturation and lightness system were obtained by standard image processing along with mathematical data treatment. The parameters affecting colour were assessed and optimized. Studies were conducted by visible spectrophotometry and digital image acquisition, respectively. The response of the optimized probe towards the concentration of CPZ was tested for several mathematical transformations of the colour coordinates, and a linear relation was found for the sum of hue and luminosity. The limit of detection is 50 μM (corresponding to about 16 μg per mL). The probe enables quick screening for CPZ in real water samples with prior sample treatment.

The influence of gait cadence on the ground reaction forces and plantar pressures during load carriage of young adults

Biomechanical gait parameters—ground reaction forces (GRFs) and plantar pressures—during load carriage of young adults were compared at a low gait cadence and a high gait cadence. Differences between load carriage and normal walking during both gait cadences were also assessed. A force plate and an in-shoe plantar pressure system were used to assess 60 adults while they were walking either normally (unloaded condition) or wearing a backpack (loaded condition) at low (70 steps per minute) and high gait cadences (120 steps per minute). GRF and plantar pressure peaks were scaled to body weight (or body weight plus backpack weight). With medium to high effect sizes we found greater anterior-posterior and vertical GRFs and greater plantar pressure peaks in the rearfoot, forefoot and hallux when the participants walked carrying a backpack at high gait cadences compared to walking at low gait cadences. Differences between loaded and unloaded conditions in both gait cadences were also observed.

Cross-Layer Admission Control to Enhance the Support of Real-Time Applications in WSN

Real-time monitoring applications may be used in a wireless sensor network (WSN) and may generate packet flows with strict quality of service requirements in terms of delay, jitter, or packet loss. When strict delays are imposed from source to destination, the packets must be delivered at the destination within an end-to-end delay (EED) hard limit in order to be considered useful. Since the WSN nodes are scarce both in processing and energy resources, it is desirable that they only transport useful data, as this contributes to enhance the overall network performance and to improve energy efficiency. In this paper, we propose a novel cross-layer admission control (CLAC) mechanism to enhance the network performance and increase energy efficiency of a WSN, by avoiding the transmission of potentially useless packets. The CLAC mechanism uses an estimation technique to preview packets EED, and decides to forward a packet only if it is expected to meet the EED deadline defined by the application, dropping it otherwise. The results obtained show that CLAC enhances the network performance by increasing the useful packet delivery ratio in high network loads and improves the energy efficiency in every network load.

Desenvolvimento de sensores colorimétricos para despiste de antibióticos

introdução de drogas que assegurem o crescimento e a preservação das espécies, mas que eventualmente se espalham para o meio aquático envolvente, promovendo alterações da biodiversidade e entrar, directamente ou indirectamente, na cadeia alimentar. Quando estas drogas são agentes antimicrobianos de uso humano, tais como a amoxicilina, tetraciclina ou sulfonamidas, há um alto risco de aparecimento de espécies bacterianas resistentes, algo que constitui uma ameaça grave para a saúde pública. Esta introdução de agentes antimicrobianos no ambiente aquático através do sector das pescas pode ser reduzida através da monitorização regular ou contínua dos níveis de antibióticos no sistema de água, durante a execução, bem como antes da descarga para o meio aquático. Para isso, é necessário métodos analíticos que permitam uma frequência analítica elevada e continua, nos tanques de cultivos dos peixes. O presente trabalho descreve para este efeito, um sensor constituído por papel quimicamente modificado por reações em monocamadas, assumindo uma coloração típica após contacto com o antibiótico . A intensidade da coloração estava relacionada com a concentração desse antibiótico. A modificação do papel foi baseada na alteração química das unidades de glucose do papel por meio de uma reação covalente com reagentes apropriados. De seguida, criou-se uma camada de quitosano sobre o papel modificado onde se adsorveu a espécie metálica capaz de mudar de cor na presença de sulfadiazina. As modificações resultantes foram avaliadas em relação a vários parâmetros, com o intuito de provocar uma variação de cor intensa face à concentração de antibiótico. Os sensores preparados foram caracterizados do ponto de vista do seu desempenho analítico, efetuou-se a construção de uma gama de concentração que permitiu obter uma resposta previsível e transversal em relação a outros antibióticos, bem como a identificação de uma relação linear entre concentração e coordenadas de cor e a aplicação de sensores em amostra de água ambiental dopados com antibiótico. Generalizando, foi possível estabelecer um processo de modificação simples de papel capaz de medir a presença e quantidade de sulfadiazina