Host-Tailored Sensors for Carnitine Potentiometric Measurements based on Surface Molecular Imprinting

Graduate Student Symposium on Molecular Imprinting 2013, na Queen’s University, Belfast, United Kingdom, 15 a 17 de Agosto de 2013

A framework for using real data with distributed low cost sensors

Currently, due to the widespread use of computers and the internet, students are trading libraries for the World Wide Web and laboratories with simulation programs. In most courses, simulators are made available to students and can be used to proof theoretical results or to test a developing hardware/product. Although this is an interesting solution: low cost, easy and fast way to perform some courses work, it has indeed major disadvantages. As everything is currently being done with/in a computer, the students are loosing the “feel” of the real values of the magnitudes. For instance in engineering studies, and mainly in the first years, students need to learn electronics, algorithmic, mathematics and physics. All of these areas can use numerical analysis software, simulation software or spreadsheets and in the majority of the cases data used is either simulated or random numbers, but real data could be used instead. For example, if a course uses numerical analysis software and needs a dataset, the students can learn to manipulate arrays. Also, when using the spreadsheets to build graphics, instead of using a random table, students could use a real dataset based, for instance, in the room temperature and its variation across the day. In this work we present a framework which uses a simple interface allowing it to be used by different courses where the computers are the teaching/learning process in order to give a more realistic feeling to students by using real data. A framework is proposed based on a set of low cost sensors for different physical magnitudes, e.g. temperature, light, wind speed, which are connected to a central server, that the students have access with an Ethernet protocol or are connected directly to the student computer/laptop. These sensors use the communication ports available such as: serial ports, parallel ports, Ethernet or Universal Serial Bus (USB). Since a central server is used, the students are encouraged to use sensor values results in their different courses and consequently in different types of software such as: numerical analysis tools, spreadsheets or simply inside any programming language when a dataset is needed. In order to do this, small pieces of hardware were developed containing at least one sensor using different types of computer communication. As long as the sensors are attached in a server connected to the internet, these tools can also be shared between different schools. This allows sensors that aren't available in a determined school to be used by getting the values from other places that are sharing them. Another remark is that students in the more advanced years and (theoretically) more know how, can use the courses that have some affinities with electronic development to build new sensor pieces and expand the framework further. The final solution provided is very interesting, low cost, simple to develop, allowing flexibility of resources by using the same materials in several courses bringing real world data into the students computer works.

Sertraline accumulation and effects in the estuarine decapod Carcinusmaenas: Importance of the history of exposure to chemical stress

Sertraline is widely prescribed worldwide and frequently detected in aquatic systems. There is, however, a remarkable gap of information on its potential impact on estuarine and coastal invertebrates. This study investigated sertraline accumulation and effects in Carcinus maenas. Crabs from a moderately contaminated (Lima) and a low-impacted (Minho) estuary were exposed to environmental and high levels of sertraline (0.05, 5, 500 μg L−1). A battery of biomarkers related to sertraline mode of action was employed to assess neurotransmission, energy metabolism, biotransformation and oxidative stress pathways. After a seven-day exposure, sertraline accumulation in crabs’ soft tissues was found in Lima (5 μg L−1: 15.3 ng L−1 ww; 500 μg L−1: 1010 ng L−1 ww) and Minho (500 μg L−1: 605 ng L−1 ww) animals. Lima crabs were also more sensitive to sertraline than those from Minho, exhibiting decreased acetylcholinesterase activity, indicative of ventilatory and locomotory dysfunction, inhibition of anti-oxidant enzymes and increased oxidative damage at ≥0.05 μg L−1. The Integrated Biomarker Response (IBR) index indicated their low health status. In addition, Minho crabs showed non-monotonic responses of acetylcholinesterase suggestive of hormesis. The results pointed an influence of the exposure history on differential sensitivity to sertraline and the need to perform evaluations with site-specific ecological receptors to increase relevance of risk estimations when extrapolating from laboratory to field conditions.

Isoflavones in food supplements: chemical profile, label accordance and permeability study in Caco-2 cells

Consumers nowadays are playing an active role in their health-care. A special case is the increasing number of women, who are reluctant to use exogenous hormone therapy for the treatment of menopausal symptoms and are looking for complementary therapies. However, food supplements are not clearly regulated in Europe. The EFSA has only recently begun to address the issues of botanical safety and purity regulation, leading to a variability of content, standardization, dosage, and purity of available products. In this study, isoflavones (puerarin, daidzin, genistin, daidzein, glycitein, genistein, formononetin, prunetin, and biochanin A) from food supplements (n = 15) for menopausal symptoms relief are evaluated and compared with the labelled information. Only four supplements complied with the recommendations made by the EC on the tolerable thresholds. The intestinal bioavailability of these compounds was investigated using Caco-2 cells. The apparent permeability coefficients of the selected isoflavonoids across the Caco-2 cells were affected by the isoflavone concentration and product matrix.

Molecularly imprinted electrochemical sensor for ochratoxin A detection in food samples

A novel electrochemical sensor for ochratoxin A (OTA) detection was fabricated through the modification of a glassy carbon electrode (GCE) with multiwalled carbon nanotubes (MWCNTs) and a molecularly imprinted polymer (MIP). The MWCNTs dramatically promoted the sensitivity of the developed sensor, while polypyrrole (PPy) imprinted with OTA served as the selective recognition element. The imprinted PPy film was prepared by electropolymerization of pyrrole in the presence of OTA as a template molecule via cyclic voltammetry (CV). The electrochemical oxidation of OTA at the developed sensor was investigated by CV and differential pulse voltammetry (DPV). The developed MIP/MWCNT/GCE sensor showed a linear relationship, when using DPV, between peak current intensity and OTA concentration in the range between 0.050 and 1.0 μM, with limits of detection (LOD) and quantification of 0.0041 μM (1.7 μg/L) and 0.014 μM (5.7 μg/L) respectively. With the developed sensor precise results were obtained; relative standard deviations of 4.2% and 7.5% in the evaluation of the repeatability and reproducibility, respectively. The MIP/MWCNT/GCE sensor is simple to fabricate and easy to use and was successfully applied to the determination of OTA in spiked beer and wine samples, with recoveries between 84 and 104%, without the need of a sample pre-treatment step.

MnFe2O4@CNT-N as novel electrochemical nanosensor for determination of caffeine, acetaminophen and ascorbic acid

For the first time, a glassy carbon electrode (GCE) modified with novel N-doped carbon nanotubes (CNT-N) functionalized with MnFe2O4 nanoparticles (MnFe2O4@CNT-N) has been prepared and applied for the electrochemical determination of caffeine (CF), acetaminophen (AC) and ascorbic acid (AA). The electrochemical behaviour of CF, AC and AA on the bare GCE, CNT-N/GCE and MnFe2O4@CNT-N/GCE were carefully investigated using cyclic voltammetry (CV) and square-wave voltammetry (SWV). Compared to bare GCE and CNT-N modified electrode, the MnFe2O4@CNT-N modified electrode can remarkably improve the electrocatalytic activity towards the oxidation of CF, AC and AA with an increase in the anodic peak currents of 52%, 50% and 55%, respectively. Also, the SWV anodic peaks of these molecules could be distinguished from each other at the MnFe2O4@CNT-N modified electrode with enhanced oxidation currents. The linear response ranges for the square wave voltammetric determination of CF, AC and AA were 1.0 × 10−6 to 1.1 × 10−3 mol dm−3, 1.0 × 10−6 to 1.0 × 10−3 mol dm−3 and 2.0 × 10−6 to 1.0 × 10−4 mol dm−3 with detection limit (S/N = 3) of 0.83 × 10−6, 0.83 × 10−6 and 1.8 × 10−6 mol dm−3, respectively. The sensitivity values at the MnFe2O4@CNT-N/GCE for the individual determination of AC, AA and CF and in the presence of the other molecules showed that the quantification of AA and CF show no interferences from the other molecules; however, AA and CF interfered in the determination of AC, with the latter molecule showing the strongest interference. Nevertheless, the obtained results show that MnFe2O4@CNT-N composite material acted as an efficient electrochemical sensor towards the selected biomolecules.

Molecularly imprinted sensor for voltammetric detection of norfloxacin

In this work, a norfloxacin selective modified glassy carbon electrode (GCE) based on a molecularly imprinted polymer (MIP) as electrochemical sensor was developed. A suspension of multi-walled carbon nanotubes (MWCNTs) was deposited on the electrode surface. Subsequently, a molecularly imprinted film was prepared by electropolymerization, via cyclic voltammetry of pyrrole (PPy) in the presence of norfloxacin (NFX) as the template molecule. A control electrode (NIP) was also prepared. Scanning electron microscopy (SEM) and cyclic voltammetry in a ferrocyanide solution were performed for morphological and electrochemical characterisation, respectively. Several experimental parameters were studied and optimised. For quantification purposes the MIP/MWCNT/GCE was immersed in NFX solutions for 10 min, and the detection was performed in voltammetric cell by square wave voltammetry. The proposed sensor presented a linear behaviour, between peak current intensity and logarithmic concentration of NFX between 1 × 10−7 and 8 × 10−6 M. The obtained results presented good precision, with a repeatability of 4.3% and reproducibility of 9% and the detection limit was 4.6 × 10−8 M (S/N = 3). The developed sensor displayed good selectivity and operational lifetime, is simple to fabricate and easy to operate and was successfully applied to the analysis of NFX in urine samples.

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

Desenvolvimento de um biossensor para Ácido Glutâmico

A presente dissertação tem com objetivo o desenvolvimento de um biossensor com base nos polímeros de impressão molecular para a deteção de uma molécula alvo, o ácido glutâmico que é convertido em glutamina pela glutamina sintetase, recorrendo à potenciometria. Nas células neoplásicas a glutamina não é sintetizada podendo-se considerar que o ácido glutâmico é um potencial agente anti-cancro. A técnica de impressão molécular utilizada foi a polimerização em bulk, combinando a acrilamida e a bis acrilamida com o ácido glutâmico. Para se verificar se a resposta potenciométrica obtida era de facto da molécula alvo foram preparados em paralelo com os sensores, materiais de controlo, ou seja, moléculas sem impressão molécular (NIP). Para se controlar a constituíção química dos vários sensores nomeadamente, do NIP e do polímero de impressão molecular (MIP) antes e após a remoção bem como a molécula foram realizados estudos de Espetroscopia de Infravermelhos de Transformada de Fourier (FTIR), Scanning electron microscope (SEM) e Espetroscopia de Raios X por dispersão em energia (EDS). Os materiais desenvolvidos foram aplicados em várias membranas que diferiam umas das outras, sendo seletivas ao ião. A avaliação das características gerais das membranas baseou-se na análise das curvas de calibração, conseguidas em meios com pHs diferentes, comparando os vários elétrodos. O pH 5 foi o que apresentou melhor resultado, associado a uma membrana que continha um aditivo, o p-tetra-octilphenol, e com o sensor com percentagem de 3%. Posto isto, testou-se em material biológico, urina, com as melhores características quer em termos de sensibilidade (18,32mV/década) quer em termos de linearidade (1,6x10-6 a 1,48x10-3 mol/L). Verificou-se ainda que aplicando iões interferentes na solução, estes não interferem nesta, podendo ser aplicados na amostra sem que haja alteração na resposta potenciométrica. O elétrodo é capaz de distinguir o ácido glutâmico dos restantes iões presentes na solução.