MIP-graphene-modified glassy carbon electrode for the determination of trimethoprim

A novel sensitive electrochemical sensor was developed by electropolymerization of pyrrole(PY)and molecularly imprinted polymer (MIP)which was synthesized onto a glassy carbon electrode (GCE) in aqueous solution using cyclic voltammetry in the presence of Trimethoprim (TMP) as template molecules. Furthermore,a previous electrode modification was performed by deposition of a suspension of graphene on the electrode's surface. The performance of the imprinted and non-imprinted (NIP) films was evaluated by impedance spectroscopy (EIS) and cyclic voltammetry (CV) of a ferric solution. The molecularly imprinted film exhibited a high selectivity and sensitivity toward TMP. The sensor presented a linear range, between peak current intensity and logarithm of TMP concentration between 1.0x10-6 and 1.0x10-4 M. The results were accurate (with recoveries higher than 94%), precise (with standard deviations less than 5%) and the detection limit was 1.3x10-7 M. The new sensor is selective, simple to construct and easy to operate. The MIP sensor was successfully applied to quantify TMP in urinesamples.

Celiac disease detection using a transglutaminase electrochemical immunosensor fabricated on nanohybrid screen-printed carbon electrodes

Celiac disease is a gluten-induced autoimmune enteropathy characterized by the presence of tissue tranglutaminase (tTG) autoantibodies. A disposable electrochemical immunosensor (EI) for the detection of IgA and IgG type anti-tTG autoantibodies in real patient’s samples is presented. Screen-printed carbon electrodes (SPCE) nanostructurized with carbon nanotubes and gold nanoparticles were used as the transducer surface. This transducer exhibits the excellent characteristics of carbon–metal nanoparticle hybrid conjugation and led to the amplification of the immunological interaction. The immunosensing strategy consisted of the immobilization of tTG on the nanostructured electrode surface followed by the electrochemical detection of the autoantibodies present in the samples using an alkaline phosphatase (AP) labelled anti-human IgA or IgG antibody. The analytical signal was based on the anodic redissolution of enzymatically generated silver by cyclic voltammetry. The results obtained were corroborated with a commercial ELISA kit indicating that the electrochemical immunosensor is a trustful analytical screening tool.

Layer-by-layer immobilization of carbon dots fluorescent nanomaterials on single optical fiber

We report within this paper the development of a fiber-optic based sensor for Hg(II) ions. Fluorescent carbon nanoparticles were synthesized by laser ablation and functionalized with PEG200 and N-acetyl-l-cysteine so they can be anionic in nature. This characteristic facilitated their deposition by the layer-by-layer assembly method into thin alternating films along with a cationic polyelectrolyte, poly(ethyleneimine). Such films could be immobilized onto the tip of a glass optical fiber, allowing the construction of an optical fluorescence sensor. When immobilized on the fiber-optic tip, the resultant sensor was capable of selectively detecting sub-micromolar concentrations of Hg(II) with an increased sensitivity compared to carbon dot solutions. The fluorescence of the carbon dots was quenched by up to 44% by Hg(II) ions and interference from other metal ions was minimal.

Avaliação do desempenho de adsorventes obtidos a partir de resíduos da indústria de curtumes na adsorção de poluentes

Na procura por uma solução de valorização dos resíduos gerados pela indústria de curtumes, o presente trabalho tem como principais objectivos a preparação de adsorventes a partir de resíduos desta actividade e a avaliação do seu desempenho na adsorção de poluentes. Para atingir este objectivo, inicialmente procedeu-se à carbonização das aparas de couro wet-white à temperatura de 800 ºC. Seguidamente, os carbonizados foram activados por activação química, tendo sido o hidróxido de potássio o agente activante escolhido. As razões mássicas hidróxido de potássio:precursor usadas na impregnação, foram iguais a 0,5:1 e 1:1. Para a razão 0,5:1, as temperaturas de activação escolhidas foram 700 e 800 ºC. Para a razão de impregnação 1:1, as temperaturas de activação usadas foram 700, 800 e 900 ºC. Para uma avaliação preliminar da capacidade de adsorção dos carvões activados produzidos, efectuou-se a determinação do número de azul de metileno. Este teste provou serem as amostras activadas a 900 ºC as que apresentaram melhores resultados (número de azul de metileno: 24g/100g) e as amostras activadas a 700 ºC, as que apresentaram menor capacidade de adsorção (1g/100g, para a razão de 0,5:1 e 7g/100g, para a razão de 1:1). Verificou-se também que amostras preparadas com iguais condições de activação (temperatura de activação e razão de impregnação), mas produzidas a partir de carbonizado de diferentes granulometrias, apresentaram diferentes desempenhos na adsorção de azul de metileno. As propriedades texturais dos carvões activados produzidos foram obtidas pela determinação das isotérmicas de adsorção de azoto a 77 K. Para tal, selecionaram-se quatro amostras: dois carvões activados a 800 ºC, com uma razão de impregnação de 1:1 e dois carvões activados a 900 ºC, com a mesma razão de impregnação, obtidos a partir de carbonizados com diferentes granulometrias. As isotérmicas obtidas são características de materiais essencialmente microporosos, com mesoporos e macroporos. Verificou-se também que a granulometria do precursor carbonizado influencia as propriedades texturais dos carvões activados produzidos. Para as temperaturas de activação usadas, 800 e 900 ºC, os carvões activados preparados a partir de carbonizado de menor granulometria apresentam melhores propriedades texturais. O carvão activado que apresentou maior área superficial específica foi obtido a 900 ºC, a partir de carbonizado finamente moído (SBET = 1475 m2/g). Determinadas as propriedades texturais dos carvões activados produzidos, realizaram-se ensaios de adsorção do corante CORIACIDE DARK BROWN VR, usado na indústria de curtumes com um carvão activado produzido no âmbito deste trabalho e com um carvão activado comercial NORIT ROW 0,8. A amostra de carvão activado produzida a partir de resíduos de wet-white escolhida para estes ensaios foi o carvão activado a 800 ºC, à razão de 1:1, a partir de carbonizado finamente moído (ww_800_1:1_carb.moído). Verificou-se que as quantidades adsorvidas pela amostra ww_800_1:1_carb.moído variaram entre os valores 7,47 e 32,07 mgcorante/gcarvão activado. Quanto ao carvão activado comercial, as quantidades adsorvidas situaram-se entre 8,95 e 69,13 mgcorante/gcarvão activado. Assim, conclui-se que o carvão activado comercial apresentou melhor desempenho na adsorção do corante da indústria de curtumes. Os carvões activados obtidos revelaram-se materiais essencialmente microporosos, com capacidade de adsorção de poluentes, como por exemplo corantes, no entanto o seu desempenho seria mais eficaz na adsorção de pequenas moléculas devido ao elevado volume de microporos que apresentaram.

Produção de hidrogénio através da gasificação da biomassa

A procura de uma forma limpa de combustível, aliada à crescente instabilidade de preços dos combustíveis fósseis verificada nos mercados faz com que o hidrogénio se torne num combustível a considerar devido a não resultar qualquer produto poluente da sua queima e de se poder utilizar, por exemplo, desperdícios florestais cujo valor de mercado não está inflacionado por não pertencer à cadeia alimentar humana. Este trabalho tem como objetivo simular o processo de gasificação de biomassa para produção de hidrogénio utilizando um gasificador de leito fluidizado circulante. O oxigénio e vapor de água funcionam como agentes gasificantes. Para o efeito usou-se o simulador de processos químicos ASPEN Plus. A simulação desenvolvida compreende três etapas que ocorrem no interior do gasificador: pirólise, que foi simulada por um bloco RYIELD, combustão de parte dos compostos voláteis, simulada por um bloco RSTOIC e, por fim, as reações de oxidação e gasificação do carbonizado “char”, simuladas por um bloco RPLUG. Os valores de rendimento dos compostos após a pirólise, obtidos por uma correlação proposta por Gomez-Barea, et al. (2010), foram os seguintes: 20,33% “char”, 22,59% alcatrão, 36,90% monóxido de carbono, 16,05%m/m dióxido de carbono, 3,33% metano e 0,79% hidrogénio (% em massa). Como não foi possível encontrar valores da variação da composição do gás à saída do gasificador com a variação da temperatura, para o caso de vapor de água e oxigénio, optou-se por utilizar apenas vapor na simulação de forma a comparar os seus valores com os da literatura. Às temperaturas de 700, 770 e 820ºC, para um “steam-to-biomass ratio”, (SBR) igual a 0,5, os valores da percentagem molar de monóxido de carbono foram, respetivamente, 56,60%, 55,84% e 53,85%, os valores de hidrogénio foram, respetivamente, 17,83%, 18,25% e 19,31%, os valores de dióxido de carbono foram, respetivamente, 16,40%, 16,85% e 17,93% e os valores de metano foram, respetivamente, 9,00%, 8,95% e 8,83%. Os valores da composição à saída do gasificador, à temperatura de 820ºC, para um SBR de 0,5 foram: 53,85% de monóxido de carbono, 19,31% de hidrogénio, 17,93% de dióxido de carbono e 8,83% de metano (% em moles). Para um SBR de 0,7 a composição à saída foi de 54,45% de monóxido de carbono, 19,01% de hidrogénio, 17,59% de dióxido de carbono e 8,87% de metano. Por fim, quando SBR foi igual a 1 a composição do gás à saída foi de 55,08% de monóxido de carbono, 18,69% de hidrogénio, 17,24% de dióxido de carbono e 8,90% de metano. Os valores da composição obtidos através da simulação, para uma mistura de ar e vapor de água, ER igual a 0,26 e SBR igual a 1, foram: 34,00% de monóxido de carbono, 14,65% de hidrogénio, 45,81% de dióxido de carbono e 5,41% de metano. A simulação permitiu-nos ainda dimensionar o gasificador e determinar alguns parâmetros hidrodinâmicos do gasificador, considerando que a reação “water-gas shift” era a limitante, e que se pretendia obter uma conversão de 95%. A velocidade de operação do gasificador foi de 4,7m/s e a sua altura igual a 0,73m, para um diâmetro de 0,20m.

Static and hydrodynamic monitoring of citalopram based on its electro-oxidation behavior at a glassy-carbon surface

The electrooxidative behavior of citalopram (CTL) in aqueous media was studied by cyclic voltammetry (CV) and square-wave voltammetry (SWV) at a glassy-carbon electrode. The electrochemical behaviour of CTL involves two electrons and two protons in the irreversible and diffusion controlled oxidation of the tertiary amine group. The maximum analytical signal was obtained in a phosphate buffer (pH ¼ 8.2). For analytical purposes, an SWV method and a flow-injection analysis (FIA) system with amperometric detection were developed. The optimised SWV method showed a linear range between 1.10 10 5–1.20 10 4 molL 1, with a limit of detection (LOD) of 9.5 10 6 molL 1. Using the FIA method, a linear range between 2.00 10 6–9.00 10 5 molL 1 and an LODof 1.9 10 6 molL 1 were obtained. The validation of both methods revealed good performance characteristics confirming applicability for the quantification of CTL in several pharmaceutical products.

Adsorption behavior of α-cypermethrin on cork and activated carbon

Studies were undertaken to determine the adsorption behavior of α-cypermethrin [R)-α-cyano-3-phenoxybenzyl(1S)-cis- 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, and (S)-α-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropanecarboxylate] in solutions on granules of cork and activated carbon (GAC). The adsorption studies were carried out using a batch equilibrium technique. A gas chromatograph with an electron capture detector (GC-ECD) was used to analyze α-cypermethrin after solid phase extraction with C18 disks. Physical properties including real density, pore volume, surface area and pore diameter of cork were evaluated by mercury porosimetry. Characterization of cork particles showed variations thereby indicating the highly heterogeneous structure of the material. The average surface area of cork particles was lower than that of GAC. Kinetics adsorption studies allowed the determination of the equilibrium time—24 hours for both cork (1–2 mm and 3–4 mm) and GAC. For the studied α-cypermethrin concentration range, GAC revealed to be a better sorbent. However, adsorption parameters for equilibrium concentrations, obtained through the Langmuir and Freundlich models, showed that granulated cork 1–2 mm have the maximum amount of adsorbed α-cypermethrin (qm) (303 μg/g); followed by GAC (186 μg/g) and cork 3-4 mm (136 μg/g). The standard deviation (SD) values, demonstrate that Freundlich model better describes the α-cypermethrin adsorption phenomena on GAC, while α-cypermethrin adsorption on cork (1-2 mm and 3-4 mm) is better described by the Langmuir. In view of the adsorption results obtained in this study it appears that granulated cork may be a better and a cheaper alternative to GAC for removing α-cypermethrin from water.

Optical fiber sensor for Hg(II) based on carbon dots

An optical fiber sensor for Hg(II) in aqueous solution based on sol–gel immobilized carbon dots nanoparticles functionalized with PEG200 and N-acetyl-l-cysteine is described. This sol–gel method generated a thin (about 750 nm), homogenous and smooth (roughness of 2.7±0.7 a˚ ) filmthat immobilizes the carbon dots and allows reversible sensing of Hg(II) in aqueous solution. A fast (less than 10 s), reversible and stable (the fluorescence intensity measurements oscillate less than 1% after several calibration cycles) sensor system was obtained. The sensor allow the detection of submicron molar concentrations of Hg(II) in aqueous solution. The fluorescence intensity of the immobilized carbon dots is quenched by the presence of Hg(II) with a Stern-Volmer constant (pH = 6.8) of 5.3×105M−1.

Deteção eletroquímica da norfloxacina e trimetoprim em amostras de urina utilizando polímero molecularmente impresso modificado e grafeno

A norfloxacina e o trimetoprim são dois antibióticos antibacterianos usados para o tratamento de infeções urinárias, intestinais e respiratórias. A maioria dos fármacos exige uma dosagem que garanta os níveis de segurança e eficácia de atuação. A necessidade de dosear os medicamentos e os seus metabolitos é assim um controlo imperioso e em muitos casos regular no tratamento de um paciente. Neste trabalho desenvolveram-se dois sensores eletroquímicos para a deteção da norfloxacina (NFX) e do trimetoprim (TMP), usando como superfície de suporte o carbono vítreo. A busca de novos materiais que conferiram maior seletividade e sensibilidade aos sistemas de deteção e por outro lado apresentem menores riscos para o paciente quando usados em dispositivos que permitam uma análise point-of-care, é especialmente importante e pode ser uma parte crucial do processo de decisão clínica. Assim, os polímeros molecularmente impresos enquadram-se nesse perfil e o seu uso tem vindo a ser cada vez mais avaliado. A impressão molecular é uma tecnologia capaz de produzir polímeros que incorporam as moléculas do analito e que após remoção por solventes específicos, permitem dotá-los de locais específicos de reconhecimento estereoquímico. A seleção do pirrol como polímero molecularmente impresso (MIP) permitiu construir com sucesso os sensores para doseamento dos antibióticos. A fim de aumentar a sensibilidade do método incorporou-se grafeno na superfície do elétrodo. Este material tem vindo a ser largamente utilizado devido às suas propriedades: estrutura molecular, condutividade elétrica e aumento da superfície são algumas das características que mais despertam o interesse para a sua aplicação neste projeto. Os sensores desenvolvidos foram incorporados em sistemas eletroquímicos. Os métodos voltamétricos aplicados foram a voltametria cíclica, a voltametria de onda quadrada e ainda a impedância. As condições de análise foram otimizadas no que respeita à polimerização do pirrol (concentração do polímero, número de ciclos de eletropolimerização e respetivos potenciais aplicados, tempo de incubação, solvente de remoção do analito), ao pH da solução do fármaco, à gama de concentrações dos antibióticos e aos parâmetros voltamétricos dos métodos de análise. Para cada um dos antibióticos um elétrodo não-impresso foi também preparado, usando o procedimento de polimerização mas sem a presença da molécula do analito, e foi usado como controlo. O sensor desenvolvido para o trimetoprim foi usado no doseamento do fármaco em amostras de urina. As amostras foram analisadas sem qualquer diluição, apenas foram centrifugadas para remoção de proteínas e algum interferente. Os sensores construídos apresentaram comportamento linear na gama de concentrações entre 102 e 107 mol/L. Os resultados mostram boa precisão (desvios padrão inferiores a 11%) e os limites de deteção foram de 8,317 e 1,307 mol/L para a norfloxacina e o trimetoprim, respetivamente. Para validação do método foram ainda efetuados ensaios de recuperação tendo obtido valores superiores a 94%.

Biosensor based on multi-walled carbon nanotubes paste electrode modified with laccase for pirimicarb pesticide quantification

This study focused on the development of a sensitive enzymatic biosensor for the determination of pirimicarb pesticide based on the immobilization of laccase on composite carbon paste electrodes. Multi- walled carbon nanotubes(MWCNTs)paste electrode modified by dispersion of laccase(3%,w/w) within the optimum composite matrix(60:40%,w/w,MWCNTs and paraffin binder)showed the best performance, with excellent electron transfer kinetic and catalytic effects related to the redox process of the substrate4- aminophenol. No metal or anti-interference membrane was added. Based on the inhibition of laccase activity, pirimicarb can be determined in the range 9.90 ×10- 7 to 1.15 ×10- 5 molL 1 using 4- aminophenol as substrate at the optimum pH of 5.0, with acceptable repeatability and reproducibility (relative standard deviations lower than 5%).The limit of detection obtained was 1.8 × 10-7 molL 1 (0.04 mgkg 1 on a fresh weight vegetable basis).The high activity and catalytic properties of the laccase- based biosensor are retained during ca. one month. The optimized electroanalytical protocol coupled to the QuEChERS methodology were applied to tomato and lettuce samples spiked at three levels; recoveries ranging from 91.0±0.1% to 101.0 ± 0.3% were attained. No significant effects in the pirimicarb electro- analysis were observed by the presence of pro-vitamin A, vitamins B1 and C,and glucose in the vegetable extracts. The proposed biosensor- based pesticide residue methodology fulfills all requisites to be used in implementation of food safety programs.

Laccase–Prussian blue film–graphene doped carbon paste modified electrode for carbamate pesticides quantification

A novel enzymatic biosensor for carbamate pesticides detection was developed through the direct immobilization of Trametes versicolor laccase on graphene doped carbon paste electrode functionalized with Prussianblue films (LACC/PB/GPE). Graphene was prepared by graphite sonication-assisted exfoliation and characterized by transmission electron microscopy and X-ray photoelectron spectro- scopy. The Prussian blue film electrodeposited onto graphene doped carbon paste electrode allowed considerable reduction of the charge transfer resistance and of the capacitance of the device.The combined effects of pH, enzyme concentration and incubation time on biosensor response were optimized using a 23 full-factorial statistical design and response surface methodology. Based on the inhibition of laccase activity and using 4-aminophenol as redox mediator at pH 5.0,LACC/PB/GPE exhibited suitable characteristics in terms of sensitivity, intra-and inter-day repeatability (1.8–3.8% RSD), reproducibility (4.1 and 6.3%RSD),selectivity(13.2% bias at the higher interference: substrate ratios tested),accuracy and stability(ca. twenty days)for quantification of five carbamates widely applied on tomato and potato crops.The attained detection limits ranged between 5.2×10−9 mol L−1(0.002 mg kg−1 w/w for ziram)and 1.0×10−7 mol L−1 (0.022 mg kg−1 w/w for carbofuran).Recovery values for the two tested spiking levels ranged from 90.2±0.1%(carbofuran)to 101.1±0.3% (ziram) for tomato and from 91.0±0.1%(formetanate)to 100.8±0.1%(ziram)for potato samples.The proposed methodology is appropriate to enable testing pesticide levels in food samples to fit with regulations and food inspections.

Adsorption kinetics of removal of yellow lanasol dyestuff using gallinaceous feathers

Gallinaceous feathers are an abundant solid waste from the poultry processing industries, which poses disposal problems. A kinetic study dealing with the adsorption process of wool reactive dye, Yellow Lanasol 4G (CI Reactive Yellow 39), on gallinaceous (Gallus gallus, Cobb 500) feathers was carried out. The main research goals of this work were to evaluate the viability of using this waste as adsorbent and to study the kinetics of the adsorption process, using a synthetic effluent. The characterization of feathers was performed by scanning electron microscopy, mercury porosimetry and B.E.T. method. The study of several factors (stirring, particles size, initial dye concentration and temperature) showed their influence over the adsorption process. An adapted version of the Schumckler and Goldstein´s unreacted core model fitted the experimental data. The best fit was obtained when the rate-limiting step was the diffusion through the reacted layer, which was expected considering the size of the dyestuff molecules. The comparison with the granular activated carbon (GAC) Sutcliffe GAC 10-30 indicate that in spite of the high adsorption capacities shown by feathers the GAC presented higher values, the values obtained were respectively 150 and 219 mg g-1, for an initial concentration of 500 mg L-1. The results obtained might open future perspectives both to the valorization of feathers and to the economical treatment of textile wastewaters.

Evaluation of dynamic pass-through of carbon prices into electricity prices – a cointegrated VECM analysis

This paper addresses the impact of the CO2 opportunity cost on the wholesale electricity price in the context of the Iberian electricity market (MIBEL), namely on the Portuguese system, for the period corresponding to the Phase II of the European Union Emission Trading Scheme (EU ETS). In the econometric analysis a vector error correction model (VECM) is specified to estimate both long–run equilibrium relations and short–run interactions between the electricity price and the fuel (natural gas and coal) and carbon prices. The model is estimated using daily spot market prices and the four commodities prices are jointly modelled as endogenous variables. Moreover, a set of exogenous variables is incorporated in order to account for the electricity demand conditions (temperature) and the electricity generation mix (quantity of electricity traded according the technology used). The outcomes for the Portuguese electricity system suggest that the dynamic pass–through of carbon prices into electricity prices is strongly significant and a long–run elasticity was estimated (equilibrium relation) that is aligned with studies that have been conducted for other markets.

Electrochemical determination of the herbicide bentazone using a carbon nanotube b-Cyclodextrin modified electrode

An electrochemical sensor has been developed for the determination of the herbicide bentazone, based on a GC electrode modified by a combination of multiwalled carbon nanotubes (MWCNT) with b-cyclodextrin (b-CD) incorporated in a polyaniline film. The results indicate that the b-CD/MWCNT modified GC electrode exhibits efficient electrocatalytic oxidation of bentazone with high sensitivity and stability. A cyclic voltammetric method to determine bentazone in phosphate buffer solution at pH 6.0, was developed, without any previous extraction, clean-up, or derivatization steps, in the range of 10–80 mmolL 1, with a detection limit of 1.6 mmolL 1 in water. The results were compared with those obtained by an established HPLC technique. No statistically significant differences being found between both methods.

Antioxidant properties of hydroxycinnamic acids: a review of structure- activity relationships

Hydroxycinnamic acids (HCAs) are important phytochemicals possessing significant biological properties. Several investigators have studied in vitro antioxidant activity of HCAs in detail. In this review, we have gathered the studies focused on the structure-activity relationships (SARs) of these compounds that have used medicinal chemistry to generate more potent antioxidant molecules. Most of the reports indicated that the presence of an unsaturated bond on the side chain of HCAs is vital to their activity. The structural features that were reported to be of importance to the antioxidant activity were categorized as follows: modifications of the aromatic ring, which include alterations in the number and position of hydroxy groups and insertion of electron donating or withdrawing moieties as well as modifications of the carboxylic function that include esterification and amidation process. Furthermore, reports that have addressed the influence of physicochemical properties including redox potential, lipid solubility and dissociation constant on the antioxidant activity were also summarized. Finally, the pro-oxidant effect of HCAs in some test systems was addressed. Most of the investigations concluded that the presence of ortho-dihydroxy phenyl group (catechol moiety) is of significant importance to the antioxidant activity, while, the presence of three hydroxy groups does not necessarily improve the activity. Optimization of the structure of molecular leads is an important task of modern medicinal chemistry and its accomplishment relies on the careful assessment of SARs. SAR studies on HCAs can identify the most successful antioxidants that could be useful for management of oxidative stress-related diseases.