Desenvolvimento de um sensor óptico para determinação de Norfloxacina

A presente dissertação descreve o desenvolvimento e a caracterização de sensores ópticos com base em membranas de poli(cloreto de vinilo), PVC, para determinação de Norfloxacina em amostras do sector da aquacultura. Estes sensores basearam-se na reacção colorimétrica entre um metal imobilizado em PVC e a Norfloxacina. O metal foi escolhido com base em ensaios prévios de reacção colorimétrica entre a Norfloxacina e várias espécies metálicas, nomeadamente, Fe(III), Al(III), Pb(II), Aluminon, Mo(II), Mn(II), Ni(II), Cu(II), Co(II), Sn(II) e V(V). A reacção mais intensa foi obtida com o Fe(III). Neste sentido, numa primeira fase foram desenvolvidos sensores baseados em Fe(III). O efeito de alguns parâmetros experimentais na resposta desses sensores foi avaliado de modo univariado. Incluem-se aqui o efeito do pH, avaliado entre 2,00 e 6,00, e o da concentração de Fe(III), variada entre cerca de 1,00x10-5 M e 2,00x10-4 M. Os melhores valores foram obtidos a pH 3, para o qual se verificou um comportamento linear entre cerca de 1,00x10-5 M e 1,70x10-4 M de Fe(III). Utilizando as condições seleccionadas anteriormente, procedeu-se à caracterização do complexo sob ponto de vista químico. Os valores obtidos apontaram para a necessidade de um excesso de Fe(III) de, pelo menos, 10 vezes, no sentido de garantir a máxima extensão de complexação. O complexo referido apresentou, nestas condições, um comportamento linear ao longo do intervalo de concentrações de cerca de 7,00x10-5 M a 7,00x10-4 M em NOR. O complexo formado foi estável ao longo de 90 minutos. As condições óptimas para análise desse complexo numa superfície sólida foram obtidas após avaliação do efeito da quantidade de Fe(III) e do tipo e quantidade de solvente mediador (o-nitrofenil octil éter, di-n-octilftalato, dibutilftalato, bis(etilhexil)sebacato, bis(etilhexil)ftalato). O bis(etilhexil)sebacato foi o solvente mediador escolhido e a relação de quantidade entre o PVC e o solvente mediador foi igual a 1:2. O procedimento de preparação do sensor sólido e subsequente optimização foi aplicado a outras espécies metálicas, para além do Fe(III), tais como, Cu(II), Mn(II) e aluminon. A conjugação de todos estes metais permitiu desenvolver um array de sensores para despistagem de Norfloxacina em águas de aquacultura. Algumas membranas sensoras foram aplicadas com sucesso no controlo de Norfloxacina em amostras de águas ambientais dopadas. Os resultados obtidos com membranas de Fe(III) e Cu(II) foram exactos, tendo-se registado valores de concentração próximos dos reais. O método proposto permitiu, por isso, a despistagem rápida e eficaz da presença de um antibiótico em águas ambientais, permitindo ainda o seu doseamento a um baixo custo. Numa perspectiva de rotina, e tendo em vista a despistagem deste antibiótico, este método revelou-se mais rápido e mais barato do que os demais métodos descritos na literatura para este efeito.

Rede de monitorização ambiental em tempo- real com sistemas móveis

A compreensão das interacções entre os oceanos, a linha de costa, a qualidade do ar e as florestas só será possível através do registo e análise de informação geo-temporalmente referenciada. Mas a monitorização de grandes áreas apresenta o problema da cobertura espacial e temporal, e os custos nela envolvidos pela impossibilidade de disseminar a quantidade de estações de monitorização necessários à compreensão do fenómeno. É necessário então definir metodologias de colocação de sensores e recolha de informação de forma robusta, económica e temporalmente útil. Nesta dissertação apresentamos uma estratégia de monitorização ambiental, para meios hídricos, (ou de grande dimensão) que baseada em sistemas móveis e alguns princípios da geoestatística, fornece uma ferramenta de monitorização mais económica, sem prejuízo da qualidade de informação. Os modelos usados na geoestatística assentam na ideia de que medidas mais próximas tendem a serem mais parecidas do que valores observados em locais distantes e fornece métodos para quantificar esta correlação espacial e incorporá-la na estimação. Os resultados obtidos sustentam a convicção do uso de veículos móveis em redes de sensores e que contribuímos para responder à seguinte questão “Qual a técnica que nos permite com poucos sensores monitorizar grandes áreas?”. A solução passará por modelos de estimação de grandezas utilizados na geoestatística associados a sistemas móveis.

Monitorização do adoçante ciclamato de sódio através de sensor óptico

O presente trabalho pretendeu desenvolver e testar um sensor óptico para detectar ciclamato de sódio, um adoçante artificial utilizado nas bebidas em geral. A primeira abordagem neste sentido baseou-se na preparação de um sensor óptico através da formação de complexos corados entre o ciclamato e várias espécies metálicas, nomeadamente Hg(II), Ba(II), Fe(II), Ag(II), Pb(II), Cd(II), Mn (II), Ni(II), Cu(II), Co(II), Sn(II) e Mg(II). Perante a ausência de resultados satisfatórios optou-se por explorar a acção do ciclamato de sódio na transferência/partilha de um corante entre duas fases líquidas imiscíveis. As fases líquidas utilizadas foram a água e o clorofórmio. Testaram-se várias famílias de corantes mas só uma classe se mostrou com as características apropriadas para o objectivo pretendido. Dentro dessa família de corantes, seleccionou-se aquele que, à partida, garantiu o melhor desempenho. O sensor foi testado em diferentes condições de pH e também na presença de potenciais interferentes de forma a estabelecer as melhores condições de utilização. O método mostrou-se bastante simples de executar, rápido na obtenção de resultados e com boas características para ser avaliado visualmente, mas sempre de acordo com os critérios de objectividade que um trabalho deste tipo requer. Além o disso permitiu ser calibrado de uma forma rápida e simples, características essenciais para a aplicação deste método na despistagem de ciclamato em análises de rotina. O método desenvolvido foi ainda aplicado à análise de vinho dopado com diferentes concentrações de ciclamato de sódio. Destes testes verificou-se a necessidade de optimização do método através da introdução de outras substâncias na fase não aquosa diminuindo a vulnerabilidade do sensor a outros interferentes. Como conclusão, o método correspondeu às expectativas, mostrando-se viável para aplicação à análise de vinhos, ainda com uma margem significativa de desenvolvimento no sentido de o tornar mais fiável e preciso.

Reduced fluoresceinamine as a fluorescent sensor for nitric oxide

A new fluorescent sensor for nitric oxide (NO) is presented that is based on its reaction with a non fluorescent substance, reduced fluoresceinamine, producing the highly fluorescent fluoresceinamine. Using a portable homemade stabilized light source consisting of 450 nm LED and fiber optics to guide the light, the sensor responds linearly within seconds in the NO concentration range between about 10–750 µM with a limit of detection (LOD) of about 1 µM. The system generated precise intensity readings, with a relative standard deviation of less than 1%. The suitability of the sensor was assessed by monitoring the NO generated by either the nitrous acid decomposition reaction or from a NO-releasing compound. Using relatively high incubation times, the sensor also responds quantitatively to hydrogen peroxide and potassium superoxide, however, using transient signal measurements results in no interfering species.

Electrochemical DNA-sensor for evaluation of total antioxidant capacity of flavours and flavoured waters using superoxide radical damage

In this paper, a biosensor based on a glassy carbon electrode (GCE) was used for the evaluation of the total antioxidant capacity (TAC) of flavours and flavoured waters. This biosensor was constructed by immobilising purine bases, guanine and adenine, on a GCE. Square wave voltammetry (SWV) was selected for the development of this methodology. Damage caused by the reactive oxygen species (ROS), superoxide radical (O2·−), generated by the xanthine/xanthine oxidase (XOD) system on the DNA-biosensor was evaluated. DNA-biosensor encountered with oxidative lesion when it was in contact with the O2·−. There was less oxidative damage when reactive antioxidants were added. The antioxidants used in this work were ascorbic acid, gallic acid, caffeic acid, coumaric acid and resveratrol. These antioxidants are capable of scavenging the superoxide radical and therefore protect the purine bases immobilized on the GCE surface. The results demonstrated that the DNA-based biosensor is suitable for the rapid assess of TAC in beverages.

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.

Man-tailored biomimetic sensor of molecularly imprinted materials for the potentiometric measurement of oxytetracycline

A novel biomimetic sensor for the potentiometric transduction of oxytetracycline is presented. The artificial host was imprinted in methacrylic acid and/or acrylamide based polymers. Different amounts of molecularly imprinted and non-imprinted polymers were dispersed in different plasticizing solvents and entrapped in a poly(vinyl chloride) matrix. Only molecularly imprinted based sensors allowed a potentiometric transduction, suggesting the existence of host–guest interactions. These sensors exhibited a near-Nernstian response in steady state evaluations; slopes and detection limits ranged 42–63 mV/decade and 2.5–31.3 µg/mL, respectively. Sensors were independent from the pH of test solutions within 2–5. Good selectivity was observed towards glycine, ciprofloxacin, creatinine, acid nalidixic, sulfadiazine, cysteine, hydroxylamine and lactose. In flowing media, the biomimetic sensors presented good reproducibility (RSD of ±0.7%), fast response, good sensitivity (65 mV/decade), wide linear range (5.0×10−5 to 1.0×10−2 mol/L), low detection limit (19.8 µg/mL), and a stable baseline for a 5×10−3M citrate buffer (pH 2.5) carrier. The sensors were successfully applied to the analysis of drugs and urine. This work confirms the possibility of using molecularly imprinted polymers as ionophores for organic ion recognition in potentiometric transduction.

IEEE 802.15.4 for wireless sensor networks: a technical overview

Low-rate low-power consumption and low-cost communication are the key points that lead to the specification of the IEEE 802.15.4 standard. This paper overviews the technical features of the physical layer and the medium access control sublayer mechanisms of the IEEE 802.15.4 protocol that are most relevant for wireless sensor network applications. We also discuss the ability of IEEE 802.15.4 to fulfil the requirements of wireless sensor network applications.

Lower protocol layers for wireless sensor networks: a survey

Wireless Sensor Networks (WSNs) have been attracting increasing interests in the development of a new generation of embedded systems with great potential for many applications such as surveillance, environment monitoring, emergency medical response and home automation. However, the communication paradigms in Wireless Sensor Networks differ from the ones attributed to traditional wireless networks, triggering the need for new communication protocols and mechanisms. In this Technical Report, we present a survey on communication protocols for WSNs with a particular emphasis on the lower protocol layers. We give a particular focus to the MAC (Medium Access Control) sub-layer, since it has a prominent influence on some relevant requirements that must be satisfied by WSN protocols, such as energy consumption, time performance and scalability. We overview some relevant MAC protocol solutions and discuss how they tackle the trade-off between the referred requirements.

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.

Taxonomy of fundamental concepts of localization in cyber-physical and sensor networks

Localization is a fundamental task in Cyber-Physical Systems (CPS), where data is tightly coupled with the environment and the location where it is generated. The research literature on localization has reached a critical mass, and several surveys have also emerged. This review paper contributes on the state-of-the-art with the proposal of a new and holistic taxonomy of the fundamental concepts of localization in CPS, based on a comprehensive analysis of previous research works and surveys. The main objective is to pave the way towards a deep understanding of the main localization techniques, and unify their descriptions. Furthermore, this review paper provides a complete overview on the most relevant localization and geolocation techniques. Also, we present the most important metrics for measuring the accuracy of localization approaches, which is meant to be the gap between the real location and its estimate. Finally, we present open issues and research challenges pertaining to localization. We believe that this review paper will represent an important and complete reference of localization techniques in CPS for researchers and practitioners and will provide them with an added value as compared to previous surveys.

Data gathering approach in dense sensor networks

Sensor/actuator networks promised to extend automated monitoring and control into industrial processes. Avionic system is one of the prominent technologies that can highly gain from dense sensor/actuator deployments. An aircraft with smart sensing skin would fulfill the vision of affordability and environmental friendliness properties by reducing the fuel consumption. Achieving these properties is possible by providing an approximate representation of the air flow across the body of the aircraft and suppressing the detected aerodynamic drags. To the best of our knowledge, getting an accurate representation of the physical entity is one of the most significant challenges that still exists with dense sensor/actuator network. This paper offers an efficient way to acquire sensor readings from very large sensor/actuator network that are located in a small area (dense network). It presents LIA algorithm, a Linear Interpolation Algorithm that provides two important contributions. First, it demonstrates the effectiveness of employing a transformation matrix to mimic the environmental behavior. Second, it renders a smart solution for updating the previously defined matrix through a procedure called learning phase. Simulation results reveal that the average relative error in LIA algorithm can be reduced by as much as 60% by exploiting transformation matrix.

LNT: a logical neighbor tree secure group communication scheme for wireless sensor networks

Secure group communication is a paradigm that primarily designates one-to-many communication security. The proposed works relevant to secure group communication have predominantly considered the whole network as being a single group managed by a central powerful node capable of supporting heavy communication, computation and storage cost. However, a typical Wireless Sensor Network (WSN) may contain several groups, and each one is maintained by a sensor node (the group controller) with constrained resources. Moreover, the previously proposed schemes require a multicast routing support to deliver the rekeying messages. Nevertheless, multicast routing can incur heavy storage and communication overheads in the case of a wireless sensor network. Due to these two major limitations, we have reckoned it necessary to propose a new secure group communication with a lightweight rekeying process. Our proposal overcomes the two limitations mentioned above, and can be applied to a homogeneous WSN with resource-constrained nodes with no need for a multicast routing support. Actually, the analysis and simulation results have clearly demonstrated that our scheme outperforms the previous well-known solutions.

Using a prioritized medium access control protocol for incrementally obtaining an interpolation of sensor readings

This paper addresses sensor network applications which need to obtain an accurate image of physical phenomena and do so with a high sampling rate in both time and space. We present a fast and scalable approach for obtaining an approximate representation of all sensor readings at high sampling rate for quickly reacting to critical events in a physical environment. This approach is an improvement on previous work in that after the new approach has undergone a startup phase then the new approach can use a very small sampling period.

RadiaLE: A framework for designing and assessing link quality estimators in wireless sensor networks

Stringent cost and energy constraints impose the use of low-cost and low-power radio transceivers in large-scale wireless sensor networks (WSNs). This fact, together with the harsh characteristics of the physical environment, requires a rigorous WSN design. Mechanisms for WSN deployment and topology control, MAC and routing, resource and mobility management, greatly depend on reliable link quality estimators (LQEs). This paper describes the RadiaLE framework, which enables the experimental assessment, design and optimization of LQEs. RadiaLE comprises (i) the hardware components of the WSN testbed and (ii) a software tool for setting-up and controlling the experiments, automating link measurements gathering through packets-statistics collection, and analyzing the collected data, allowing for LQEs evaluation. We also propose a methodology that allows (i) to properly set different types of links and different types of traffic, (ii) to collect rich link measurements, and (iii) to validate LQEs using a holistic and unified approach. To demonstrate the validity and usefulness of RadiaLE, we present two case studies: the characterization of low-power links and a comparison between six representative LQEs. We also extend the second study for evaluating the accuracy of the TOSSIM 2 channel model.