Orientador: Maria Del Pilar Taboada Sotomayor / Banca: Iara Lucia Tescarollo Dias / Banca: Emerson Schwingel Ribeiro / Resumo: O presente trabalho está baseado na construção de sensores biomiméticos para monitoramento sensível e seletivo do agrotóxico metribuzin (MTZ). Para isto, eletrodos à base de pasta de carbono e nanotubos de carbono foram modificados com diversos complexos potenciais catalisadores biomiméticos das enzimas P450, que são enzimas que catalisam um grande número de reações incluindo os agrotóxicos. O complexo que apresentou perfil biomimético e melhores resultados na determinação amperométrica do metribuzin foi à ftalocianinacobalto (II) [CoPc]. Quando construídos sensores à base de pasta de carbono modificada com CoPc, os melhores resultados foram obtidos usando 15% (m/m) de complexo na preparação da pasta e realizando as medidas em tampão Britton-Robinson 0,08 mol L-1 (pH 2,0), aplicando potencial de -690 mV vs Ag|AgCl. Sob estas condições obteve-se uma faixa linear de resposta de 2,4 x 10-5 a 2,0 x 10-4 mol L-1, com uma boa sensibilidade e LOD e LOQ de 4,3 x 10-6 e 1,4 x 10-5 mol L-1, respectivamente. Estudos relacionados a elucidar a biomimeticidade do sensor, incluíram avaliação da influência da velocidade de varredura empregando voltametria cíclica, exploração do perfil hiperbólico da resposta do sensor e estudo de interferentes e de seletividade. A seguir, foi avaliada a influencia de nanotubos de carbono de paredes múltiplas (MWCNT) na preparação da pasta no intuito de tentar aumentar a detectabilidade do sensor modificado com ftalocianinacobalto (II). Entretanto, os resultados obtidos não foram àqueles esperados, devido principalmente, à grande quantidade de material aglutinante (Nujol® que é isolante) necessário para a obtenção da pasta. Assim, a seguir, foi realizada a avaliação de eletrodos impressos à base de grafite, contendo MWCNT a 0,3% e CoPc a 5%, 10% e 15% (m/m). Sob as condições de... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This work is based on the construction of biomimetic sensors for monitoring sensitive and selective pesticide metribuzin (MTZ). For this, the base electrodes of carbon paste and carbon nanotubes have been modified with various complex catalysts potential biomimetic of P450 enzymes, which are enzymes that catalyze a large number of reactions including pesticides. The complex profile that showed better results in biomimetic and amperometric determination of metribuzin was the ftalocianinacobalto (II) [CoPc]. When constructed sensors based on a modified carbon paste CoPc with the best results were obtained using 15% (m/ m) complex in the preparation of the folder and making the measurements in Britton-Robinson buffer 0,08 mol L-1 (pH 2,0), by applying potential to -690 mV vs Ag | AgCl. Under these conditions gave a linear response range of 2.4 x 10-5 to 2.0 x 10-4 mol L-1, and with good sensitivity and LOQ and LOD of 4,3 x 10-6 and 1 , 4 x 10-5 mol L-1, respectively. Related studies to elucidate the biomimeticidade sensor, included evaluation of the influence of scan rate using cyclic voltammetry, exploitation of hyperbolic profile of the sensor response and the study of interferences and selectivity. Next, we evaluated the influence of carbon nanotubes multi-walled (MWCNT) in the preparation of the folder in order to try to increase the detectability of the sensor modified with ftalocianinacobalto (II). However, the results were not those expected, mainly due to the large amount of binder material (Nujol ® which is an insulator) necessary for obtaining the paste. Thus, the following evaluation was made electrodes printed based on graphite containing MWCNT CoPc 0,3% and 5%, 10% and 15% (m / m). Under the above conditions optimized for the analysis carbon paste, the printed electrode that provided the best... (Complete abstract click electronic access below) / Mestre

Orientador: Maria Del Pilar Taboada Sotomayor / Banca: Marcos Roberto de Vasconcelos Lanza / Banca: Rosa Amália Fireman Dutra / Resumo: O presente trabalho está baseado no desenvolvimento de um sistema biomimético para monitoramento sensível e seletivo do metabólito TCP (3,5,6-tricloro-2-piridinol), proveniente do agrotóxico clorpitifós, o qual é mais solúvel que o próprio agrotóxico e cuja ocorrência em águas subterrâneas e superficiais é mais provável e perigosa. Foi construído um sensor biomimético com detecção voltamétrica por onda quadrada, os eletrodos, foram confeccionados à base de pasta de carbono modificada com o complexo cloro-5,10,15,20-tetraquis(pentafluorofenil)-21H,23H-porfirina ferro (III), o qual apresenta uma estrutura química semelhante à do sítio ativo da enzima P450. O sensor construído apresentou as melhores respostas em tampão fosfato 0,20 mol L-1 e pH 6,0, usando a voltametria de onda quadrada a 50 Hz, 150 mV de amplitude e 1,5 mV de E. Com os parâmetros otimizados o sensor apresentou limites de detecção e de quantificação de 1,9 e 5,2 μmol L-1, respectivamente. Estudos realizados para averiguar a biomimeticidade do sensor, incluíram: velocidade de varredura por voltametria cíclica, exploração do perfil hiperbólico da resposta no sensor e avaliação da seletividade. O sensor foi satisfatoriamente usado na análise em diversos tipos de amostras de interesse ambiental. Foram feitos testes de recuperação e nas amostras de solo, águas superficiais e subterrâneas obtendo recuperação de 91%, 107% e 96% respectivamente, mostrando que o sensor pode ser usado como método alternativo para quantificação de TCP em diferentes matrizes. O sensor também foi empregado no monitoramento da eficiência de polímeros de impressão molecular (MIP) para TCP. Buscando obter o polímero biomimético mais eficiente para o analito, foram usadas ferramentas computacionais que permitiram escolher o melhor monômero (acrilonitrila)... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This work is based on developing a biomimetic system for sensitive and selective monitoring of the TCP (3,5,6-trichloro-2-pyridinol), the principal metabolite of the pesticide chlorpyrifos, which is more soluble than the pesticide and whose occurrence in groundwater and surface water is more likely and dangerous. For this, a biomimetic sensor was constructed and the square wave voltammetric was used for measurements. The electrodes were fabricated using carbon paste modified with the complex chloro-5,10,15,20-tetrakis-(pentafluorophenyl)-21H,23H-porphyrin iron(III), which has a chemical structure similar to the active site of the enzyme P450. The sensor presented the best responses in phosphate buffer 0.20 mol L-1 and pH 6.0, using the square wave voltammetry with 50 Hz, amplitude of potential of 150 mV and ΔE of 1.5 mV. With the optimized parameters the sensor showed limits of detection and quantification of 1.9 and 5.2 μmol L-1, respectively. Studies conducted to investigate the mimicking of the sensor, included evaluation of the influence on scan rate in the cyclic voltammetry, the verification of the hyperbolic profile of the sensor response and evaluation of selectivity. The sensor has been satisfactorily applied in the analysis of different samples of environmental interest. Recovery experiments in samples of soil, surface water, and groundwater showed values of 91%, 107% and 96% respectively, showing that the sensor can be used as an alternative method for the quantification of TCP in different matrices. The sensor was also used to monitor the efficiency of molecularly imprinted polymers (MIP) for TCP. In order to obtain the most efficient biomimetic polymer to this analyte were used computational tools that allowed select the best monomer (acrylonitrile). In order to verify the results obtained by the theoretical... (Complete abstract click electronic access below) / Mestre

No description available.

Carbon nanotubes (CNTs) have been extensively studied for their electrical and mechanical properties since its discovery. Owing to their minute dimensions, good mechanical, electrical and chemical properties, different groups started to utilize CNTs as nano sensors or actuators for different applications in nanoelectronic or nano-electro-mechanical systems (NEMS). In order to build practical CNTs based devices, fast and batch techniques to build them have to be developed. To manipulate these nano-sized tubes, atomic force microscopy (AFM) is typically used to manipulate each of them one-by-one. However, this is time-consuming and unrealistic for batch fabrication. In this dissertation, dielectrophoretic manipulation of carbon nanotubes was employed to rapidly and batch fabricate practical nano sensors. The proposed technology will potentially enable fully automated assembly of CNTs based devices. We have also shown that this electrokinetic based manipulation technique is compatible with room-temperature MEMS fabrication processes, and hence, MEMS structures embedded with carbon nanotubes sensing elements can be built. This encapsulation process ensures that the multi-walled carbon nanotubes (MWNTs) elements can be protected from moisture and contaminates in an operational environment, and thus, allows the sensors to be useful for potential applications such as temperature measurement in water, sensing human touch and body temperature, or as ultra-sensitive sensors in manufacturing plants. Different structures of the polymer thin films embedded CNTs sensors were designed and fabricated on silicon and polymer substrates and also integrated to polymer diaphragm and microfluidic channel for micro and nano scale sensing. In this work, CNTs were found as a novel sensing elements for ultra-low-power micro thermal, fluid-flow and piezoresistive pressure sensors---which may serve as alternative sensors for silicon based sensors when bio-compatibility and low-cost applications are required. / Fung Kar Man. / "August 2005." / Adviser: Wen Tung Li. / Source: Dissertation Abstracts International, Volume: 67-07, Section: B, page: 4058. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references (p. 91-98). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract in English and Chinese. / School code: 1307.

Sun Winston. / "December 1999." / Thesis (Ph.D.)--Chinese University of Hong Kong, 1999. / Includes bibliographical references (p. 149-159). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / Abstracts in English and Chinese.

This work investigates advanced single-electron transistor (SET) devices for detection of charge motion in solid-state systems. In particular, novel, nanoscale twin-SET and double-island SET (DISET) detectors are introduced as sensitive charge detectors. Some advantages over conventional SET detectors in terms of noise performance, sensitivity and versatility are pointed out. With the prospect of present, transistor-based microelectronics facing serious limitations due to quantum effects and heat dissipation, alternative computing paradigms ??? such as quantum computers, quantum-dot cellular automata and single-electronics ??? have emerged, promising an extension of highlevel integration and computing power beyond the above limitations. The most promising proposals are based on solid-state systems, and readout of a computational result often requires ultra-sensitive charge detectors capable of sensing the motion of single charges on fast timescales. SETs have been shown to combine all these qualities. However, random fluctuations of the background charge in solid-state systems can affect SETs and cause errors during readout. A twin-SET detector is presented that consists of two independent SETs, which were used to detect controlled single electron transfers on a small, floating metal double-dot. By cross-correlating the two SET signals, rejection of random charge noise is successfully demonstrated, thus decreasing the error probability during readout. Detection of single-electron transfer in a double-dot is also demonstrated using a double-island SET. In addition, conductance suppression in this novel DISET detector allows the detection of electrostatically degenerate charge con- figurations of a double-dot, which cannot be achieved with single-island SETs. We consider the noise performance of the DISET, and an intuitive definition of the DISET charge sensitivity suggests that under certain conditions, DISETs can have a better charge sensitivity than conventional SETs, which would be attractive for quantum limited measurements. Finally we present the first study of a DISET operated at radio-frequencies (rf-DISET), compatible with charge detection on ms timescales. This capability is a prerequisite when reading out the charge state of quantum mechanical systems. A very good charge sensitivity (5.6 x 10i6 e/pHz) and noise temperature (2.1 K) of the rf-DISET setup are reported.

"February 2003" / Bibliography: p. 121-135. / xii, 135 p. : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / This thesis is a theoretical evaluation of the (single) first photon detection (FPD) technique as a limiting case of time-resolved transillumination (TI) for diagnostic purposes. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physics and Mathematical Physics, 2003

This work investigates advanced single-electron transistor (SET) devices for detection of charge motion in solid-state systems. In particular, novel, nanoscale twin-SET and double-island SET (DISET) detectors are introduced as sensitive charge detectors. Some advantages over conventional SET detectors in terms of noise performance, sensitivity and versatility are pointed out. With the prospect of present, transistor-based microelectronics facing serious limitations due to quantum effects and heat dissipation, alternative computing paradigms ??? such as quantum computers, quantum-dot cellular automata and single-electronics ??? have emerged, promising an extension of highlevel integration and computing power beyond the above limitations. The most promising proposals are based on solid-state systems, and readout of a computational result often requires ultra-sensitive charge detectors capable of sensing the motion of single charges on fast timescales. SETs have been shown to combine all these qualities. However, random fluctuations of the background charge in solid-state systems can affect SETs and cause errors during readout. A twin-SET detector is presented that consists of two independent SETs, which were used to detect controlled single electron transfers on a small, floating metal double-dot. By cross-correlating the two SET signals, rejection of random charge noise is successfully demonstrated, thus decreasing the error probability during readout. Detection of single-electron transfer in a double-dot is also demonstrated using a double-island SET. In addition, conductance suppression in this novel DISET detector allows the detection of electrostatically degenerate charge con- figurations of a double-dot, which cannot be achieved with single-island SETs. We consider the noise performance of the DISET, and an intuitive definition of the DISET charge sensitivity suggests that under certain conditions, DISETs can have a better charge sensitivity than conventional SETs, which would be attractive for quantum limited measurements. Finally we present the first study of a DISET operated at radio-frequencies (rf-DISET), compatible with charge detection on ms timescales. This capability is a prerequisite when reading out the charge state of quantum mechanical systems. A very good charge sensitivity (5.6 x 10i6 e/pHz) and noise temperature (2.1 K) of the rf-DISET setup are reported.

This work investigates advanced single-electron transistor (SET) devices for detection of charge motion in solid-state systems. In particular, novel, nanoscale twin-SET and double-island SET (DISET) detectors are introduced as sensitive charge detectors. Some advantages over conventional SET detectors in terms of noise performance, sensitivity and versatility are pointed out. With the prospect of present, transistor-based microelectronics facing serious limitations due to quantum effects and heat dissipation, alternative computing paradigms ??? such as quantum computers, quantum-dot cellular automata and single-electronics ??? have emerged, promising an extension of highlevel integration and computing power beyond the above limitations. The most promising proposals are based on solid-state systems, and readout of a computational result often requires ultra-sensitive charge detectors capable of sensing the motion of single charges on fast timescales. SETs have been shown to combine all these qualities. However, random fluctuations of the background charge in solid-state systems can affect SETs and cause errors during readout. A twin-SET detector is presented that consists of two independent SETs, which were used to detect controlled single electron transfers on a small, floating metal double-dot. By cross-correlating the two SET signals, rejection of random charge noise is successfully demonstrated, thus decreasing the error probability during readout. Detection of single-electron transfer in a double-dot is also demonstrated using a double-island SET. In addition, conductance suppression in this novel DISET detector allows the detection of electrostatically degenerate charge con- figurations of a double-dot, which cannot be achieved with single-island SETs. We consider the noise performance of the DISET, and an intuitive definition of the DISET charge sensitivity suggests that under certain conditions, DISETs can have a better charge sensitivity than conventional SETs, which would be attractive for quantum limited measurements. Finally we present the first study of a DISET operated at radio-frequencies (rf-DISET), compatible with charge detection on ms timescales. This capability is a prerequisite when reading out the charge state of quantum mechanical systems. A very good charge sensitivity (5.6 x 10i6 e/pHz) and noise temperature (2.1 K) of the rf-DISET setup are reported.

This work investigates advanced single-electron transistor (SET) devices for detection of charge motion in solid-state systems. In particular, novel, nanoscale twin-SET and double-island SET (DISET) detectors are introduced as sensitive charge detectors. Some advantages over conventional SET detectors in terms of noise performance, sensitivity and versatility are pointed out. With the prospect of present, transistor-based microelectronics facing serious limitations due to quantum effects and heat dissipation, alternative computing paradigms ??? such as quantum computers, quantum-dot cellular automata and single-electronics ??? have emerged, promising an extension of highlevel integration and computing power beyond the above limitations. The most promising proposals are based on solid-state systems, and readout of a computational result often requires ultra-sensitive charge detectors capable of sensing the motion of single charges on fast timescales. SETs have been shown to combine all these qualities. However, random fluctuations of the background charge in solid-state systems can affect SETs and cause errors during readout. A twin-SET detector is presented that consists of two independent SETs, which were used to detect controlled single electron transfers on a small, floating metal double-dot. By cross-correlating the two SET signals, rejection of random charge noise is successfully demonstrated, thus decreasing the error probability during readout. Detection of single-electron transfer in a double-dot is also demonstrated using a double-island SET. In addition, conductance suppression in this novel DISET detector allows the detection of electrostatically degenerate charge con- figurations of a double-dot, which cannot be achieved with single-island SETs. We consider the noise performance of the DISET, and an intuitive definition of the DISET charge sensitivity suggests that under certain conditions, DISETs can have a better charge sensitivity than conventional SETs, which would be attractive for quantum limited measurements. Finally we present the first study of a DISET operated at radio-frequencies (rf-DISET), compatible with charge detection on ms timescales. This capability is a prerequisite when reading out the charge state of quantum mechanical systems. A very good charge sensitivity (5.6 x 10i6 e/pHz) and noise temperature (2.1 K) of the rf-DISET setup are reported.