Luminescent quantum dots have attracted great interest in recent years among biological researchers since they provide solutions to problems associated with use of organic fluorophores in cellular studies. Quantum dots show high photostability, high emission quantum yield, narrow and symmetric emission peaks and size-dependent wavelength tunability. The objective of my PhD studies was to develop CdSe/ZnS quantum dot-based probes and utilize them in cellular assays. The first phase of the work was to develop luminescent quantum dot fluorescence resonance energy transfer (FRET) based probes for protease activity. The probes were based on FRET interactions between quantum dots that serve as donors and rhodamine molecular acceptors that were immobilized to the surface of the quantum dots through peptide linkers, which contained selective enzymatic cleavage sites. Upon enzymatic cleavage of the peptide linkers, the rhodamine molecules no longer provided an efficient energy transfer channel to the quantum dots, which brightened the previously quenched quantum dots. The probes were applied to detect enzyme activity, screen enzyme inhibitors, and discriminate between normal and cancerous cells primarily because of the difference in the proteolytic activity in extracellular matrices. The second phase of my work was to take advantage of FRET and quantum dots to develop pH sensor. First quantum dots were modified with metallothionein (MT) to be water-soluble and biocompatible. The MT-coated quantum dots were labeled with Rhodamine through the formation of amide bonds with å-amine group of lysine in MT peptide to form the probes. FRET efficiency between quantum dots (donor) and rhodamine (acceptor) was pH dependent. The final phase of my studies focused on the first preparation of reversible quantum dot-based cellular probes for labile iron. The MT coated quantum dots was modified with EDTA to form probes. When captured by the EDTA molecules, iron ions quenched the emission of quantum dots. Removal of iron from the quantum dot surface by free EDTA or other iron chelators with higher binding affinity resulted in a rise in the luminescence of quantum dots. The analytical properties of the probes including sensitivity, selectivity, and reversibility were characterized. Intracellular assays in iron-enriched astrocytes will be carried out.

abstract: A new type of electronics was envisioned, namely edible electronics. Edible electronics are made by Food and Drug Administration (FDA) certified edible materials which can be eaten and digested by human body. Different from implantable electronics, test or treatment using edible electronics doesn’t require operations and perioperative complications. This dissertation bridges the food industry, material sciences, device fabrication, and biomedical engineering by demonstrating edible supercapacitors and electronic components and devices such as pH sensor. Edible supercapacitors were fabricated using food materials from grocery store. 5 of them were connected in series to power a snake camera. Tests result showed that the current generated by supercapacitor have the ability to kill bacteria. Next more food, processed food and non-toxic level electronic materials were investigated. A “preferred food kit” was created for component fabrication based on the investigation. Some edible electronic components, such as wires, resistor, inductor, etc., were developed and characterized utilizing the preferred food kit. These components make it possible to fabricate edible electronic/device in the future work. Some edible electronic components were integrated into an edible electronic system/device. Then edible pH sensor was introduced and fabricated. This edible pH sensor can be swallowed and test pH of gastric fluid. PH can be read in a phone within seconds after the pH sensor was swallowed. As a side project, an edible double network gel electrolyte was synthesized for the edible supercapacitor. / Dissertation/Thesis / Doctoral Dissertation Chemical Engineering 2019

The successful fabrication and characterization of two chemiresistive platforms for biomolecule detection was demonstrated by this work. The Si/Silica based single walled nanotube thin film (SWNTTF) platform was developed to understand the effect of device geometry on pH and M13 bacteriophage sensing capabilities as well as the underlying mechanisms governing SWNTTF chemiresistive biosensors. The dominant mechanism of sensing switched from direct chemical doping to electrostatic gating when the target analyte changed from H+/OH- ions in pH testing to whole viruses. The experimental limit of detection for M13 for this platform was 0.5pM and an increased sensitivity as well as variability was observed in devices with smaller channel widths. Preliminary device calibration was completed in order to correlate a resistance response to a bulk M13 concentration. The polyethylene terephthalate (PET) based SWNTTF platform was developed to demonstrate the commercial potential of SWNTTF chemiresistive biosensors by detecting relevant concentrations of brain natriuretic peptide (BNP) on economically viable substrates. The pH response of these chemiresistors confirmed that chemical doping was the cause for resistance change in the SWNTTFs. The preliminary results demonstrated successful BNP detection at 50pg/mL using both aptamers and antibodies as recognition elements. Using SWNTTFs as the transducing element of chemiresistors allowed for further understanding of electrical mechanisms of sensing as well as achieving sensitive, real-time and reproducible electrical virus and biomolecule detection. Although these platforms do not achieve ultrasensitive limits of detection, they demonstrate the commercial potential of platforms using SWNTTFs as the transducing element of electrical biomolecule sensors.

Orientador: Jose Alexandre Diniz / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Eletrica e Computação / Made available in DSpace on 2018-08-12T04:29:31Z (GMT). No. of bitstreams: 1 Barros_AngelicaDenardide_M.pdf: 3382435 bytes, checksum: 06e6858052deff3336f5e44a60b55e08 (MD5) Previous issue date: 2008 / Resumo: O presente trabalho tem como objetivo a caracterização de filmes finos de óxido de titânio para aplicação em transistores de efeito de campo sensíveis a íons, do inglês ion sensitive field effect transistors (ISFETs). Para isso, filmes finos de titânio de diferentes espessuras foram depositados através de uma evaporadora por feixe de elétrons sobre substrato de silício. Posteriormente, estes filmes foram oxidados e recozidos utilizando diferentes temperaturas através de um forno de processamento térmico rápido, do inglês rapid thermal process (RTP). Os filmes de óxido de titânio (TiOx) foram então caracterizados de forma estrutural através das técnicas Elipsometria, Espectroscopia Infravermelho, Espectroscopia RAMAN, Microscopia de Força Atômica e Espectroscopia de Retroespalhamento Rutheford. Dependendo da temperatura do patamar de tratamento térmico, foram obtidos filmes com diferentes concentrações de oxigênio, o que influenciou na espessura final, no índice de refração, na rugosidade da superfície e nos contornos de grão da superfície dos filmes. Através da caracterização estrutural foi possível verificar a formação de filmes de TiOx compostos principalmente da estrutura cristalina rutilo do TiO2, mas que também apresentaram a estrutura cristalina anatase, além da formação de uma fina camada de Ti2O3 e SiO2 entre o substrato de silício e o filme de TiOx. A caracterização elétrica realizada através da análise das curvas I-V e C-V, obtidas a partir de capacitores confeccionados através da deposição de eletrodos de aluminio (Al/Si/TiOx/Al), demostraram a obtenção de dielétricos de boa qualidade com valores de constante dielétrica entre 12 e 33, densidade de carga na interface da ordem de 1010/cm2 e densidade de corrente de fuga entre 1 e 10-4 A/cm2. Transistores de efeito de campo foram confeccionados para a obtenção de curvas IDxVDS e log IDxTensão. Foi encontrado valor de tensão de Early igual a -1629V, resistência de saída, ROUT, igual a 215MO e slope de 100mV/dec para o dielétrico de TiOx obtido com tratamento térmico em 960°C. O filme de TiOx tratado térmicamente em 600°C foi testado como sensor através de medidas C-V adaptadas e apresentou deslocamento da VFB em função da variação do pH da solução testada, apresentando potencial como sensor de pH. / Abstract: This work presents the characterization of thin titanium oxide films as potential dielectric to be applied in ion sensitive field effect transistors. The films were obtained through rapid thermal oxidation and annealing of titanium thin films of different thicknesses deposited by Ebeam evaporation on silicon wafers. These films were analyzed by Ellipsometry, Infrared Spectroscopy, Raman Spectroscopy, Atomic Force Microscopy and Rutherford Backscattering Spectroscopy. The final thicknesses of the thin films, roughness, surface grain countors, refractive indexes and oxigen concentration depend on the oxidation and annealing temperature. Structural characterization showed the presence of other oxides such Ti2O3, an interfacial SiO2 layer between the dielectric and the substrate and the anatase crystalline phase of TiO2 films besides the mainly found crystalline phase rutile. Electrical characterizations were obtained through I-V and C-V curves of Al/Si/TiOx/Al capacitors. These curves showed that the films had high dielectric constants between 12 and 33, interface charge density about 1010/cm2 and leakage current density about 1 and 10-4 A/cm2. Field effect transistors were made in order to analyze IDxVDS and log IDxBias curves. Early tension value of -1629V, ROUT value of 215MO and slope of 100mV/dec were calculated for the TiOx thin film thermally treated with 960°C. The TiOx thin film thermally treated with 600°C was successfully tested as pH sensor through adapted C-V measurements, which showed shifts in the VFB according to the H+ concentration in tested solutions. / Mestrado / Eletrônica, Microeletrônica e Optoeletrônica / Mestre em Engenharia Elétrica

[pt] A detecção da corrosão metálica em estruturas complexas e de difícil acesso apresenta dificuldades que até o presente não foram satisfatoriamente contornadas nos diversos setores industriais. Os sensores para avaliação da corrosão metálica baseiamse normalmente em corpos de sacrifício ou na monitoração da reação catódica que ocorre junto com o processo de oxidação e redução da corrosão. Condições ambientais, como temperatura, pressão, vazão, composição química e pH, têm influência direta sobre a agressividade do meio e seu conhecimento é fundamental para a previsão das taxas de corrosão. Na indústria do petróleo a corrosão metálica pode significar a falha prematura de equipamentos e vazamentos, causando onerosas operações de manutenção e pondo em risco a segurança e o meio ambiente. O presente trabalho mostra a concepção e desenvolvimento de um sensor de pH a fibra ótica para monitoração permanente de poços de petróleo. Dois princípios de medição foram avaliados. O primeiro, baseia-se na medida da variação do índice de refração efetivo em uma rede de Bragg, especialmente preparada para este fim, imersa em um meio contendo indicadores comerciais de pH. A segunda concepção utiliza a variação de volume proporcionada por um polímero sensível ao pH para deformar uma rede de Bragg. Os resultados experimentais obtidos demonstraram que a segunda técnica possibilita uma maior sensibilidade para as condições de operação do sensor. Esta segunda solução viabiliza também a utilização de múltiplos sensores, em uma única fibra óptica, monitorando ao mesmo tempo outras grandezas físicas que influenciam diretamente as taxas de corrosão, como pressão, temperatura e vazão. O sensor foi avaliado em meio ácido, sob diferentes condições de temperatura, produzindo resultados se sensibilidade melhor 0,01 unidades de pH. Novas investigações ainda precisam ser conduzidas para se chegar a um protótipo que possa ser testado em condições reais de operação de um poço de petróleo. / [en] Evaluation of corrosion rates in hard-to-access equipments, such as those found in petroleum production, is still a difficult task. Sensors for corrosion rate evaluation are normally based on sacrifice bodies or in the cathodic reaction that occurs with the oxidation and reduction reactions of the corrosion process. Environmental conditions like temperature, pressure, chemical composition, and pH, are fundamental factors of environment severity and have a direct influence on corrosion rate predictions. In the Petroleum Industry, metallic corrosion may cause premature failure of equipments and fluid leaks, often resulting in expensive maintenance operations and posing safety and environmental risks. This work presents new concepts for fiber optic pH sensors that may be applied for permanent monitoring of petroleum wells. Two measurements principles were evaluated. The first one is based on measurements of refractive index changes in commercial pH indicators. The second solution explores a pH sensitive polymer, whose changes in volume strains a fiber Bragg grating. Experiments reported here show that the second technique has a better sensitivity, particularly under the operation conditions found in oil wells. It also allows the use of multiple fiber optic sensors simultaneously monitoring other physical quantities, such as temperature, pressure, and flow rate, which directly affect corrosion rates. The sensor was tested in acid environment, with special attention paid to temperature, solubility and response time. The sensitivity achieved was better than 0.01 pH units. More experiments still need to be performed in order to produce a prototype that will be testes in real operation conditions in producing petroleum well.

The monitoring of pH and free chlorine concentration in drinking water is important for water safety and public health. However, existing laboratory-based analytical methods are laborious, inefficient, and costly. This thesis focuses on the development of an easy-to-use, sensitive, and low-cost drinking water quality monitoring system for pH and free chlorine. An inkjet printing technology with a two-step thermolysis process in air is developed to deposit palladium/palladium oxide (Pd/PdO) films as potentiometric pH sensing electrodes. The redox reaction between PdO and hydronium ions generates the sensor output voltage. A large PdO percentage in the film provides a high sensitivity of ~60 mV/pH. A defect-free Pd/PdO film with small roughness contributes to a fast response and a high stability. When the Pd ink is thermalized in low vacuum, the deposited Pd/PdO film shows a bilayer structure. The residual oxygen in the low vacuum environment assists the decomposition of organic ligands for Pd to form a thin and continuous layer beneath submicron Pd aggregates. The oxidized bilayer film behaves as a temperature sensor with a sensitivity of 0.19% resistance change per °C, which can be used to compensate the sensed pH signals. Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is drawn by hand to form a free chlorine sensor. Free chlorine oxidises PEDOT:PSS, whose resistivity increment indicates the free chlorine concentration in the range of 0.5-500 ppm. Also, we simplified an amperometric free chlorine sensor based on amine-modified pencil leads. The simplified sensor is calibration-free, potentiostat-free, and easy-to-use. The pH, temperature, and free chlorine sensors are fabricated on a common substrate and connected to a field-programmable gate array board for data processing and display. The sensing system is user-friendly, cheap, and can accurately monitor real water samples. / Thesis / Doctor of Philosophy (PhD) / Sensitive, easy-to-use, and low-cost pH and free chlorine monitoring systems are important for drinking water safety and public health. In this thesis, we develop an inkjet printing technology to deposit palladium/palladium oxide films for potentiometric pH sensors and resistive temperature sensors. The different electrical and electrochemical properties of the palladium/palladium oxide films are realized by creating different film morphologies using different ink thermolysis atmospheres. The developed pH and temperature sensors are highly sensitive, fast in response, and stable. For free chlorine sensors, a hand drawing process is used to deposit poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), which is an indicator for the free chlorine concentration over a wide range. We also developed a calibration-free free chlorine sensors based on modified pencil leads. Such a free chlorine sensor is integrated with the pH and temperature sensors, and an electronic readout system for accurate on-site drinking water quality monitoring at low cost is demonstrated.

Den fundamentala principen för tillverkning av papper är inte en särskilt komplicerad sådan. Men för att pappret skall erhålla specifika egenskaper blir processen alltmer komplicerad. Bland annat tillsätts olika typer av kemikalier och processen övervakas ständigt av olika system. Ett av dessa system mäter pH-halten i pappersmassan. Mätsystemet är dock utsatt för frekventa mätfel vilket medför en felaktig dosering av den koldioxid som används för att sänka pH-värdet. Detta kan slutligen ha negativ påverkan på papprets egenskaper. Syftet bakom arbetet är att mätsystemet ska bidra till en jämn reglering av pH och därigenom garantera jämn papperskvalitet. För detta arbete har en frågeställning och ett antal mål och delmål etablerats. De övergripande målen omfattar att etablera en statistisk modell över mätfel och beräkna eventuella ekonomiska besparingar. För att uppfylla mål och besvara frågeställningen måste en grunduppfattning byggas uppför berörda delar av tillverkningsprocessen, pH-värdets påverkan i processen, pH-sensorns mätprincip, mätsystemets utformning och rutiner som berör mätsystemet. Med denna grund undersöks uppkomsten av mätfel för de sex mätpunkterna. Detta utförs med två tillvägagångssätt: Sammanställning av lagrade historiska data och sammanställningar avprovtagningar utförda under kontrollerade förhållanden. De aspekter som undersöks är magnitud, frekvens och hur dessa förhåller sig till olika processrelaterade värden. En kalkyl för kostnader berörande mätsystemet upprättas även. Denna omfattar aktuella kostnader för koldioxid och underhåll. I resultatet presenteras en statistisk modell över mätfel, uppdelat på historiska och i närtid. Den historiska modellen visar, för samtliga behandlade positioner, en medelavvikelse på <0,3 pH-enheter. Den min- och maximala avvikelsen kan däremot uppgå till >0,8 pH-enheter. Modellen för närtid visar på kraftiga avvikelser för fyra av de sex behandlade systempositionerna, som relaterar både till papperskvalitet och ytvikt. Denna statistiska modell används sedan för att beräkna möjliga besparingar. Här påvisades att viss besparing fanns, både för koldioxid och för underhållskostnader. Slutsatsen för detta arbete är att ett mätfel existerar för majoriteten av de behandlade positionerna. Det har även kunnat påvisas ett samband med de undersökta processrelaterade aspekterna, men resultatet kan inte garanteras fullständigt. Med detta kunde även en möjlig besparing av koldioxid uppskattas vid bättre mätnoggrannhet. Besparingen uppgick till c:a 200 tkr, vilket i jämförelse med företagets omsättning endast utgör 0,075‰ av denna. / The fundamental principle for manufacturing paper is not a complicated one. However, for the paper to acquire specific properties, the process becomes increasingly complicated.Among other things, different chemicals are added, and the process is continuouslymonitored by various systems. One of these systems measures the pH-level of the pulp. This system is however constantly affected by measuring errors, which in turn leads to the incorrect dosage of the carbon dioxide used to lower the pH-level. This could in turn have a negative impact on the properties of the final paper. The underlaying purpose of this project is for the measuring system to ensure an even regulation of pH and therethrough guarantee an even paper quality. For this project, several question at issue, goals and subgoals have been established. The general goals cover establishing a statistical model for the error and estimate possible economical savings. To fulfil the goals and answer the questions at issue, firstly a basic understanding must be established for: concerned parts of the manufacturing process, the effect pH-level has on the process, the measuring principle of the pH-sensor, the design of the measuring systemand the routines concerning the measuring system. With this basis, the occurrence of measuring error is examined for the six measuring points. This is accomplished with two methods: The compilation of historical data and the compilation of manual measurementsexecuted under controlled conditions. The aspects examined are magnitude, frequency and the relation to process related values. Finally, a calculation for costs regarding the measuring system was established. This includes current carbon dioxide and maintenance costs. The result presents a statistical model for the measuring error, divided into historical and near time. The historical model shows that for all the addressed positions, a mean deviation occurred <0.3 pH-units. However, the minimum and maximum deviation could reach >0.8 pH-units. The model for near time shows significant deviations for four out of the six covered positions, which in turn shows relations to both paper quality and surface weight. With this statistical model possible savings were calculated. This in turn showed the possibility of savings for both carbon dioxide and maintenance. The conclusion for this project is the existence of a measuring error. Also, a connection between this and the process related aspects could be established. Although, the result cannot be completely guarantied. With this, possible savings through better accuracy could be estimated. Though, these were only in the size of 0.075‰ of the company’s total revenue.

This paper presents the design, simulation, assembly and testing of a force-compensated hydrogel-based pH sensor. In the conventional deflection method, a piezoresistive pressure sensor is used as a chemical-mechanical-electronic transducer to measure the volume change of a pH-sensitive hydrogel. In this compensation method, the pH-sensitive hydrogel keeps its volume constant during the whole measuring process, independent of applied pH value. In order to maintain a balanced state, an additional thermal actuator is integrated into the close-loop sensor system with higher precision and faster dynamic response. Poly (N-isopropylacrylamide) (PNIPAAm) with 5 mol% monomer 3-acrylamido propionic acid (AAmPA) is used as the temperature-sensitive hydrogel, while poly (vinyl alcohol) with poly (acrylic acid) (PAA) serves as the pH-sensitive hydrogel. A thermal simulation is introduced to assess the temperature distribution of the whole microsystem, especially the temperature influence on both hydrogels. Following tests are detailed to verify the working functions of a sensor based on pH-sensitive hydrogel and an actuator based on temperature-sensitive hydrogel. A miniaturized prototype is assembled and investigated in deionized water: the response time amounts to about 25 min, just half of that one of a sensor based on the conventional deflection method. The results confirm the applicability of the compensation method to the hydrogel-based sensors.

No description available.

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第22508号 / 農博第2412号 / 新制||農||1078(附属図書館) / 学位論文||R2||N5288(農学部図書室) / 京都大学大学院農学研究科応用生命科学専攻 / (主査)教授 加納 健司, 教授 三芳 秀人, 教授 宮川 恒 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM