Orientador: Hideko Yamanaka / Co-orientador: Antonio Aparecido Pupim Ferreira / Banca: Assis Vicente Benedetti / Banca: Zeki Naal / Resumo: Os corantes azo estão entre os mais utilizados pela indústria têxtil brasileira, representando de 20-40% dos corantes empregados para tingir algodão, rayon, nylon, seda, lã e couro. Um fator preocupante relacionado a estas substâncias é que estudos utilizando microorganismos e células de mamíferos têm demonstrado que diversos corantes azo apresentam atividade genotóxica, mesmo em baixas concentrações. Além disso, atualmente ainda não estão vigorando métodos oficiais para efetiva remoção dos corantes presentes nos efluentes gerados no processo de tingimento dos tecidos, e isso faz com que essas substâncias possam chegar à agua destinada ao consumo, e assim, o desenvolvimento de dispositivos sensores para o monitoramento dos corantes em água se torna de grande importância. Diante disso, o presente trabalho versa sobre o desenvolvimento de um imunossensor impedimétrico para detecção e quantificação do corante azo Disperso Red 1 (DR1) em baixos níveis de concentração em água tratada e para tal, duas estratégias metodológicas foram estudadas. A primeira delas se fundamentou na construção do imunossensor empregando eletrodos impressos de ouro modificados com monocamadas auto-organizadas. Monocamadas tioladas de cistamina, ácido lipóico e p-aminotiofenol foram estudadas para promoção do acoplamento dos anticorpos sobre a superfície do eletrodo. Caracterizações realizadas por voltametria cíclica (VC) e espectroscopia de impedância eletroquímica (EIS) demonstraram a efetiva imobilização dos anticorpos sobre a superfície dos eletrodos impressos, com aumento sucessivo do recobrimento e no valor de resistência de transferência de carga (Rct), respectivamente. No entanto, para todas as rotas estudadas encontraram-se dificuldades em se obter adequada repetibilidade entre as diferentes medidas e estabilidade das etapas de modificação, além de não ser observada... / Abstract: Azo dyes are among the most used by Brazilian textile industry, representing 20-40% of dyes used for dyeing cotton, rayon, nylon, silk, wool and leather. A worrying factor related to these substances is that studies using micro-organisms and mammalian cells have shown that many azo dyes have genotoxic activity, even at low concentrations. Besides, currently there are not oficial methods for effective removal of dyes present in the effluents generated in the dyeing process, and this leads these substances can reach the water for consumption, and thus the development of sensor devices for monitoring the dyes in water becomes of great importance. Therefore, this project is focused on development of an impedimetric immunosensor for detection and quantification of the azo dye Disperse Red 1 (DR1) at low concentration levels in treated water and for this, two methodological strategies were studied. The first one was based on the construction of the immunosensor employing gold printed electrodes modified with self-assembled monolayers. Thiolated monolayers of cystamine, lipoic acid and p-aminothiophenol were studied to promote the coupling of the antibodies on the electrode surface. Characterizations performed by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) demonstrated the effective immobilization of antibodies on the surface of the printed electrodes, with successive increase in the surface coverage and in the charge transference resistance (Rct), respectively. However for all ways investigated, difficulties in obtaining adequate repeatability between measures of stability and modification steps were observed, as well a non-linear relationship between the values of ΔRct and the concentration of antigen DR1, which was due by the heterogeneity of the surface of different printed electrodes. Thus, the second strategy employed glassy carbon electrode for immunosensor construction... / Mestre

Microcystin-LR (MCLR) is hepatotoxic to animals and humans with disruption of liver structure causing cytoskeletal damage, necrosis and pooling of blood in the liver, leading to large increase in liver weight. It is also a strong liver tumor promoter and protein phosphatase inhibitor. Microcysin-LR binds protein phosphatases 1 and 2A, and influences regulation of cellular protein phosphorylation. In the present study, a colloidal gold based immunoassay test strip was developed for Microcystin-LR detection. The detection limit was found to be 1 ng/mL. 5 nm colloidal gold test strips exhibits more efficient for detection, compared with 20 nm colloidal gold test strips. The interaction between Microcystin-LR antibody (immunoglobulin G) and colloidal gold nanoparticles was investigated by various analytical methods, including Ultraviolet/Visible (UV/VIS), Fourier Transform Infrared (FTIR) and Fluorescence spectroscopy as well as transmission electron microscopy (TEM). / by Jiesi Xu. / Thesis (M.S.)--Florida Atlantic University, 2010. / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2010. Mode of access: World Wide Web.

O desenvolvimento de sensores eletroquímicos para glicose integrados a cateteres tem como requisitos básicos a sua miniaturização e funcionamento por períodos relativamente longos no ambiente intravenoso. A função de tais sensores é o acompanhamento de forma continuada e em tempo real, a evolução clínica de pacientes internados em unidades de terapia intensiva (UTIs). Dentre os sensores para glicose, os biossensores amperométricos baseados na reação enzimática de glicose oxidase se mostrou o mais promissor. Diferentes procedimentos para a construção de tais microssensores implantáveis foram desenvolvidos. Um conjunto de eletrodos, constituído fios de platina (mais adiante cobre, com diâmetro 0,18 mm) e de prata (diâmetro 0,20 mm) revestidos com poli-vinil-formol foram posicionados no interior de uma agulha de aço inoxidável (30,0 mm de comprimento e 0,80 a 1,2 mm de diâmetro) e fixados com resina epóxi, constituindo um dispositivo único com os eletrodos de trabalho, referência e auxiliar, respectivamente. A otimização do sensor envolveu a platinização eletroquímica da superfície do eletrodo de trabalho, o que aumentou a sua área efetiva e favoreceu a deposição do material enzimático. A presença de um detergente não iônico favoreceu a formação de um filme uniforme de enzimas e a eletropolimerização de 1,2-diaminobenzeno (em presença de albumina de soro bovino) foi utilizada para a formação de um filme com a característica de minimizar a interferência de espécies neutras. A adição de um filme de Náfion® à superfície do sensor aumentou a seletividade. O sensor resultante caracterizou-se por possuir um tempo de resposta curto (~6 s), linearidade de 1,0 até 12,5 mmol dm-3 com um limite de detecção de 1,0 mmol dm-3 , diminuição na resposta de espécies eletroativas (ácido ascórbico 2,0% e paracetamol 10,5% em relação à glicose) e uma vida útil superior a sete dias, em tampão fosfato 0,05 mol dm-3 . Para possibilitar o implante de tais sensores, foram exploradas diferentes metodologias de esterilização, sendo a mais favorável a irradiação com acelerador de elétrons com doses acumulativas. Sensores revestidos com acetato de celulose e Náfion® (a melhor condição) apresentaram perda de atividade da ordem de 15%, após serem irradiados. / The development of electrochemical sensors for glucose integrated into catheters has as basic requisite its miniaturization and the requirement of functioning for relatively long periods in the intravenous environment. The function of such sensors is the continuous monitoring on real time of the clinical evolution of patients hospitalized in intensive therapy units (UTIs). Amongst the sensors for glucose, amperometric biosensors based on the enzymatic reaction of glucose oxidase has been considered as the most promising ones. Different procedures for the construction of such microsensors to be implanted have been developed. A set of electrodes, constituted by a platinum wire (along this work, it was substituted by copper wires) with 0.18 mm diameter and a silver wire with 0.20 mm diameter coated with poly-vinyl-formol were positioned inside a stainless needle (30.0 mm length and 0.80 to 1.2 mm diameter) and fixed with epoxy resin, resulting in a single device containing the working, reference and auxiliary electrodes, respectively. The optimization of the sensor involved the electrochemical platinization of the working electrode surface, increasing its effective area and favoring the deposition of the enzymatic material. The presence of a non-ionic detergent favored the formation of a uniform film of enzyme and the electropolymerization of 1,2-diaminobenzene (in the presence of albumin and bovine serum) was used for the formation of a film able to ® interference of neutral species. The addition of a Nafion® film to the sensor surface increased its selectivity. The resultant sensor was characterized for its short time -3 response (~6 s), linearity between 1.0 and 12.5 mmol dm-3 with a detection limit of 1.0 mmol dm-3 , reduction in the interference of electroactive species (2.0% ascorbic acid and 10.5% paracetamol in relation to glucose) and a useful life larger than seven days, in 0.05 mol dm-3 phosphate buffer. To make possible the implantation of such sensors, different methodologies of sterilization were explored, being the most favorable the irradiation with electron accelerator using accumulating doses. Sensors coated with cellulose acetate and Nafion® (the best condition) presented loss of activity (around 15%), after the irradiation.

Orientador: Maria Del Pilar Taboada Sotomayor / Banca: Marcos Roberto de Vasconcelos Lanza / Banca: André Luiz dos Santos / Resumo: O presente trabalho mostra o desenvolvimento do primeiro biossensor descrito na literatura para determinação de antibióticos β-lactâmicos, usando pasta de carbono modificada com a enzima β-lactamase, e sua aplicação em amostras de leite de vaca in natura. A partir de estudos prévios de otimização da preparação do biossensor, o grafite em pó foi ativado com carbodiimida para permitir a ligação covalente da enzima β-lactamase que, junto com o mediador de elétrons ftalocianina de cobalto ofereceram variações na corrente catódica na presença da penicilina G, sendo esta escolhida para representar os antibióticos β-lactâmicos. Utilizando este procedimento para a construção dos biossensores, foi possível registrar voltamogramas cíclicos e amperogramas que permitiram quantificar a benzilpenicilina (penicilina G) em condições de análise também otimizadas, que incluíram estudo da quantidade de mediador na pasta; o pH, tipo e concentração do eletrólito usado para realização das medidas e o potencial aplicado na amperometria. Com o método otimizado foi possível detectar penicilina G em amostras de leite in natura, fortificadas com o antibiótico, com alta exatidão (erro relativo de 1%) e boa precisão (desvio padrão relativo de 8,3%, n = 3), mostrando que o biossensor desenvolvido é uma ferramenta promissora para detecção de penicilinas, e que ao serem realizados mais estudos para diminuir seu limite de quantificação, poderá se tornar uma um método de análise alternativo aos kits comerciais existentes / Abstract: This work describes the development of the first biosensor described in the literature for the determination of β-lactam antibiotics using a carbon paste electrode modified with the enzyme β-lactamase, and its application in samples of fresh cow's milk. After optimizing the biosensor preparation procedure, the graphite powder was activated with carbodiimide to allow covalent binding of the enzyme β-lactamase, which together with the electron mediator, cobalt phthalocyanine, offered variations in cathodic currents in the presence of penicillin G, which was chosen as representative of the β-lactam antibiotics. Using this procedure for the construction of biosensors, it was possible to record cyclic voltammograms and amperograms that enabled quantification of benzylpenicillin (penicillin G) under analytical conditions that had been optimized in terms of the amount of mediator in the paste, the pH, the type and concentration of the electrolyte used in the measurements, and the applied amperometric potential. With the optimized method, it was possible to detect penicillin G in samples of fresh milk fortified with the antibiotic, with high accuracy (error of 1%) and adequate precision (RSD of 8.3%, n=3), demonstrating that the proposed biosensor is a promising tool for the detection of penicillins. Once quantitation limits have been further improved, the analytical method could become an alternative to existing commercial kits / Mestre

This research developed a biosensor for kinase drug discovery applications. In particular it combined electronic techniques with optical techniques to understand the phosphorylation of proteins. There are two major electronic characteristics of phosphorylation that aid in its detection and subsequently biosensor development: first is the release of a proton upon phosphorylation of a protein (change in pH) and second is the addition of negative charge to the protein upon its phosphorylation. The work in this thesis reports an electrolyte–insulator–semiconductor sensing structures to detect the pH changes associated with phosphorylation and metal–insulator–semiconductor structures to detect the charge change upon phosphorylation of proteins. Major application of the developed devices would be to screen inhibitors of kinase that mediate phosphorylation of proteins. Inhibitors of kinase act as drugs to prevent or cure diseases due to the phosphorylation of proteins. With the advancements in VLSI and microfluidics technology this method can be extended into arrays for high throughput screening for discovering drugs.

O presente trabalho buscou investigar a formação da placa de aterosclerose através de caracterização da autofluorescência do tecido e do plasma na presença de marcadores fluorescentes. Para realizar o estudo, coelhos foram divididos em dois grupos: um grupo controle onde os animais foram submetidos a uma dieta normal e um grupo experimental onde os animais foram submetidos a uma dieta hipercolesterolêmica. Foram realizadas duas experimentações animais: na primeira os animais foram sendo eutanasiados ao longo do experimento e suas artérias foram coletadas. Na segunda os animais foram acompanhados por no máximo 80 dias. Durante o experimento apenas o sangue foi coletado e os animais foram eutanasiados no final do experimento. Dois marcadores fluorescentes foram utilizados no trabalho: o complexo európio-clorotetraciclina (EuCTc) e o corante tioflavina T (ThT). Analisouse inicialmente a fluorescência dos marcadores na presença do plasma dos coelhos tanto para o grupo controle, quanto para o grupo experimental em função dos tempos de dieta. Para o complexo EuCTc observou-se duas bandas de emissão, com excitação em 400 nm, uma característica da clorotetraciclina, em 515 nm e uma em 617 nm característica do íon európio. A análise da banda do íon európio indicou um incremento da banda de emissão do complexo na presença do plasma do grupo experimental em relação ao grupo controle. Para o corante ThT também foi observado um aumento na banda de emissão em 480 nm, com excitação em 413 nm, para o grupo experimental em comparação com o grupo controle. A potencialidade de utilização do complexo EuCTc e EuCTcMg (EuCTc na presença do íon magnésio) para marcação da placa de aterosclerose nas artérias, foi estudada através da análise de microscopia de fluorescência. Observou-se que a emissão do complexo melhora muito a visualização da placa quando comparada com a autofluorescência. Observou-se, através de microscopia de tempo de vida de fluorescência, que há uma transferência de energia entre os fluoróforos presentes na placa e os complexos EuCTc e EuCTcMg. Essa transferência de energia ocasionou em uma diminuição drástica no tempo de vida de fluorescência dos fluoróforos nessa região. Por fim, estudou-se a geração de segundo harmônico do colágeno na placa de aterosclerose, sendo obtidas diferenças na quantidade e organização do colágeno para os diferentes grupos experimentais. / This study aimed to investigate the formation of atherosclerotic plaque by the characterization of the autofluorescence of the tissue and plasma in the presence of fluorescent markers. For this study, rabbits were divided into two groups: a control group and an experimental group submitted to a hypercholesterolemic diet. The animal experimentation was performed twice, the first animals were being euthanized during the experiment and their arteries were collected. In the second experiment, the animals were followed for a maximum of 80 days and only during the experiment the blood was collected. The animals were euthanized at the end of experimentation. Two fluorescent markers were used in this study: europiumchlortetracycline complex (EuCTc) and the dye Thioflavin T (ThT). Firstly, it was analyzed the markers fluorescence in the presence of rabbits plasma for both, the control and the experimental groups with different diet times. For EuCTc complex, it was observed two bands of emission with excitation at 400 nm, first, a characteristic of chlortetracycline at 515 nm and at 617 nm characteristic of the europium ion. Analyzing only the band of europium ion, it was observed a greater increase of the complex in the presence of plasma in the experimental group. For ThT dye the emission band at 480 nm with excitation at 413 nm for the experimental group, in comparison with the control group. I was analysed the possibility to use EuCTc and EuCTcMg complex (EuCTc the Mg ion present) for marking the atherosclerotic plaque in arteries by fluorescence microscopy analysis. The results showed that the emission of the complex increase dramatically compared to the autofluorescence. Also, there was evidence of energy transfer between the fluorophores present of the plaque and EuCTc and EuCTcMg complex by fluorescence lifetime microscopy. This energy transfer generated a drastic decrease in the fluorescence lifetime of fluorophores. Finally, the generation of second harmonic of collagen in the atherosclerotic plaque was studied and it was obtained differences in the amount of collagen and organization in the different experimental groups.

As the rapid development of the applications of unconventional semiconductors in the 21th century, the new electronic and bioengineering revolutions based on solid state devices have become possible, that is facilitated through the understanding of electron or energy transfer process at the functionalized interfaces of organic semiconductors and two-dimensional (2D) materials. Especially in applications of photovoltaics and biosensors, the attributes of the interfaces play an important role in performance advancement. In this thesis, I have focused on the utilization of organic small molecule semiconductors as energy cascade materials to modify the interfaces between donor and acceptor of P3HT/PC₆₁BM binary organic solar cell, so as to improve the device performance. The charge transfer process at the interface of P3HT and functionalized graphene has also been investigated through P3HT/functionalized graphene blending photovoltaic devices. Moreover, I have concentrated on the interface of single layer MoS₂ and fluorescently-labeled DNA, where the electrons were transferred from fluorescent groups of DNA to MoS₂, resulting in fluorescence quenching. This quenching characteristic can be useful in other related biosensors. / In Chapter 1, an introduction to organic semiconductors and two-dimensional materials for applications in photovoltaics and biosensors has been presented. In Chapter 2, the experimental details used in this thesis have been discussed. / In Chapter 3, a novel small organic semiconductor molecule (CPA) with ambipolar attribute as an energy cascade material has been employed, to fabricate bulk heterojucntion solar cells. The organic photovoltaic devices with ternary structures, demonstrates a step of energy cascade to assist charge transfer between the electron-donating P3HT and electron-accepting PC₆₁BM. The ternary structure offers a distinct platform and an easily applicable approach to overcome shortcomings in P3HT-PC₆₁BM system by increasing the attainable product of short circuit current (JSC) and open circuit voltage (VOC). This ternary structure also retains the simplicity of a single processing step for photoactive layer. / In Chapter 4, to explore the potential of the p-type small organic semiconductor DTDCTB as energy cascade material in ternary blend bulk heterojunction (BHJ) solar cells, I have studied a BHJ system based on poly (3-hexylthiophene) (P3HT), [6,6]-phenyl C₆₁ butyric acid methyl ester (PC₆₁BM) and DTDCTB. This ternary structure demonstrates the improvement of power conversion efficiency (PCE) as compared to that of the binary devices composed of P3HT/PC₆₁BM alone. A systematic spectroscopic study was carried out to elucidate the underlying mechanism. Wavelength-dependent external quantum efficiency measurement confirmed the DTDCTB contribution to the increased photocurrent. Photoinduced spectroscopy and transient photovoltage measurements unambiguously revealed that the charges generated in DTDCTB were efficiently transferred to and transported in P3HT and PC₆₁BM. The results also suggested that despite the realization of cascade charge transfer, the bimolecular charge recombination process in the ternary system is still dominated by the P3HT/PC₆₁BM interface. / In Chapter 5, a simple method by using aryl diazonium salt reaction has been devised to achieve covalent bond formation by altering the hybridization of carbon atom in configuration of sp² to sp³. Afterwards the group of benzoic acid has been grafted onto pristine graphene, to open a band gap of this two-dimensional material. It was well functionalized, dissolved in organic solvents to provide the various of fabrication processes for electron devices. The LUMO of functionalized graphene below the LUMO of P3HT and close to that of PC₆₁BM indicates its suitability as an electron-acceptor for OPV applications. Then the bulk heterojunction solar cells composed of P3HT/functionalized graphene composite as active layer have been further prepared, achieving a PCE efficiency of 1.1%. / In Chapter 6, a novel MoS₂-based fluorescent biosensor for DNA detections via hybridization chain reactions (HCRs) has been demonstrated. MoS₂, as an emerging nanomaterial, has excellent fluorescence quenching ability and distinct adsorption properties for single- and double-stranded DNA. In the sensing method, MoS₂ nanosheets were used to suppress the background signal and control the “on” and “off” states of fluorescence emission of the detection system with and without the presence of the target DNA. In addition, the signal generation was amplified through the target-triggered HCRs between two hairpin probes. The utilization of MoS₂ and HCRs guaranteed the high sensitivity of the detection strategy with the detection limit of 15pM. The biosensor also exhibited very good selectivity over mismatched DNA sequences. The detection took place in solutions and requires only one “mix-and-detect” step. The high sensitivity, selectivity, and operational simplicity demonstrate that MoS₂ can be a promising nanomaterial for versatile biosensing. / In Chapter 7, I provide the conclusions and a brief prospect of the further development in ternary system of perovskite solar cells and in based-two dimensional materials micro-fluidic biological monitoring FET. / 對於二十一世紀，隨著人們對非传统半导体材料应用的發展有著迫切的需求，新的基於固態器件的電子工程和生物工程的革命正在悄然進行，這是基於對有機半導體材料和二維層狀材料的功能化的界面上發生的電子或者能量轉移的理解，特別是在太陽能電池器件和生物傳感器方面上的應用。本論文主要是關注與利用有機半導體小分子作為能級梯級材料去调节P3HT/PC₆₁BM二元有機光伏器件中給體與受體見的界面，從而得到更好性能的器件。同時也關注了P3HT和功能化的石墨烯界面上的電荷轉移，并通過P3HT/功能化石墨烯混合有機光伏器件來研究界面上的電荷轉移。另外，還關注了單層硫化鉬和螢光標記的DNA間的界面，在這個界面上DNA螢光基團的能量會轉移到二硫化鉬上從而導致螢光淬滅，並且應用這一淬滅特性在生物傳感上。 / 在第一章中，本論文對有機半導體和二維材料在光伏器件和生物傳感器件中的應用給出了一個簡單的介紹。第二章展示了論文涉及到的檢測方法。 / 在第三章中，本論文利用一種新型的具有雙極性的有機半導體小分子(CPA)作為能級梯級材料去製作異質結太陽能器件。這些具有三元體系結構的太陽能器件展示了能級梯級變化的過程，這個過程是為了改善電子給體P3HT和電子受體PC₆₁BM間的電荷轉移。這種三元體系結構提供了一種顯著而且簡單的方法來克服P3HT-PC₆₁BM二元體系的不足，并通過提高其短路電流和開路電壓的乘積來實現，同時保持簡單的一步光敏層的製作方式。 / 在第四章中，為了探索P型有機半導體小分子DTDCTB能否作為級聯材料在有機異質結太陽能器件中使用，本論文研究了三元體系包含P3HT，PC₆₁BM和DTDCTB的有機異質結太陽能器件。這種三元結構器件展現出更佳的性能對比與P3HT/PC₆₁BM二元體系器件。另外，三元體系中電荷轉移的內在機制通過一系列系統的光譜來闡明。光誘導光譜和瞬態光電壓測試明確的揭示了DTDCTB中產生的電荷會被有效的通過P3HT和PC₆₁BM傳輸走。這些結果還表明，儘管存在級聯電荷傳輸，但是雙分子間的電荷複合過程主要發生在P3HT/PC₆₁BM界面。 / 第五章提出一個簡單的通過使用芳香基重氮鹽反應的方法，實現了碳碳共價鍵合成的反應，這種反應是通過改變碳原子sp²雜化成sp³雜化的方式進行的，而且可以移植苯甲酸官能團到原味的石墨烯上來打開石墨烯的帶隙。石墨烯這種二維層狀材料通過明確的的功能化后，可以溶在有機溶劑中從而提供了其作為電子器件的製作工藝的多元化。功能化后的石墨烯的LUMO能級比P3HT的LUMO能級要低，並且接近于PC₆₁BM的LUMO能級，這一特性意味著功能化后的石墨烯作為電子受體在有機光伏器件中的應用是可行的。因此，本論文進一步展示了以P3HT和功能化后的石墨烯複合材料作為光敏層的異質結太陽能器件，並且其具有1.1%的光電轉化效率。 / 在第六章中，本論文提出了一種新型基於二硫化鉬的螢光生物傳感器，這一傳感器通過雜交連鎖反應(HCRs)應用於DNA檢測。二硫化鉬作為新興的納米材料，有著對單鏈或者雙鏈DNA的良好螢光淬滅和顯著的吸附特性。在此檢測方法中，二硫化鉬納米片被用來抑制背景信號，並且通過存在或者不存在目標DNA來控制檢測體系中螢光發射的開啟和閉合。另外，檢測信號通過兩個髮夾型DNA探針間的目標觸發的HCR方法放大。通過使用二硫化鉬和HCR實現了高靈敏度的檢測，其檢測極限是15pM。這個傳感器對於DNA的錯配具有良好的選擇性。這個檢測在溶解中進行，並且僅僅需要簡單的一步混合來實現。高的靈敏度、選著性和工藝簡單等特性表明了二硫化鉬這種納米材料可以在多種生物檢測中使用。 / 第七章三元體系鈣鈦礦結構光伏器件和基於二維材料微流生物檢測器件的應用。 / Ye, Lei. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2014. / Includes bibliographical references. / Abstracts also in Chinese. / Title from PDF title page (viewed on 04, October, 2016). / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only.

由於表面等離子體激元可以將電磁場限制在金屬表面，從而產生強烈的場強增強效果，因此在納米光子學和生物光子學方面具有廣泛的應用價值，其中包括高性能發光二級管、光伏電池、超高分辨率光學成像和超靈敏分子檢測等。尤其在單分子和醫學診斷方面，基於表面等離子體共振的生物傳感器獲得了越來越多的青睞。本論文包括兩部份。第一部份著重討論二維週期性洞陣列的表面等離子體特性，而第二部份則是研究這種洞陣列結構在表面等離子體共振傳感方面的應用。 / 在第一部份中，表面等離子體模式被分為非簡並模式(m，O) 和簡並模式(m，±n)兩種情況分別加以討論。首先，結合實驗結果和理論模型，我們對非簡並模式的衰減壽命和激發效率進行了研究。通過光干涉光刻法和薄膜沉積技術，一系列不同幾何結構的洞陣列樣品被製備出來，且這些樣品具有很高的重複性。利用角分辨色散關係進行模式識別以及確定這些模式的衰減壽命和激發效率。通過調整起偏器和檢偏器的相對方向，表面等離子體模式的非輻射和輻射衰竭均可加以研究。結果發現，衰減壽命強烈依賴於單洞的幾何結構，而且這種行為可以用簡單的靜電模型并考慮高階修正加以解釋。從非輻射衰減和輻射衰減平衡的角度出發，激發效率對幾何結構和共振波長的依賴性也可以理解。對於簡并模式，由於存在稱合，對稱模式和反對稱模式分別被p 偏振激發和S偏振激發。它們的對稱性和對於衰減壽命和共振波長的修正可以用干涉法和模式耦合理論來理解。最後，利用多模耦合方程，我們對色散關係圖譜隨著洞深度增加而演化的情況也進行了探討。 / 第二部份對基於表面等離子體共振的生物傳感器與陣列幾何結構的關係進行了研究。結果發現，激發效率和衰減壽命對表面等離子體共振傳感器的分辨率都起到了關鍵性作用。在共振中，峰值高度和帶寬主要由表面等離子體的衰減速率控制。較低的衰減速率導致較清晰的峰值線型，從而產生較高的傳感器分辨率。因此，通過調整陣列的幾何結構以產生非常低得輻射衰減速率，表面等離于體共振傳感器的品質因數可高達104.8/RIU ，這已經超過了基於梭鏡和納米粒子對應器件的性能表現。 / Surface plasmon polaritons (SPPs) generate a strong localized electromagnetic field on metal surface and thus are promising for nano- and bio-photonics including high performing light-emitting diodes and photovoltaic cells, super-high resolution optical imaging, ultra-high sensitive bimolecular detection, etc. In particular, the application of SPPs on surface plasmon resonance (SPR) biosensor has drawn much more attention recently because of the attempt to realize single molecule detection in medical diagnosis. / This thesis contains two parts. The first part focuses on studying the basic plasmonic properties of two-dimensional periodic hole arrays while the second part concentrates on the application of hole arrays on SPR sensing. / In the first part, SPPs modes on hole arrays are classified into nondegenerate mode (m, 0) and degenerate mode (m, ±n). For nondegenerate mode, its decay lifetime and generation efficiency are studied both experimentally and theoretically. By combining interference lithography and thin film deposition, a set of arrays with a wide range of geometry has been fabricated with high reproducibility. The dispersion relations of arrays are studied by angle-dependent reflectivity for mode identification and detenninations of SPP decay lifetime and generation efficiency. In particular, through orienting the polarization of the specular reflection either parallel or orthogonal to that of the incidence, we can access both the nonradiative and radiative decays of SPPs at different resonance wavelengths. As a result, it is found that decay lifetime is strongly dependent on the geometry of single hole and its behaviors can be understood by using a simple quasi-static model taking into account of the higher order correction as well as numerical simulation deduced by finite-difference timedomain. The dependence of generation efficiency on hole geometry or resonance wavelength can be understood in tenns of trade-off between nonradiative and radiative decay rates. Once these two decay rates equals to each other, the optimum generation efficiency is realized and the field enhancement gets the maximum. And the optimum parameters can be achieved by adjusting the hole geometry or the resonance wavelength. For degenerate mode, due to the coupling between (m, +n) and (m, -n) modes, a symmetric and an anti-symmetric modes are excited under pand s-polarized excitation, respectively. Their symmetries and modifications to the decay lifetime and resonance wavelength can be understood by using the interference method and coupled mode theory. Finally, generalized coupled mode equations are employed to know about the evolution of dispersion relation as hole depth increases. / The dependence of SPR biosensor on the generation and decay of SPPs are studied in the second part. Both the generation efficiency and decay lifetime of SPPs are found to be critical in governing the resolution of SPR biosensor. In SPR, the peak height and linewidth are primarily controlled by the decay rate of SPPs. Lower decay rate leads to sharper peak profile, which results in higher SPR resolution. Therefore, by tailoring the geometry of hole arrays to achieve a very low radiative decay rate, a SPR biosensor with figure of merit (FOM) reaching l04.8/RIU can be realized, which surpasses those of prism and nanoparticle counterparts. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Zhang, Lei = 表面等離子體激元對於週期性金屬納米結構幾何形狀的依賴性及其在生物傳感中的應用 / 張磊. / "November 2011." / Thesis (Ph.D.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references (leaves 116-125). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese. / Zhang, Lei = Biao mian deng li zi ti ji yuan dui yu zhou qi xing jin shu na mi jie gou ji he xing zhuang de yi lai xing ji qi zai sheng wu chuan gan zhong de ying yong / Zhang Lei. / Chapter Chapter1 --- Introduction --- p.1 / Chapter Chapter2 --- Theoretical Background --- p.7 / Chapter 2.1 --- Maxwell's equations --- p.7 / Chapter 2.2 --- Classic electromagnetic theory for dielectric properties of matter --- p.9 / Chapter 2.3 --- Surface plasmon polaritons at the dielectric/metal interface --- p.11 / Chapter 2.4 --- Excitation of surface plasmon polaritons --- p.16 / Chapter 2.4.1 --- Prism coupling --- p.17 / Chapter 2.4.2 --- Grating coupling --- p.17 / Chapter 2.5 --- lones calculus --- p.19 / Chapter 2.6 --- Finite-difference time-domain method --- p.22 / Chapter Chapter 3 --- Sample Preparation --- p.25 / Chapter 3.1 --- Interference lithography --- p.25 / Chapter 3.1.1 --- Substrate preparation --- p.26 / Chapter 3.1.2 --- Exposure --- p.27 / Chapter 3.1.3 --- Pattern development --- p.30 / Chapter 3.2 --- Thin film deposition --- p.30 / Chapter Chapter 4 --- Experimental Setups and Calibration --- p.33 / Chapter 4.1 --- Experimental setup for measuring dispersion relation --- p.33 / Chapter 4.2 --- Experimental setup calibration --- p.35 / Chapter 4.2.1 --- Calibration of spectrometer --- p.36 / Chapter 4.2.2 --- Calibration of movement stages --- p.38 / Chapter 4.3 --- Data presentation for dispersion relation --- p.40 / Chapter 4.4 --- Summary --- p.41 / Chapter Chapter 5 --- Understanding of Fundamental Properties of SPPs --- p.43 / Chapter 5.1 --- Excitation of SPPs on 2D hole arrays --- p.44 / Chapter 5.2 --- Properties of non degenerate modes and theoretical explanation --- p.53 / Chapter 5.2.1 --- Dependence of lifetime on hole geometry and theoretical explanation --- p.55 / Chapter 5.2.2 --- Dependence of generation efficiency on hole geometry and theoretical explanation --- p.63 / Chapter 5.3 --- Properties of degenerate modes and theoretical explanation --- p.70 / Chapter 5.3.1 --- Dependence of properties of degeneration modes on hole geometry by FDTD --- p.72 / Chapter 5.3.1.1 --- (0, ±l)[subscript s,a] modes --- p.72 / Chapter 5.3.l.2 --- (-1, ±l)[subscript s,a] modes --- p.76 / Chapter 5.3.2 --- Understanding of excitation of degenerate modes by using interference method --- p.79 / Chapter 5.3.3 --- Understanding of coupling between degenerate modes by using coupled mode theory --- p.85 / Chapter 5.4 --- Evolution of dispersion relation as hole depth increases --- p.90 / Chapter 5.5 --- Summary --- p.95 / Chapter Chapter 6 --- Surface Plasmon Resonance Based Label Free Biosensor --- p.98 / Chapter 6.1 --- Basics of surface plasmon resonance (SPR) based biosensor --- p.98 / Chapter 6.2 --- State-of-the-art SPR biosensor --- p.101 / Chapter 6.3 --- SPR biosensor by using 2D metallic hole arrays --- p.102 / Chapter 6.4 --- Summary --- p.111 / Chapter Chapter 7 --- Conclusions --- p.112 / References --- p.116 / Publications --- p.126

MEMS (Microelectromechanical Systems) acoustic sensors are a promising platform for Point-of-Care biosensing. In particular, piezoelectrically driven acoustic sensors can provide fast results with high sensitivity, can be miniaturized and mass produced, and have the potential to be fully integrated with sample handling and electronics in handheld devices. Furthermore, they can be designed as multiplexed arrays to detect multiple biomarkers of interest in parallel. In order to develop a microfabricated biosensing platform, a specific and high affinity biodetection platform must be optimized, and the microfabricated sensors must be designed to have high sensitivity and maintain good performance in a liquid environment. A biomolecular sensing system that uses high affinity peptide aptamers and a passivation layer has been optimized for the detection of proteins of interest using the quartz crystal microbalance with dissipation monitoring (QCM-D). The resulting system is highly specific to target proteins, differentiating between target IgG molecules and other closely related IgG subclasses, even in complex environments such as serum. Piezoelectrically actuated MEMS resonators are designed to operate in flexural microplate modes, with several modes shown to be ideally suited for fluid based biosensing due to improved performance in the liquid environment. The increase in quality factor of these MEMS microplate devices in liquid, as compared to air, is further investigated through the analytical and finite element modeling of MEMS fluid damping mechanisms, with a focus on acoustic radiation losses for circular microplate devices. It is found that the impedance mismatch at the air-water interface of a droplet is a key contributor to reduced acoustic radiation losses and thus improved device performance in water. Microplate acoustic sensors operating in flexural plate wave and microplate flexural modes are then integrated with a fluidic cell to facilitate protein sensing from fluid samples. Flexural plate wave devices are used to measure protein mass adsorbed to the sensor surface and initial results toward microplate flexural mode protein sensing are presented. Finally, challenges and areas of future research are discussed to outline the path towards finalization of a sensing platform taking advantage of the combination of the sensitive MEMS acoustic sensor capable of operating in a liquid environment and the specific and high affinity biomolecular detection system. Together, these form the potential basis of a novel Point-of-Care platform for simple and rapid monitoring of protein levels in complex samples.

Law Wing Cheung. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references. / Abstracts in English and Chinese. / Abstract --- p.I / Acknowledgements --- p.V / List of Publications related to this project --- p.VI / Contents --- p.VII / Chapter Chapter 1 --- Introduction --- p.1-1 / Chapter Chapter 2 --- Literature Review / Chapter 2.1 --- Surface Plasmon Waves --- p.2-2 / Chapter 2.2 --- Excitation of Surface Plasmon --- p.2-4 / Chapter 2.2.1 --- Surface Plasmon Coupling Schemes --- p.2-6 / Chapter 2.3 --- Detection Techniques used in SPR sensors --- p.2-13 / Chapter 2.3.1 --- Angular Interrogation --- p.2-14 / Chapter 2.3.2 --- Wavelength Interrogation --- p.2-15 / Chapter 2.3.3 --- Intensity Interrogation --- p.2-16 / Chapter 2.3.4 --- Phase Interrogation --- p.2-16 / Chapter 2.3.5 --- Commercial SPR biosensors --- p.2-18 / Chapter 2.3.6 --- Comparison between Detection Techniques --- p.2-19 / Chapter 2.4 --- Applications of SPR biosensors --- p.2-21 / Chapter Chapter 3 --- Principle of Surface Plasmon Resonance Sensing Technology / Chapter 3.1 --- SPR Phenomenon --- p.3-1 / Chapter 3.2 --- Conditions for Surface Plasmon Resonance --- p.3-5 / Chapter 3.3 --- Wave-vectors --- p.3-7 / Chapter 3.4 --- Surface Plasmon Resonance described by Fresnel's Theory --- p.3-8 / Chapter 3.5 --- Concept of Surface Plasmon Resonance Biosensing --- p.3-10 / Chapter Chapter 4 --- Experiments / Chapter 4.1 --- Highly sensitive differential phase-sensitive surface plasmon resonance biosensor based on Mach-Zehnder configuration --- p.4-1 / Chapter 4.1.1 --- Materials required --- p.4-1 / Chapter 4.1.2 --- Experimental Setup --- p.4-2 / Chapter 4.1.3 --- Principle of Differential Phase Measurement --- p.4-3 / Chapter 4.1.4 --- Photodetector Circuitry --- p.4-6 / Chapter 4.1.5 --- Digital Signal Processing --- p.4-7 / Chapter 4.1.6 --- Polymer based Micro-fluidic System Integrated with SPR Biosensor --- p.4-9 / Chapter 4.2 --- Phase-sensitive Surface Plasmon Resonance Biosensor using the Photoelastic Modulation Technique --- p.4-12 / Chapter 4.2.1 --- Materials required --- p.4-12 / Chapter 4.2.2 --- Experimental Setup --- p.4-13 / Chapter 4.2.3 --- Principle of Photoelastic Modulation Technique and Signal Processing --- p.4-14 / Chapter 4.2.4 --- Operation Principle of Photoelastic Modulator --- p.4-17 / Chapter 4.3 --- Sample Preparations --- p.4-18 / Chapter 4.3.1 --- Glycerin-water Mixtures --- p.4-18 / Chapter 4.3.2 --- "PBS, BSA and BSA antibody" --- p.4-19 / Chapter 4.3.3 --- "RPMI, Trypsin, Cells and SDS" --- p.4-20 / Chapter Chapter5 --- Results amd Discussions / Chapter 5.1 --- Experimental setup I: Highly sensitive differential phase-sensitive surface plasmon resonance biosensor based on Mach-Zehnder configuration --- p.5-1 / Chapter 5.1.1 --- Measuring various glycerin-water concentration mixture with silver-gold sensing layer --- p.5-1 / Chapter 5.1.2 --- Comparison between the sensitivity of our setup and reported setup based on phase detection --- p.5-4 / Chapter 5.1.3 --- Discussion on 0.01° system resolution --- p.5-7 / Chapter 5.1.4 --- Experiment on monitoring BSA-BSA antibody binding reaction --- p.5-9 / Chapter 5.1.5 --- Matching oil and glass slide --- p.5-11 / Chapter 5.1.6 --- Experiments on monitoring BSA-BSA antibody binding reaction with integrated microfluidic system --- p.5-12 / Chapter 5.1.7 --- Experiment on observing cell adhesion properties on gold surface under the influence of trypsin --- p.5-14 / Chapter 5.1.8 --- Discussion on the non-specific binding between trypsin and gold surface --- p.5-16 / Chapter 5.1.9 --- Modifying the gold surface with BSA layer --- p.5-17 / Chapter 5.1.10 --- Experiment on observing cell adhesion properties on the gold surface under the influence Sodium Dodecyl Sulfate (SDS) --- p.5-18 / Chapter 5.2 --- Experimental setup II: Phase-sensitive surface plasmon resonance biosensor using the photoelastic modulation technique --- p.5-21 / Chapter 5.2.1 --- Measurement on difference glycerin-water concentration mixture --- p.5-21 / Chapter 5.2.2 --- Experiment on monitoring BSA-BSA antibody binding reaction --- p.5-23 / Chapter Chapter 6 --- Conclusions and Future Works / Chapter 6.1 --- Conclusions --- p.6-1 / Chapter 6.2 --- Future Works --- p.6-2 / References --- p.R-1 / Appendix / Chapter A. --- Phase Extraction Routine written by Matlab --- p.A-1 / Chapter B. --- Mathematical expressions for calculating the phase angle in the experiment of SPR biosensor using the Photoelastic Modulation Technique --- p.A-6 / Chapter C. --- Relationship between Concentration and Refractive Index of Glycerin-Water Mixture --- p.A-11 / Chapter D. --- Physical Properties of Bovine Serum Albumin --- p.A-12 / Chapter E. --- Simulation Curve written by Matlab --- p.A-13