Submitted by Angela Maria de Oliveira (amolivei@uepg.br) on 2018-02-07T12:42:14Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Rolf de Campos.pdf: 5588727 bytes, checksum: d81ab37d8cd335285d51711794fbbc44 (MD5) / Made available in DSpace on 2018-02-07T12:42:14Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Rolf de Campos.pdf: 5588727 bytes, checksum: d81ab37d8cd335285d51711794fbbc44 (MD5) Previous issue date: 2017-07-05 / Fundação Araucária de Apoio ao Desenvolvimento Científico e Tecnológico do Paraná / Esta tese descreve as interações entre o surfactante não iônico p-(1,1,3,3 tetrametilbutil) fenil polietilenoglicol (denominado Triton X) e dodecil sulfato de sódio (SDS) com o polímero catiônico 3-cloreto-n-propilpiridínio silsesquioxano (SiPy) na presença da ftalocianina tetrasulfonada de níquel (NiTsPc), as quais foram avaliadas utilizando medidas de tensão superficial e viscosidade. Os efeitos dessas interações também foram estudados quando estes polieletrólitos foram transferidos para filmes finos pela técnica LbL sobre substrato condutor (óxido de estanho dopado com índio – ITO), quartzo e silício. Observou-se, por meio de técnica espectroscópica de absorção na região do UVVis, que há um efeito sinérgico proporcionado pela interação dos polieletrólitos catiônico (SiPy/surfactante) e aniônico (NiTsPc) nos filmes LbL. Por técnicas espectroscópicas FTIR e Raman, e técnicas eletroquímicas tais como impedância eletroquímica e voltametria cíclica, foi constatado que há coexistência de micelas mistas e puras e que a adsorção destes agregados tem um papel importante na superfície dos filmes LbL. Foi também realizada a síntese e a caracterização de nanopartículas de hidróxido de níquel, em sua fase α, estabilizadas pelo polímero SiPy, e pelo surfactante zwiteriônico 3-(1- alquil-3-imidazólio)propano-sulfonado. O surfactante ImS3-14 foi escolhido por sua interação preferencial com ânions, tornando-o um excelente limitante para o crescimento das nanopartículas de Ni(OH)2. A formação dos agregados foi caracterizada por espalhamento dinâmico de luz e potencial zeta, para determinar tamanho e carga das nanopartículas, respectivamente. Após a síntese das nanopartículas, estas foram depositadas através da técnica LbL em vários substratos. O crescimento dos filmes foi acompanhado por UV-VIS e sua caracterização foi realizada pelas técnicas de FTIR, Raman, AFM e MEV-FEG. As características eletroquímicas dos filmes foram estudadas por voltametria cíclica (VC) e espectroscopia de impedância eletroquímica (EIE). / This thesis describes the interactions between the nonionic surfactant p-(1,1,3,3- tetramethylbutyl)phenyl-polyethylene glycol (Triton X) and sodium dodecyl sulfate (SDS) with the cationic polymer 3-chloride-n-propylpyridinium silsesquioxane (SiPy) in the presence of nickel phthalocyanine tetrasulfonate (NiTsPc), which they were evaluated using surface tension and viscosity measurements. The effects of these interactions were also studied when these polyelectrolytes were transferred to thin films by the LbL technique on conductive substrate (indium doped tin oxide - ITO), quartz and silicon. It has been observed by UV-Vis absorption spectroscopy there is a synergistic effect provided by the interaction of the cationic polyelectrolytes (SiPy / surfactant) and anionic (NiTsPc) polyelectrolytes in the LbL films. Spectroscopic techniques, such as, FTIR and Raman, and electrochemical techniques, electrochemical impedance and cyclic voltammetry, it was observed that there is a coexistence of mixed and pure micelles. The adsorption of these aggregates plays an important role on the surface of the LbL films. The synthesis and characterization of nickel hydroxide nanoparticles, in their α phase, stabilized by the SiPy polymer, and by the zwitterionic surfactant 3- (1-alkyl-3 - imidazolium) propane sulfonate was realized. The surfactant ImS3-14 was chosen for its preferential interaction with anions, making it an excellent stabilizer for the growth of the Ni(OH)2 nanoparticles. The formation of the aggregates was characterized by dynamic scattering of light (DLS) and zeta potential to determine size and charge, respectively. After the synthesis of the nanoparticles, they were deposited by the LbL technique on several substrates. The growth of the films was accompanied by UV-VIS and their characterization was evaluated by FTIR, Raman, AFM and MEV-FEG techniques. The electrochemical characteristics of the films were studied using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS).

La cellulose étant l'un des biopolymères les plus abondants, elle est employée dans ce travail de thèse sous sa forme nano-fibrille (2 à 5nm de diamètre et plusieurs microns de long) pour préparer des nanomatériaux durables. Les microfibrilles de cellulose (MFC) chargées positivement ou négativement sont assemblées en couches minces dans ces nanomatériaux par la méthode « Layer by Layer » (LbL) par trempage, pulvérisation ou spin assisté. Les différences entre ces films LbL à base de MFC et les films LbL à base de polymères standards sont discutées brièvement et sont reliées à la forme nanofibrillaire de la cellulose. Les MFC réagissent comme des nano-objets anisotropes et rigides. Les films LbL de MFC sont ensuite intégrés à des membranes de séparation, entre la couche polymérique de séparation et le support poreux, pour améliorer le débit à travers ces membranes. Ces films minces sont également déposés sur des aérogels de cellulose pour améliorer la stabilité de ces aérogels en milieu aqueux. Dans les deux applications, les résultats était encouragent et montre une validation de principe. / Cellulose, one of the most abundant biopolymers, is used in this PhD work in its nanofibrillated form, 2-5 nm in diameter and microns long, to prepare sustainable nanomaterials. Both positively and negatively charged microfibrillated celluloses (MFC) are assembled in these nanomaterials using the versatile Layer by Layer (LbL) assembly methods: dipping, spray assisted-deposition and spin-assisted deposition. A brief comparison between the MFC based LbL assembled films and the standard polymeric LbL films is carried out. Thedifferences between the two species are related to the fibrillar form of cellulose. MFC behaves like rigid anisotropic nano-objects. MFC LbL assembled films are then integrated in separation membranes between active polymeric separation layers and a mechanically stable porous support to improve the flux through these membranes. MFC LbL assembled films are also coated on cellulosic aerogels to improve the wet stability of these aerogels. In both cases, results were encouraging and showed a proof of concept.

År 2020 listade Världshälsoorganisationen (WHO) cancer som den globalt ledande dödsorsaken med över 10 miljoner dödsfall årligen. Av dessa 10 miljoner fall förekommer nästan 70% i låg- till medelinkomstländer - en siffra som på grund av den låga prioriteringen av cancerbehandling- och diagnostik förväntas öka till 85% redan år 2030. Att utveckla enkla, specifika och prisvärda verktyg för diagnostik kommer därför att bli avgörande för förebyggandet av cancer på en global nivå. För att komma ett steg närmare denna utveckling optimerades och testades i denna studie ett mikrofluidiskt system, utvecklat genom layer-bylayer- metoden, baserat på cellulosa nanofibriller med förmågan att isolera och fånga cirkulerande tumörceller. För att uppnå en termodynamisk jämvikt optimerades systemets hydrodynamiska parametrar optimerades för att uppnå en homogen fördelning med hög densitet av det cellulosa-baserade systemet i det mikrofluidiska chippet. Då jämvikt är grundläggande för att maximera det efterföljande beläggningen av antikroppar, och därmed hur effektivt celler isoleras, modifierades parametrar såsom koncentration, flödeshastighet, inkubationstid med fler tills att önskad effekt uppnåtts. Således koncepttestades systemet genom att fånga celler spetsade i blod och därmed demonstrera att systemet kan användas i syfte att isolera cancerceller från blodprov. Detta öppnar upp för utveckling av liknande diagnostiska verktyg som kan användas för att isolera lågfrekventa celler direkt från blod. / In 2020, the World Health Organization (WHO) listed cancer as the leading cause of death worldwide, reaching a staggering number of 10 million cancer-related deaths annually. Of these 10 million deaths, nearly 70% occurred in low- and middle-income countries; a number that is expected to increase to 85% by 2030 due to the lack of resources as well as low priority of the development of cancer treatment and diagnosis. Hence, the development of a sophisticated, specific and affordable diagnostic tool will be crucial for global cancer prevention and control. In this study, a cellulose nanofibril-based Layer-by-Layer system for immuno-capture of tumour cells in a microfluidic device was optimized and tested for the development of a simple and cost-effective diagnostic tool for use in resource-limited areas. In the pursuit of a thermodynamic equilibrium, the hydrodynamic parameters of the system were optimized to achieve a homogeneous distribution with a high surface density of the cellulose-based system across the microfluidic channels. Since an equilibrated system is essential to maximize the antibody coating, and thereby cell capture efficiency, parameters including but not limited to concentration, flow rate and incubation time were altered until a desired effect had been achieved. Thus, as proof-of-concept, the system was tested by capturing cancer cells spiked into whole blood, thereby demonstrating that the system can be utilized for the purpose of isolating cancer cells from blood samples. This paves the way for the development of similar clinical diagnostic tools for the isolation of rare cells directly from whole blood.

Die Arbeit untersucht den Einfluss des pH - Wertes auf die Fluoreszenzintensität von Multischichtsystemen während des Beschichtungsvorgangs von Siliziumdioxidpartikeln mit kovalent an Polyallylaminhydrochlorid (PAH) gebundenem Rhodamin - B - Isothiocyanat. Durch eine konsequente Pufferung mit 2 -(N - Morpholino)ethansulfonsäure während der Beschichtung kann eine Verbesserung der Homogenität der Schichtbildung und eine Erhöhung der Fluoreszenzintensität erreicht werden. Außerdem liegt eine lineare Steigerung der Fluoreszenzintensität proportional zur Anzahl der fluoreszenten Schichten vor. Weiterhin sollen kolloidale Partikel unter konstanter Pufferung zusätzlich zu Rhodamin – B – Isothiocyanat mit an PAH – gebundenem Fluoresceinisothiocyanat beschichtet werden. Dieses Farbstoffpaar weist bei Annäherung eine Fluoreszenzsteigerung durch einen Fluoreszenzresonanzenergietransfer aus. Durch Variation von Schichtanzahl und Abstand wurden verschiedene Partikelpopulationen hergestellt, die sich in Ihrer Fluoreszenzintensität analog zu einem Bead Array Assay im Durchflusszytometer klar differenzieren lassen und dabei auch eine gleichmäßige Steigerung der Fluoreszenzintensität analog zur Anzahl der fluoreszenten Schichten aufweisen.

An electrochromic (EC) material is able to change colour under the influence of an electric potential. The development of energy efficient smart windows for architectural applications is at present the subject of intense research for both economic and environmental reasons. Thus there is now a considerable research effort to develop smart windows with natural colour switching properties, i.e. shades of grey. In this regard, a promising metal oxide with a brown-black anodic colouring state is NiO or hydrated nickel oxide (also called nickel hydroxide , Ni(OH)2). The present work outlines the preparation and optimisation of EC nickel oxide-based ceramic precursor films onto various conducting substrates towards smart window applications. The literature review chapter outlines the different methods used for generating ceramic materials, a review of electrochromism and history of nickel oxide-based EC materials are also provided. Thins films have been deposited by an electrochemical cathodic deposition and by aerosol assisted chemical vapour deposition (AACVD) technique. For hydrated NiO films prepared by electrochemical cathodic deposition, various deposition factors at small-scale area (30 x 7 mm) have been investigated in order to optimise the films properties towards EC applications. With deposition on fluorine-doped tin oxide (SnO2:F, FTO) on glass, use of nickel nitrate (0.01 mol dm-3) solution at an applied current of -0.2 mA (-0.1 mA cm-2) for 800 s was optimal for preparing uniform deposits with a porous interconnecting flake-like structure, which is generally regarded as favourable for the intercalation/deintercalation of hydroxide ions during redox cycling. The as-deposited hydrated NiO films showed excellent transmittance modulation (Δ%T = 83.2 at 432 nm), with average colouration efficiency (CE) of 29.6 cm2 C-1 and low response times. However, after 50 voltammetric cycles, the cycle life was found to fade by 17.2% from charge measurements, and 28.8 % from in-situ transmittance spectra measurements. In an attempt to prepare films with improved durability, AACVD has been used for the first time in the preparation of thin-film EC nickel(II) oxide (NiO). The as-deposited films were confirmed to be cubic NiO from analysis of powder X-ray diffraction data, with an optical band gap that decreased from 3.61 to 3.48 eV with an increase in film thickness (in the range 330 820 nm). The EC properties of the films were investigated as a function of film thickness, following 50, 100 and 500 conditioning oxidative voltammetric cycles in aqueous KOH (0.1 mol dm-3). Light modulation of the films increased with the number of conditioning cycles. EC response times were < 10 s and generally longer for the colouration than the bleaching process. The films showed excellent stability when tested for up to 10000 colour/bleach cycles. Using a calculation method based on the integration of experimental spectral power distributions derived from in-situ visible region spectra over the CIE 1931 colour-matching functions, the colour stimuli of the NiO-based films, and the changes that take place on reversibly switching between the bleached and coloured forms have been calculated. Films prepared by both deposition techniques gave positive a* and b* values to produce orange. However, in combination with low L* values, the films were perceived as brown-grey. Hydrated NiO prepared via electrochemical cathodic deposition suffers from two well-known limitations; firstly, it shows catalytic properties towards the oxygen evolution reaction (OER), which is a process very close to the Ni(II)/Ni(III) redox process. Secondly, hydrated NiO shows poor cycling durability in alkaline solution. The co-deposition of single or bimetallic additives is an effective way to overcome these problems. Electrochemical studies revealed that the combination of cobalt (10%) with lanthanum (5%) was found to be the optimal composition for preparing hydrated NiO films with improved film durability. Finally, the emphasis of this work was on scale-up of deposition. Therefore, optimised deposition conditions from small scale (3.0 x 0.7 cm) have been used to successfully deposit films on two different sized large-area (10 x 7.5 and 30 x 30 cm) conducting substrates.

Esta tese descreve a fabricação, caracterização e possíveis aplicações de compósitos poliméricos nanoestruturados obtidos pela técnica de automontagem. Três sistemas distintos foram analisados: i) nanocompósitos contendo azopolímeros e azocorantes, ii) nanocompósitos contendo compostos de coordenação macrocíclicos (ftalocianinas), e iii) nanocompósitos contendo materiais do tipo doador-receptor, à base de poli(p-fenileno vinileno) (PPV) e azocorantes. Nos compósitos contendo azobenzeno, exploramos as propriedades de birrefringência e a formação de grades de relevo fotoinduzidas. Dois compostos contendo azobenzeno foram utilizados: um copolímero com cromóforos de azobenzeno ligados covalentemente à cadeia principal (Ma-co-DR13) e um azocorante comercial de baixo peso molecular, Brilliant Yellow (BY). Verificou-se através de experimentos de armazenamento óptico que o tempo de escrita até a saturação é muito maior (cerca de 30 min.) que em filmes de azopolímeros produzidos por outras técnicas como casting, em que este tempo é da ordem de dezenas de segundos. O longo tempo foi atribuído às fortes interações eletrostáticas entre as camadas dos filmes automontados, restringindo o processo de reorientação molecular, necessário à indução da birrefringência. Verificamos também que a presença de água entre as camadas do filme exerce influência significativa sobre o tempo de escrita. O tempo característico de escrita diminui de 8 min. para um filme seco para 2 min. após imersão em água. Este efeito é completamente reversível, ou seja, o tempo característico volta a aumentar se o filme for mantido em dessecador durante alguns dias. Grades de relevo foram inscritas nos filmes de BY e analisadas com micro-espectroscopia Raman. Os resultados mostraram um grau variável de fotodegradação no processo de inscrição das grades, dependendo do policátion ou dos parâmetros de fabricação dos filmes, como o pH das soluções. Qualitativamente, a menor ocorrência de fotodegradação foi observada em filmes de poli(alilamina hidroclorada) (P AH) e BY, preparados em soluções de pH = 10. Para os filmes fabricados com ftalocianina tetrasulfonada de ferro (FeTsPc), a combinação das técnicas de espectroscopia no UV-VIS. e no infavermelho (modos transmissão e reflexão) revelou a existência de ligações não-usuais específicas entre o átomo central de ferro da FeTsPc e os grupos não ionizados (NH2) da PAH, usada como policátion. A existência dessas interações ainda não havia sido relatada na literatura e é devida à estrutura de camadas extremamente finas de PAH e FeTsPc. A espessura média de uma bicamada de PAHlFeTsPc foi estimada em cerca de 10 \'Angstron\'. No terceiro tópico abordado, estudamos o processo de transferência de energia entre camadas automontadas de poli(p-fenileno vinileno) (PPV) e do azocorante BY. A transferência de energia pôde ser controlada não só pela variação da distância entre doador e receptor, mas principalmente pelo foto alinhamento das moléculas do BY (receptor) numa direção perpendicular à direção preferencial de emissão do PPV. Esse fotoalinhamento diminui a transferência de energia entre PPV e BY, resultando em um aumento de até 4 vezes na intensidade da fotoluminescência do filme. / This thesis describes the fabrication and possible applications of layer-by-Iayer (LBL) nanostructured films for three distinct systems comprising i) azopolymers and azodyes, ii) organometallic molecules (phthalocyanines) and iii) luminescent polymers and azodyes. Optically induced birefringence and surface relief gratings (SRGs) were studied in the azobenzene-containing composites, using a side-chain azopolymer (Ma-co-DR13) and a commercially available azodye, viz. Brilliant Yellow (BY). Optical storage experiments showed that the writing time required to induce birefringence (up to the saturation) in LBL films of Ma-co-DR13 is ca. 30 min, which is considerably longer than the times required in cast films of azopolymers (tens of seconds). The long writing time was attributed to the electrostatic interactions between the layers in the LBL film, which preclude photoisomerization or the reorientational processes for the azobenzene molecules.ln addition, entrained water in the films was found to affect the writing time. For example, the characteristic writing time decreases from 8 min. for a dry film to ca.2 min. for a film immersed for some minutes in water. This effect was completely reversible. Surface relief gratings were inscribed on LBL films from BY and analyzed with micro-Raman spectroscopy. The Raman spectra revealed that the process for SRG inscription is not entirely light-driven, with the occurrence of photodegradation. Such photodegradation can be minimized upon the appropriate choice of the polycations as well as the experimental conditions used for film fabrication. The lowest level of photodegradation was observed for films of poly(allylamine hydrochloride) (PAH) and BY fabricated from pH 10 solutions. Organometallic supramolecular composites were built using iron tetrasulfonated phthalocyanine (FeTsPc) and P AH as polycation. The combination of electronic and vibrational spectroscopic techniques showed the presence of unusual specific interactions between the central atom of FeTsPc and non-protonated groups from P AH (NH2). These interactions are believed to occur due to the intimate contact between the materials in the very thin PAH/FeTsPc LBL films, whose thickness was 10 ?Angstron? per bilayer. In the poly(p-fenilene vinylene) (PPV) (donor) and BY (acceptor) system, the resonant energy transfer process was exploited to control luminescence. The quenching in luminescence could be controlled by varying the distance between the PPV and BY layers, similarly to what has been reported in the literature. The novelty in this work, however, was the fine-tuning of luminescence achieved with the photoalignment of the acceptor molecules (BY). For example, the intensity of the photoluminescence increased 4 times upon the photoalignment for 10 min. of the BY chromophores.

O presente trabalho utilizou a técnica de automontagem camada-por-camada para produzir eletrodos híbridos de poli(o-metoxianilina) e nanopartículas de pentóxido de vanádio. Foram obtidos filmes acusticamente rígidos, homogêneos com relação à massa depositada e com crescimento linear com o número de bicamadas depositadas. A caracterização eletroquímica foi realizada por voltametria cíclica, onde esse filme apresentou alta capacidade de intercalação/desintercalação de íons lítio e de forma reversível. A capacidade eletroquímica desse filme foi então comparada com filmes automontados de poli(dialildimetilamônio)/V2O5 e polialilamina/V2O5. O filme de Poli(dialildimetilamônio) apresentou um crescimento irregular com dissolução das nanopartículas, o que resultou em uma capacidade eletroquímica extremamente inferior ao filme de poli(o-metoxianilina). O filme de polialilamina apresentou uma deposição mais eficiente de V2O5 que o filme de poli(o-metoxianilina), entretanto essa maior quantidade de pentóxido de vanádio não refletiu em um aumento da capacidade do eletrodo. Os resultados de espectroscopia de impedância eletroquímica mostram que o filme de polialilamina é significativamente mais resistivo que o filme de poli(o-metoxianilina). Essa diminuição da condutividade, associada ao fato de que a poli(o-metoxianilina) também participa do processo de eletrointercalação, explicam seu melhor desempenho frente a intercalação de lítio. A difusão iônica do lítio nos filmes automontados foi estudada por varredura linear a diferentes velocidades, foi observado que o coeficiente de difusão no filme com polialilamina é uma ordem de grandeza menor que no filme de poli(o-metoxianilina). Por fim, o desempenho eletroquímico do filme de poli(o-metoxianilina)/V2O5 foi comparado no eletrólito composto por um líquido iônico hidrofóbico [bis(trifluorometanosulfonil)imideto de 1-butil-2,3-dimetil-imidazólio] com um solvente orgânico convencional (carbonato de propileno). O eletrodo se mostrou estável no líquido iônico, com maior capacidade específica e menor perda de capacidade. O desempenho superior ao eletrólito convencional está relacionado com a natureza iônica do líquido iônico e com a dissolução do filme em carbonato de propileno. Esses resultados, associados com o fato de que o líquido iônico estudado é compatível com ânodos de lítio metálico, indicam cátodos de poli(o-metoxianilina)/V2O5 em eletrólitos de (bis(trifluorometanosulfonil)imideto de 1-butil-2,3-dimetil-imidazólio podem desenvolver baterias de lítio de alta capacidade, durabilidade e segurança. / The present work used layer-by-layer technique to assemble hybrid electrodes of poly(o-methoxyaniline) and vanadium pentoxide nanoparticles. The film obtained was acoustically rigid, with homogeneous mass deposition and linear growth over the bilayer deposition. The electrochemical characterization was performed by cyclic voltammetry and the film showed high capacity for lithium intercalation and high reversibility in the extraction process. This film\'s capacity was compared with self-assembled poly(diallyldimetylammonium)/V2O5 and polyallylamine/V2O5. In the poly(diallyldimetylammonium) film, dissolution of the nanoparticles was observed, which reflected on a very low electrochemical capacity. The deposition of vanadium pentoxide was more efficient in polyallylamine, but even with a higher amount of V2O5, this electrode presented a smaller electrochemical capacity than poly(o-methoxyaniline)/ V2O5. Electrochemical impedance spectroscopy measurements showed that the film with polyallylamine was much more resistive than the film with poly(o-methoxyaniline). The smaller conductivity and the fact that poly(o-methoxyaniline) also participates in the electroinsertion processes explains the higher performance of poly(o-methoxyaniline)/ V2O5 electrode. Linear sweep experiments with different scan rates were performed to study the chemical diffusion of lithium in the layer-by-layer films. It was observed that the diffusion coefficient in the polyallylamine film is ten times smaller than in the poly(o-methoxyaniline) film. The capacity poly(o-methoxyaniline)/V2O5 electrode was also compared in different electrolytes; a hydrophobic ionic liquid [1-butyl- 2,3-dimethyl-imidazolium bis(trifluoromethanesulfonyl)imide] and an organic solvent (propylene carbonate). In ionic liquid the film was stable, had higher capacity and better cyclability, which is related to the ionic nature of the electrolyte and the fact that in propylene carbonate, dissolution of the film was observed. These results, and the possibility of using metallic lithium as anode in [1-butyl-2,3-dimethyl-imidazolium bis(trifluoromethanesulfonyl)imide], indicates the feasibility of using ionic liquids and poly(o-methoxyaniline)/V2O5 cathodes in safe, durable and high performance lithium batteries.

<p>The aims of this study are to first immobilize positively charged gold nanorods to negatively charged cell culture surfaces. Second, to use polyelectrolytes for controlling the distance between gold nanorods and fluorophores. This is used to optimally determine the distance, of which maximum fluorescence enhancement is achieved, between gold nanorods and fluorophores. In order to approach these aims, we use UV/VIS absorption spectroscopy, fluorescence spectroscopy, atomic force microscopy, and ellipsometry. The results show that we could control the immobilization of gold nanorods on plastic microwell plates and create reproducible polyelectrolyte layers, in order to control the distance between the gold nanorods and fluorophores. In addition, the localized surface plasmon resonance wavelength red shifted as the PELs increased. In conclusion, we found that the maximum fluorescence enhancement of the fluorophores (Cy7) is about 2.3 times at a fluorophores-nanoparticles separation of approximately 9-12 nm. This work contributes some research information towards the design of optical biochip platforms based on plasmon-enhanced fluorescence.</p>

In dieser Arbeit wird die Beschichtung von kolloidalen Templaten mit Hilfe der Layer-by-layer Technik beschrieben. Mit ihr ist es möglich, die Oberfläche der Template mit sehr dünnen und gut definierten Filmen zu versehen. Durch Auflösung der Template werden Kapseln hergestellt, die je nach Zusammensetzung der Beschichtung unterschiedliche Eigenschaften aufweisen. / In this thesis the coating of colloid templates using the layer-by-layer technique is described. The surface of the templates is modified with thin, well defined films. After dissolving the templates, hollow capsules with different properties are obtained.

The aims of this study are to first immobilize positively charged gold nanorods to negatively charged cell culture surfaces. Second, to use polyelectrolytes for controlling the distance between gold nanorods and fluorophores. This is used to optimally determine the distance, of which maximum fluorescence enhancement is achieved, between gold nanorods and fluorophores. In order to approach these aims, we use UV/VIS absorption spectroscopy, fluorescence spectroscopy, atomic force microscopy, and ellipsometry. The results show that we could control the immobilization of gold nanorods on plastic microwell plates and create reproducible polyelectrolyte layers, in order to control the distance between the gold nanorods and fluorophores. In addition, the localized surface plasmon resonance wavelength red shifted as the PELs increased. In conclusion, we found that the maximum fluorescence enhancement of the fluorophores (Cy7) is about 2.3 times at a fluorophores-nanoparticles separation of approximately 9-12 nm. This work contributes some research information towards the design of optical biochip platforms based on plasmon-enhanced fluorescence.