Estruturas líquidas cristalinas estão presentes em materiais compostos por moléculas com anisotropia de forma e são caracterizadas por uma ordem orientacional de longo alcance. Na mesofase nemática as moléculas alongadas tendem a se alinhar paralelas entre si, a direção média de orientação define é caracterizada por um vetor unitário, chamado de diretor n. Os cristais líquidos liotrópicos são obtidos usualmente a partir da dispersão de moléculas anfílicas em água. Essas moléculas anfílicas, por terem uma parte polar e uma parte apolar, tendem a formar agregados anisotrópicos, com a parte polar da molécula na superfície. Esse tipo de estrutura esta presente em todos os seres vivos e o exemplo mais clássico é a membrana da célula. A existência de uma superfície de contorno ou uma fronteira modifica as propriedades de um material na vizinhança dessa fronteira. Isso é particularmente verdadeiro para os cristais líquidos, que são muitos sensíveis as condições de contorno, mesmos quando estas não são tão intensas. De fato essa propriedade e bastante útil para a fabricação de dispositivos eletro-ó pticos. Um dos efeitos de superfície mais evidente é a mudança no ordenamento das moléculas devido a quebra de simetria na superfície. Nas fases nemáticas esse efeito microscópico resulta na formação de uma camada superficial com uma ordem posicional que se estende ao longo de uma certa distância no volume. 0 outro efeito resulta da origem a mudanças significativas no estado orientacional das moléculas no volume devido a presença de forças superficiais. Esse efeito é conhecido como ancoramento. Na ausência de campos extemos ou condições de contorno qualquer orientação é igualmente provável. Neste trabalho serão apresentados os resultados de investigação das propriedades de cristais líquidos liotrópicos na interface com um substrata. Estudamos o comportamento dinâmico da camada superficial quando o campo magnético é aplicado e induz uma re­ orientação do diretor. Nesse estudo são utilizadas amostras de cristal líquidos liotrópicos. / Liquid crystalline structures are found in materials made from molecules which are anisotropic in shape; such material are characterized mainly by a long range orientational order. In the nematic phase, the rodlike molecules tend to align parallel to each other. The average orientation defines a unit vector, called director n. Lyotropic liquid crystals are usually obtained by the dispersion of amphiphilic molecules in water. Due the fact that these molecules present a polar head and a non-polar tail, they tend to form aggregates with the polar part at the aggregate surface. This type of struc­ ture is present in all living being; the most classical example is the cell membrane. The existence of a boundary surface affects the properties of a material close to this boundary. This particularly true for liquid crystals, which are very sensitive to boundary conditions, even when weak. Indeed, this property is quite useful in the fabrication of electro-optic devices. One of the most obvious surface effect is the change in the molecules organization due to a breaking of the symmetry at the boundary surface. In the nematic phases, this microscopic effect results in the formation of a surface la yer with a positional order that extends through the bulk up to a certain distance from the surface. The other effect of the surface results in a change in the orientational state of the molecules in the volume due to the sur face forces. This macroscopic effect is known as anchoring. In the absence of any external field or boundary conditions, all molecular orientation is equally probable. In this work, we will present some results of the investigation of the properties of lyotropic liquid crystals at the interface with a solid substrate. We have studied the dy­ namic of the surface layer when a applied magnetic field induces a reorientation of the nematic director. In this study different systems were used: lyotropic liquid crystals in the nematic phase, ferronematics (nematic phase doped with ferrofluid) and filled nematics (nematic phase doped with silica nano-spheres). By means of transmittance measurements.

abstract: One of the single-most insightful, and visionary talks of the 20th century, “There’s plenty of room at the bottom,” by Dr. Richard Feynman, represented a first foray into the micro- and nano-worlds of biology and chemistry with the intention of direct manipulation of their individual components. Even so, for decades there has existed a gulf between the bottom-up molecular worlds of biology and chemistry, and the top-down world of nanofabrication. Creating single molecule nanoarrays at the limit of diffraction could incentivize a paradigm shift for experimental assays. However, such arrays have been nearly impossible to fabricate since current nanofabrication tools lack the resolution required for precise single-molecule spatial manipulation. What if there existed a molecule which could act as a bridge between these top-down and bottom-up worlds? At ~100-nm, a DNA origami macromolecule represents one such bridge, acting as a breadboard for the decoration of single molecules with 3-5 nm resolution. It relies on the programmed self-assembly of a long, scaffold strand into arbitrary 2D or 3D structures guided via approximately two hundred, short, staple strands. Once synthesized, this nanostructure falls in the spatial manipulation regime of a nanofabrication tool such as electron-beam lithography (EBL), facilitating its high efficiency immobilization in predetermined binding sites on an experimentally relevant substrate. This placement technology, however, is expensive and requires specialized training, thereby limiting accessibility. The work described here introduces a method for bench-top, cleanroom/lithography-free, DNA origami placement in meso-to-macro-scale grids using tunable colloidal nanosphere masks, and organosilane-based surface chemistry modification. Bench-top DNA origami placement is the first demonstration of its kind which facilitates precision placement of single molecules with high efficiency in diffraction-limited sites at a cost of $1/chip. The comprehensive characterization of this technique, and its application as a robust platform for high-throughput biophysics and digital counting of biomarkers through enzyme-free amplification are elucidated here. Furthermore, this technique can serve as a template for the bottom-up fabrication of invaluable biophysical tools such as zero mode waveguides, making them significantly cheaper and more accessible to the scientific community. This platform has the potential to democratize high-throughput single molecule experiments in laboratories worldwide. / Dissertation/Thesis / Doctoral Dissertation Biomedical Engineering 2019

This thesis describes a number of novel experiments contributing to the understanding of protein adsorption from both a fundamental and applied perspective. The first three papers involve the use of the localized surface plasmon resonance of gold nanospheres to measure protein conformational dependencies during heat and acid denaturation. Thermal denaturation of BSA is shown to proceed differently depending on the size of nanosphere to which it is conjugated. Activation energies are extracted for thermal denaturing on nanoparticles. These energies decrease with decreasing radius of curvature. Under pH perturbation in the acid region, the multiple transition states of bulk BSA are suppressed, and only one apparent transition around pH 4 is evident. Smaller spheres (diameter < 20nm) do not exhibit any transition. A significant finding of all three studies is that the state and stability of BSA depends strongly upon local curvature. The last two papers investigate protein adsorption relevant to the biomaterial field. Investigation of protein adsorption to polyHEMA hydrogels is carried out using a quartz crystal microbalance. Single and mixed protein adsorption kinetics for BSA, lysozyme and lactoferrin are extracted and interpreted. Selected commercial cleaning solutions are shown to be no more effective than simple buffer solution. Examination of commercial lenses indicates that the morphology of adsorption is material dependent and that siloxane-based hydrogels only deposit low levels of protein. A unique fibril-like morphology is identified on galyfilcon A. Protein morphology is discussed in terms of bare lens morphology, roughness, and surface composition.

This thesis describes a number of novel experiments contributing to the understanding of protein adsorption from both a fundamental and applied perspective. The first three papers involve the use of the localized surface plasmon resonance of gold nanospheres to measure protein conformational dependencies during heat and acid denaturation. Thermal denaturation of BSA is shown to proceed differently depending on the size of nanosphere to which it is conjugated. Activation energies are extracted for thermal denaturing on nanoparticles. These energies decrease with decreasing radius of curvature. Under pH perturbation in the acid region, the multiple transition states of bulk BSA are suppressed, and only one apparent transition around pH 4 is evident. Smaller spheres (diameter < 20nm) do not exhibit any transition. A significant finding of all three studies is that the state and stability of BSA depends strongly upon local curvature. The last two papers investigate protein adsorption relevant to the biomaterial field. Investigation of protein adsorption to polyHEMA hydrogels is carried out using a quartz crystal microbalance. Single and mixed protein adsorption kinetics for BSA, lysozyme and lactoferrin are extracted and interpreted. Selected commercial cleaning solutions are shown to be no more effective than simple buffer solution. Examination of commercial lenses indicates that the morphology of adsorption is material dependent and that siloxane-based hydrogels only deposit low levels of protein. A unique fibril-like morphology is identified on galyfilcon A. Protein morphology is discussed in terms of bare lens morphology, roughness, and surface composition.

Carbon nanotubes (CNTs) have become one of the most interesting allotropes of carbon due to their intriguing mechanical, electrical, thermal and optical properties. The synthesis and electron emission properties of CNT arrays have been investigated in this work. Vertically aligned CNTs of different densities were synthesized on copper substrate with catalyst dots patterned by nanosphere lithography. The CNTs synthesized with catalyst dots patterned by spheres of 500 nm diameter exhibited the best electron emission properties with the lowest turn-on/threshold electric fields and the highest field enhancement factor. Furthermore, CNTs were treated with NH3 plasma for various durations and the optimum enhancement was obtained for a plasma treatment of 1.0 min. CNT point emitters were also synthesized on a flat-tip or a sharp-tip to understand the effect of emitter geometry on the electron emission. The experimental results show that electron emission can be enhanced by decreasing the screening effect of the electric field by neighboring CNTs. In another part of the dissertation, vertically aligned CNTs were synthesized on stainless steel (SS) substrates with and without chemical etching or catalyst deposition. The density and length of CNTs were determined by synthesis time. For a prolonged growth time, the catalyst activity terminated and the plasma started etching CNTs destructively. CNTs with uniform diameter and length were synthesized on SS substrates subjected to chemical etching for a period of 40 minutes before the growth. The direct contact of CNTs with stainless steel allowed for the better field emission performance of CNTs synthesized on pristine SS as compared to the CNTs synthesized on Ni/Cr coated SS. Finally, fabrication of large arrays of free-standing vertically aligned CNT/SnO2 core-shell structures was explored by using a simple wet-chemical route. The structure of the SnO2 nanoparticles was studied by X-ray diffraction and electron microscopy. Transmission electron microscopy reveals that a uniform layer of SnO2 is conformally coated on every tapered CNT. The strong adhesion of CNTs with SS guaranteed the formation of the core-shell structures of CNTs with SnO2 or other metal oxides, which are expected to have applications in chemical sensors and lithium ion batteries.

No description available.

Les biocapteurs sont utilisés quotidiennement pour déterminer la présence de molécules biologiques dans une matrice complexe, comme l’urine pour les tests de grossesses ou le sang pour les glucomètres. Les techniques courantes pour la détection des autres maladies nécessitent fréquemment le marquage de l’analyte avec une autre molécule, ce qui est à éviter pour fin de simplicité d’analyse. Ces travaux ont pour but la maximisation de la sensibilité d’une surface d’or ou d’argent nanotrouée, afin de permettre la détection de la liaison de molécules biologiques par résonance des plasmons de surface localisés (LSPR), en utilisant la spectroscopie de transmission. Un biocapteur portable, rapide et sans marquage pour quantifier des analytes d’intérêt médical ou environnemental pourrait être construit à partir de ces travaux. Dans l’objectif d’étudier de nombreuses configurations pour maximiser la sensibilité, le temps et le coût des méthodes de fabrication de nanostructures habituelles auraient limité le nombre de surfaces nanotrouées pouvant être étudiées. Un autre objectif du projet consiste donc au développement d’une technique de fabrication rapide de réseaux de nanotrous, et à moindres coûts, basée sur la lithographie de nanosphères (NSL) et sur la gravure au plasma à l’oxygène (RIE). La sensibilité à la variation d’indice de réfraction associée aux liaisons de molécules sur la surface du métal noble et la longueur d’onde d’excitation du plasmon de surface sont influencées par les caractéristiques des réseaux de nanotrous. Dans les travaux rapportés ici, la nature du métal utilisé, le diamètre ainsi que la périodicité des trous sont variés pour étudier leur influence sur les bandes LSPR du spectre en transmission pour maximiser cette sensibilité, visant la fabrication d’un biocapteur. Les surfaces d’argent, ayant un diamètre de nanotrous inférieur à 200 nm pour une périodicité de 450 nm et les nanotrous d’une périodicité de 650 nm démontre un potentiel de sensibilité supérieur. / Biosensors are used daily to determine the presence of biomolecules in a complex matrix, like urine for pregnancy test or blood with a glucometer. The usual biodetection methods require the addition of a tag on the analyte, which is to be avoided to design a simple analytical method. The objective of this work is to maximize the sensitivity of a gold or silver nanohole arrays to detect the biomolecules liaisons close to the metal surface by localized surface plasmon resonance (LSPR) in transmission spectroscopy. A portable and effective biosensor to quantify analytes could be built based on this work, without a tagging step. To achieve the objective of evaluating numerous configurations for maximal sensitivity, the time and cost of the usual nanostructures fabrication methods would have limited the number of nanohole arrays in metal surface that could have been studied in this project. This fact motivated another objective of this project, the development of a fast and low cost fabrication method for nanohole arrays using nanospheres lithography (NSL) followed by reactive ions etching (RIE). The plasmon sensitivity and wavelength excitation are influenced by the nanohole arrays characteristics. In the work presented here, the chemical composition of the metal surface, the diameter and the periodicity of the nanohole arrays are shown to the influence the LSPR bands. The transmission maximum and minimum position of some LSPR bands are sensitive to refractive index change, which can be exploited in a biosensor format to detect biomolecules. The optimization of these nanohole arrays characteristics allows the maximization of this sensitivity to build a biosensor. The best index refraction sensitive results were with silver surfaces, with nanohole diameters smaller than 200 nm for a periodicity of 450 nm and the nanoholes with a periodicity of 650 nm show a potential for an increased sensitivity.

Les biocapteurs sont utilisés quotidiennement pour déterminer la présence de molécules biologiques dans une matrice complexe, comme l’urine pour les tests de grossesses ou le sang pour les glucomètres. Les techniques courantes pour la détection des autres maladies nécessitent fréquemment le marquage de l’analyte avec une autre molécule, ce qui est à éviter pour fin de simplicité d’analyse. Ces travaux ont pour but la maximisation de la sensibilité d’une surface d’or ou d’argent nanotrouée, afin de permettre la détection de la liaison de molécules biologiques par résonance des plasmons de surface localisés (LSPR), en utilisant la spectroscopie de transmission. Un biocapteur portable, rapide et sans marquage pour quantifier des analytes d’intérêt médical ou environnemental pourrait être construit à partir de ces travaux. Dans l’objectif d’étudier de nombreuses configurations pour maximiser la sensibilité, le temps et le coût des méthodes de fabrication de nanostructures habituelles auraient limité le nombre de surfaces nanotrouées pouvant être étudiées. Un autre objectif du projet consiste donc au développement d’une technique de fabrication rapide de réseaux de nanotrous, et à moindres coûts, basée sur la lithographie de nanosphères (NSL) et sur la gravure au plasma à l’oxygène (RIE). La sensibilité à la variation d’indice de réfraction associée aux liaisons de molécules sur la surface du métal noble et la longueur d’onde d’excitation du plasmon de surface sont influencées par les caractéristiques des réseaux de nanotrous. Dans les travaux rapportés ici, la nature du métal utilisé, le diamètre ainsi que la périodicité des trous sont variés pour étudier leur influence sur les bandes LSPR du spectre en transmission pour maximiser cette sensibilité, visant la fabrication d’un biocapteur. Les surfaces d’argent, ayant un diamètre de nanotrous inférieur à 200 nm pour une périodicité de 450 nm et les nanotrous d’une périodicité de 650 nm démontre un potentiel de sensibilité supérieur. / Biosensors are used daily to determine the presence of biomolecules in a complex matrix, like urine for pregnancy test or blood with a glucometer. The usual biodetection methods require the addition of a tag on the analyte, which is to be avoided to design a simple analytical method. The objective of this work is to maximize the sensitivity of a gold or silver nanohole arrays to detect the biomolecules liaisons close to the metal surface by localized surface plasmon resonance (LSPR) in transmission spectroscopy. A portable and effective biosensor to quantify analytes could be built based on this work, without a tagging step. To achieve the objective of evaluating numerous configurations for maximal sensitivity, the time and cost of the usual nanostructures fabrication methods would have limited the number of nanohole arrays in metal surface that could have been studied in this project. This fact motivated another objective of this project, the development of a fast and low cost fabrication method for nanohole arrays using nanospheres lithography (NSL) followed by reactive ions etching (RIE). The plasmon sensitivity and wavelength excitation are influenced by the nanohole arrays characteristics. In the work presented here, the chemical composition of the metal surface, the diameter and the periodicity of the nanohole arrays are shown to the influence the LSPR bands. The transmission maximum and minimum position of some LSPR bands are sensitive to refractive index change, which can be exploited in a biosensor format to detect biomolecules. The optimization of these nanohole arrays characteristics allows the maximization of this sensitivity to build a biosensor. The best index refraction sensitive results were with silver surfaces, with nanohole diameters smaller than 200 nm for a periodicity of 450 nm and the nanoholes with a periodicity of 650 nm show a potential for an increased sensitivity.

Im ersten Teil der Arbeit werden Signalverstärkungsmechanismen für Raman-Spektroskopie erschlossen und evaluiert. Die als geeignet bewerteten Methoden finden im zweiten Teil ihre Anwendung zur Untersuchung der vibronischen Eigenschaften von dünnen Manganphthalocyaninschichten, die anschließend mit Kalium interkaliert werden. Hierbei sind verschiedene Phasen identifizierbar, die ein ganzzahliges Verhältnis von Kaliumatomen zu Manganphthalocyaninmolekülen besitzen. Im dritten Teil werden die elektrischen Eigenschaften durch die Verwendung dieses Materialsystems als aktives Medium eines Feldeffekttransistors untersucht.

Im ersten Teil der Arbeit werden Signalverstärkungsmechanismen für Raman-Spektroskopie erschlossen und evaluiert. Die als geeignet bewerteten Methoden finden im zweiten Teil ihre Anwendung zur Untersuchung der vibronischen Eigenschaften von dünnen Manganphthalocyaninschichten, die anschließend mit Kalium interkaliert werden. Hierbei sind verschiedene Phasen identifizierbar, die ein ganzzahliges Verhältnis von Kaliumatomen zu Manganphthalocyaninmolekülen besitzen. Im dritten Teil werden die elektrischen Eigenschaften durch die Verwendung dieses Materialsystems als aktives Medium eines Feldeffekttransistors untersucht.:1. Einleitung 2. Theoretische Grundlagen der angewendeten Effekte 3. Experimentelle Details 4. Herstellung, Charakterisierung und Optimierung von Substraten für Raman-Oberflächenverstärkungseffekte 5. Untersuchung zu Verstärkungsmechanismen des Raman-Effekts an dünnen organischen Schichten 6. Interkalation mit Kalium in dünne Schichten aus Manganphthalocyanin 7. MnPc unter Spannungs- und Stromeinfluss - Der Feldeffekttransistor 8. Zusammenfassung Anhang Literatur Abbildungsverzeichnis Eidesstattliche Versicherung Lebenslauf Liste wissenschaftlicher Leistungen Danksagung