La manipulation de micro- et nano- particules en solution peut être réalisée grâce aux interactions de ces objets avec des champs électromagnétiques. La lumière ou bien encore les champs électriques continus (DC) ou alternatifs (AC) peuvent être utilisés. Dans le cas d’un champ électrique non uniforme appliqué entre deux électrodes séparées par quelques micromètres, des gradients de champs très intenses et localisés sont ainsi créés. Ces gradients de champ localisés au niveau des électrodes engendrent la création de mouvements de charges composant la solution (effets électro-hydrodynamique). Mais aussi des charges confinées au niveau des particules à l’interface liquide/solide. Les particules en suspension subissent alors une force attractive ou répulsive appelée diélectrophorèse. Cette force est décrite dans la littérature pour des particules isolantes de taille supérieure à 200 nm. Dans cette étude par détection optique (videomicroscopie par champ sombre ou spectroscopie en microfluidique) la gamme de taille de particules est élargie (40-150 nm) pour étudier leurs réponses diélectrophorètique. En effet la diélectrophorèse dépend de la taille des particules, de son environnement et des paramètres du champ appliqué (fréquence, amplitude, topologie) La diélectrophorèse est mise en compétition avec le mouvement Brownian pour des particules d’or d’aussi petites tailles. La réponse pour des nanoparticules d’or en solution alors connue, il est envisageable de faire varier les paramètres, comme l’environnement de la particule ou bien la complexité des systèmes étudiés. / The manipulation of micro- and nano- particles in solution can be achieved through the interactions of these objects with electromagnetic fields. Emitted light, continuous (DC) or alternating (AC) electric fields can be used. In the case of a non-uniform electric field applied between two electrodes separated by a few micrometers, very intense and localized field gradients are created. These field gradients localised close to the electrodes generates a motion of the mass solution (electro-hydrodynamic effects). The charges confined onto particles at the liquid/solid interface are also subjected to motion. Suspended particles undergo an attractive or repulsive force called dielectrophoresis.This force is described in the literature for insulating particles larger than 200 nm. In this study optical detection was used (dark field videomicroscopy or microfluidic spectroscopy) to expand the range of particle size (40-150 nm) and to study their dielectrophoretic responses. Indeed, the dielectrophoresis is dependent on the size of particles, their environment and the parameters of the applied electric field (frequency, amplitude, topology). The dielectrophoresis is in competition with the Brownian motion of these gold nanoparticles. By, knowing the dielectrophoretic response of these particles in solution, it is possible to vary parameters, such as the suspension composition of the particles or the complexity of the systems studied.

Title: Multifunctional biomolecular assemblies for parallelized analysis of biomolecular interactions Author: Markéta Bocková Department / Institute: Institute of Physics, Charles University Supervisor of the doctoral thesis: Prof. Jiří Homola, Ph.D., DSc., Institute of Photonics and Electronics, The Czech Academy of Sciences Abstract: Surface plasmon resonance (SPR) biosensors represent the most advanced optical method for the direct, real-time monitoring of biomolecular interactions without the need for labelling. This doctoral thesis aims to advance the SPR biosensor method and to expand its utility in the investigation of biomolecular interactions. This encompasses activities on two major fronts of SPR biosensor research - immobilization methods and biosensing methodologies. Methods for the immobilization of biomolecules were researched with the aim of enabling the immobilization of a broad range of biomolecules on the SPR biosensor surface in a spatially controlled manner. The development of novel biosensing methodologies was pursued in order to address the current limitations of SPR biosensors associated with non-specific adsorption and limited analyte transport, and thus to improve the accuracy and robustness of SPR biosensor measurements. Finally, advances in the development of immobilization...

Lignin is one of the main components of wood and plants that acts as a kind of glue providing mechanical strength. It is a main polymer component composed from three phenolic structures, i.e. p-hydroxyphenyl (H), guaiacyl (G) and syringyl (S) units. It currently draws a lot of attention due to its eco-friendly. Recently, it has been shown that it is possible to produce lignin nanoparticles, small spherical particle that are composed out of lignin, that could possibly be used to replace the hazardous silver nanoparticles that are today used frequently in numerous applications. Lignin nanoparticles could potenitally also be used as functional coatings, as well as biologically degradable adhesives and float switches. Five samples, of nanoparticles, were investigated in this study. The first contained pure lignin nanoparticles, the second pure silver nanoparticles, and the three remaining samples contained lignin-coated silver nanoparticles, extracted from acetone, tetrahydrofuran (THF), and dimetylformamid (DMF) solvents. All samples were characterized using spectroscopic methods, e.g. infrared- and dark-field imaging, as well as UV-Vis-, fluorescence-, and Raman spectroscopy. In this thesis it was shown that lignin-coated silver nanoparticles exhibit surface plasmon resonance which induces a heat effect upon infrared irradiation. To identify the phenolic structures of lignin, UV-Vis spectroscopy was used. It was found that the spectra of the samples exhibited several intense bands. The objective of the UV-Vis spectroscopy was to examine the absorbance characteristics of the lignin-coated silver nanoparticles. Possible surface plasmon resonance wavelengths were determined, and two of the phenolic structures were identified. In this study, Raman spectroscopy was used to define characteristic bands of the samples. This was done to investigate if the lignin nanoparticles have the same characteristics as bulk lignin. Raman spectroscopy provide structural information of lignin. Furthermore, p-hydroxyphenyl, guaiacyl and syringyl structures could be identified with an excitation wavelength of 532nm. A comparison of the spectra of the lignin-containing samples indicated the the Raman features of the specimens were similar meanwhile almost no signs of silver were present, which might show that the particles were fully covered with lignin. Main lignin bands were identified and assigned. The fluorescent properties of the nanoparticles were investigated by obtaining emission spectra for blue-, green- and UV light excitation. The spectra were deconvoluted into their Gaussian components. Emission spectra were obtained for blue-, green- and UV light excitation. It was found that the fluorescence, after UV light exposure, increased with time of exposure. Dark-field microscopy was used to generate light scattering images of the particles. As a result, optical images with different colors (white, yellow, blue and red) could be revealed. The color information, that is related to the size of the particles, was used to estimate ratios of the different particle sizes. The lignin-coated silver nanoparticles, extracted from acetone, exhibited a strong surface plasmon resonance effect, which could be due to the absorbance at 463nm. The lignin-coated silver nanoparticles, extracted from DMF, exhibited a medium surface plasmon resonance effect, which could be due to the absorbance at 362nm. The lignin-coated silver nanoparticles, extracted from the THF solvent, exhibited a weak surface plasmon resonance effect, which could be due to the absorption at 379-380nm. The pure lignin- and silver nanoparticles merely showed bulk heating but no surface plasmon resonance effect could be detected. / Lignin är en av huvudbeståndsdelarna av trä och plantor som fungerar likt ett lim som ger mekanisk styrka. Lignin är en biopolymer, som består av tre fenylgrupper: p-hydroxifenyl (H), guaiacyl (G) och syringyl (S). På senaste tid har det visat sig att det är möjligt att tillverka lignin nanopartiklar, det är små sfäriska partiklar som är helt gjorda av lignin, som skulle kunna ersätta de miljöfarliga silver nanopartiklarna som i nuläget används i många olika tillämpningar. Lignin nanopartiklar kan potentiellt också användas som funktionella ytbeläggningar, såväl som biologiskt nedbrytbara lim och flottörer. Fem prover, av nanopartiklar, undersöktes i denna studie. Det första provet innehöll lignin nanopartiklar, det andra silver nanopartiklarna, och de tre återstående proverna innehöll ligninbelagda silver nanopartiklar, extraherade från aceton, tetrahydrofuran (THF) och dimetylformamid (DMF). Alla prover karakteriserades med hjälp av spektroskopiska metoder: infraröd- och mörkfältavbildning, liksom UV-Vis-, fluorescens- och Ramanspektroskopi. I denna avhandling visades att ligninbelagda silver nanopartiklar uppvisar ytplasmonsresonans, vilket inducerar en värmeeffekt vid infraröd bestrålning. För att identifiera ligninets fenylgrupper användes UV-Vis-spektroskopi. Det visade sig att spektra från proverna uppvisade flera intensiva band. Målet med UV-Vis-spektroskopin var att undersöka absorptionsegenskaperna hos de ligninbelagda silvernanopartiklarna. Möjliga ytplasmonresonansvåglängder bestämdes och två av fenylgrupperna identifierades. I denna studie användes Ramansspektroskopi för att definiera karakteristiska band för proverna. Detta gjordes för att undersöka om lignin nanopartiklarna har samma egenskaper som bulk lignin. Ramanspektroskopi ger information om ligninets struktur. Vidare identigierades p-hydroxifenyl-, guaiacyl- och syringylstrukturerna med en excitationsvåglängd på 532nm. En jämförelse av spektra för de lignininnehållande proverna indikerade att provernas Raman-kännetecken var liknande medan nästan inga tecken på silver fanns, vilket kan visa att partiklarna var täckta med lignin. Huvudsakliga ligninband kunde identifieras. Fluorescensegenskaperna, hos nanopartiklarna, undersöktes genom de erhållna emissionspektra efter exponering av blå-, grön- och UV-ljus. De erhållna spektra dekonvoluterades till dess gaussiska komponenter. Det visade sig att fluorescensen, efter exponering av UV-ljus, ökade med exponeringstiden. Mörkfältmikroskopi användes för att generera bilder på partiklarna. De resulterade i bilder med olika färger (vitt, gult, blått och rött) som motsvarade olika partikelstorlekar och geometrier. På så sätt kunde färhållandena mellan de olika partikelstorlekarna uppskattas. De ligninbelagda silver-nanopartiklarna, extraherade från aceton-lösningen, uppvisade en stark ytplasmonresonanseffekt, vilket kan bero på absorptionen (från absorptionsspektrat) vid 463nm. De ligninbelagda silver-nanopartiklarna, extraherade från DMF-lösningen, uppvisade en medelstark ytplasmonresonanseffekt, vilket kan bero på absorptionen vid 362nm. De ligninbelagda silver-nanopartiklarna, extraherade från THF-lösningen, uppvisade en svag ytplasmonresonanseffekt, vilket kan bero på absorptionen vid 379-380nm. De rena lignin- och silver-nanopartiklarna uppvisade endast uppvärmning men ingen ytplasmonresonanseffekt.

A system was developed to perform real-time biological threat agent (BTA) detection with a small autonomous unmanned aerial vehicle (UAV). Biological sensors just recently reached a level of miniaturization and sensitivity that made UAV integration a feasible task. A Surface Plasmon Resonance (SPR) biosensor was integrated for the first time into a small UAV platform, allowing the UAV platform to collect and then quantify the concentration of an aerosolized biological agent in real-time. A sensor operator ran the SPR unit through a groundstation laptop and was able to wirelessly view detection results in real time. An aerial sampling mechanism was also developed for use with the SPR sensor. The collection system utilized a custom impinger setup to collect and concentrate aerosolized particles. The particles were then relocated and pressurized for use with the SPR sensor. The sampling system was tested by flying the UAV through a ground based plume of water soluble dye. During a second flight test utilizing the onboard SPR sensor, a sucrose solution was autonomously aerosolized, collected, and then detected by the combined sampling and SPR sensor subsystems, validating the system\'s functionality. The real-time BTA detection system has paved the way for future work quantifying biological agents in the atmosphere and performing source localization procedures. / Master of Science

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21113号 / 工博第4477号 / 新制||工||1696(附属図書館) / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 田中 勝久, 教授 三浦 清貴, 教授 作花 哲夫 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

No description available.

表面プラズモン共鳴型超音波センサは高分解能な光音響顕微鏡用超音波受波器として期待されている．本研究では，サブナノ秒パルスレーザを利用したポンププローブシステムを構築してサブナノ秒域における表面プラズモン共鳴センサの熱・弾性的な過渡応答を光学的に評価した。特にプローブ光の反射率変化として観測される過渡応答の発生メカニズムについて，実験と理論の両方のアプローチから検討しており，観測される過渡応答は金属薄膜のプラズマ周波数の変化に起因することを明らかにした。 / Surface plasmon resonance (SPR) sensor has been expected as a ultrasonic sensor used in high resolution photoacoustic microscopy (PAM). In this thesis, thermoelastic transient responses in SPR sensor were evaluated by a pump probe system with a developed sub-nanosecond pulsed laser. Especially, the mechanism of the transient response to be observed as a reflectivity change of the probe light was studied by two approaches of the experiment and the theoretical estimation. As consequence of these approaches, it was revealed that the transient response was caused by the change of the plasma frequency in a thin metal film of SPR sensor. / 博士(工学) / Doctor of Philosophy in Engineering / 同志社大学 / Doshisha University

Surface plasmon resonances of metal nanostructures have been studied intensely in recent years. The strong plasmon-mediated electric field enhancement and field confinement well beyond the diffraction limit has been demonstrated to improve the performance of optical devices including ultrasensitive sensors, light emitters, and optical absorbers. A plasmon resonance mode of particular recent interest is the gap plasmon resonance that occurs on closely spaced metallic structures. In contrast to plasmon resonances supported by isolated metal nanostructures, coupled nanostructures provide additional spectral and spatial control over the plasmon resonance response. For example, the resonance frequencies of metal nanoparticle dimers depend strongly on the gap size between the nanoparticles. Gap plasmons can produce local electric field enhancement factors that are several orders of magnitude stronger and more confined than surface plasmon resonances of isolated plasmonic nanospheres. The reliance of gap plasmons on few-nanometer separation between nanostructures makes it difficult to prepare gap-plasmon supporting structures with predictable resonance frequency and field enhancement. A structure that avoids this challenge is the film-coupled nanoparticle (NP). Similar to nanoparticle dimers, a nanoparticle on a supporting metallic film (or NP-on-a-mirror) can offer a strong coupling between the particle and its local environment, in this case the supporting film instead of adjacent nanoparticles, enabling strongly confined gap-plasmon modes. The NP-on-a-mirror geometry has been shown to produce reproducible gap plasmon resonances in a chemically and thermally robust, easy to fabricate structure. In this Thesis, we first present a scheme for controlling the gap plasmon resonance frequency of single gold nanoparticles using aluminum oxide coated metal films. We demonstrate experimentally and numerically that the gap-plasmon resonance of single gold nanoparticles can be tuned throughout the visible range by controlling the aluminum oxide thickness via anodization. In a separate study of Au NP on Al2O3 coated gold films it is shown that the oxide coating improves the stability of the structure under intense laser irradiation. An combined experimental and numerical analysis of the spectral response of Au NP on rough Au films shows that a film roughness of a few nanometer can affect the gap plasmon resonance in the absence of an oxide spacer layer. A photoluminescence study of single gold nanoparticles on an Al2O3 coated gold film shows that the gap-plasmon resonance of this type of plasmonic structure can increase gold photoluminescence by more than four orders of magnitude. Related numerical simulations reveal that the local photoluminescence enhancement of a gold nanoparticle on an Al2O3 coated gold film can be as high as one million near the particle-film junction. Finally, a new plasmonic sensing element was proposed based on our findings in the previous chapters. This proposed hole-in-one structure offers several attractive features including an easily optically accessible gap plasmon mode, while maintaining a relatively simple fabrication method. Taken together, the research presented in this Thesis demonstrates how the resonance frequency, field enhancement, mode polarization, structural stability, and structure reliability can be controlled at the nanoscale. The knowledge gained in the course of this work could lead to further development of nanophotonic devices that utilize extremely confined optical fields and precisely controlled resonance frequencies.

Localized surface plasmon resonance (LSPR) is induced in metal nanoparticles by resonance between incident photons and conduction electrons in nanoparticles. For noble metal nanoparticles, LSPR can lead to strong absorbance of ultraviolet-violet light. Although it is well known that LSPR depends on the size and shape of nanoparticles, the inter-particle spacing, the dielectric properties of metal and the surrounding medium, the temperature dependence of LSPR is not well understood. By thermally annealing gold nanoparticle arrays formed by nanosphere lithography, a shift of LSPR peak upon heating has been shown. The thermal characteristics of the plasmonic nanoparticles have been further used to detect chemicals such as explosive and mercury vapors, which allow direct visual observation of the presence of mercury vapor, as well as thermal desorption measurements

Current major demands in SPR sensor development are system miniaturization and throughput improvement. Structuring an array of integrated optical SPR sensor heads on a semiconductor based optoelectronic platform could be a promising solution for those issues, since integrated optical waveguides have highly miniaturized dimension and the optoelectronic platform enables on-chip optical-to-electrical signal conversion. Utilizing a semiconductor based platform to achieve optoelectronic functionality poses requirements to the senor head; the sensor head needs to have reasonably small size while it should have reasonable sensitivity and fabrication tolerance. This research proposes a novel type of SPR sensor head and demonstrates a fabricated device with an array of integrated optical SPR sensor heads endowed with optoelectronic functionality. The novel integrated optical SPR sensor head relies on mode conversion efficiency for its operational principle. The beauty of this type of sensor head is it can produce clear contrast in SPR spectrum with a highly miniaturized and simple structure, in contrast to several-millimeter-scale conventional absorption type or interferometer type sensor heads. The integrated optical SPR sensor with optoelectronic functionality has been realized by structuring a dielectric waveguide based SPR sensor head on a photodetector-integrated semiconductor substrate. A large number of unit sensors have been fabricated on a substrate with a batch fabrication process, which promises a high throughput SPR sensor system or low-priced disposable sensors.