<p>Nanotechnology has experienced a tremendous rise in the last decade. The synthesis of nanomaterials of defined structure and controlled properties is one of the most challenging part. Solution processing bottom-up fabrication techniques enables the facile synthesis of low dimension and ordered structures with low cost through the self-assembly of basic building blocks. Biotemplating has become an emerging field in which natural biomolecular objects are utilized for creating functional, hierarchical, controlled patterned structures with nanometric precision. It is a capital effective, eco-friendly and energy-efficient synthetic process. Viral biotemplating has shown great potential in electronics, environmental and biomedical devices. In recent years, in-planta produced Tobacco Mosaic Virus (TMV) and its variants have been used to produce metal nanorods and nanowires of monodisperse structures under mild conditions without the use of harsh chemical treatments although there remains much to be understood. Mass production of biotemplate, programming of viral particles of desired functionalities, manipulation for biomineralized metal materials of good quality have not been sufficiently studied to allow for directed synthesis. The fundamental studies on platform development for viral biotemplate production, design of viral proteins carrying engineered properties, and the hydrothermal synthesis of biotemplated metal nanomaterials, which create great uniformity and high coverage are of interest in this dissertation. Three experimental studies are outlined.<br></p><p><br></p><p>A novel virus biotemplate, Barley stripe mosaic virus (BSMV) virus-like particle is designed and engineered through genetic engineering. By fusing the Origin of Assembly from TMV to the transcript encoding BSMV capsid protein, the self-assembly of BSMV-VLP nanorod from microbial-based protein expression system was achieved for the first time. An alternate platform for viral particle production has been developed. Optimization of VLP expression, purification and processing conditions are performed. This developed alternative E. coli production platforms offer unique opportunities for genetic engineering and faster protein expression; therefore, the development of our system enables rapid design-build-test cycles for the engineering and production of BSMV-VLPs with desired properties. Results in this project shows the power of genetic engineering and serves as a springboard for genetic engineering of the VLPs.<br></p><p><br></p><p>Programming on BSMV-VLP is further used to decouple the VLP assembly into governing internal molecular interactions. To drive the nucleic acid free helical BSMV-VLP rod assembly and further increase the stability of capsid proteins, an identification of Caspar Carboxylate cluster in BSMV is performed. Various carboxylate residues were selected through protein crystal structure and examined systematically through experimental work. By introducing mutations on selected residues, the intersubunit carboxylate interaction of the proteins was significantly altered, resulting in an in vivo production of nucleic-acid free BSMV-VLP assembly for the first time. The change in interactions leads to increased stability of the modified VLP, enabling the formation of longer nanorods with lengths over one micrometer. Moreover, both wild-type and mutated BSMV-VLPs were shown to have great structural stability across a wide range of pHs. Overall, we exhibit experimental identification to systematically probe the key carboxylate interactions to increase the stability of proteins and drive RNA-free BSMV-VLP assembly. This project greatly expands the potential usefulness of the engineered BSMV-VLP biotemplates for a wide variety of applications.<br></p><p><br></p><p>Finally, to demonstrate the versatile uses of BSMV-VLP in biotemplating, the new biotemplate was utilized to expand understandings on the directed synthesis of metal nanostructures. By using the hydrothermal synthesis, VLPs were successfully utilized to synthesize monometallic palladium nanorods with a wide range of length scales. The VLP-mediated nanorods are more uniformly and fully-covered than the ones synthesized with in planta-produced BSMV virion. Besides, the synthesis shows an effective control over the metal nanorod diameter. The capability of BSMV-VLP was readily expanded from the synthesis of monometallic nanorods to bimetallic hybrid. In the absence of an exogenous reducing agent, mineralization of platinum, gold and copper was successfully demonstrated on the VLP. It is attributed to lower reduction barrier introduced by already-deposited palladium nanoparticles which serve as nucleation sites for subsequent metal reduction. The formation of bimetallic complexes was further supported by STEM, EDS and XPS analysis evidenced the presences of multiple metals. Overall, BSMV-VLP-mediated biotemplating using the hydrothermal synthesis has been confirmed to be a promising and feasible approach to create organic-inorganic complex nanocomposite.<br></p><p><br></p><p>Lastly, to move toward an application, the synthesized Pd nanorods coated with full coverage and great uniformity of nanoparticles were utilized as an exciting hydrogen sensing material. The developed hydrogen sensing system using a quartz crystal microbalance shows a fast response toward hydrogen as well as the ability of hydrogen detection and quantification of the adsorption capacity. This study serves as an entry point and opens up enormous possibility for next-generation of Pd-virus hybrid hydrogen sensors.<br></p><p><br></p><p>Taken together, this dissertation has demonstrated the engineering and production of a novel BSMV virus-like particle bacterial system. This alternative platform and developed parameter space for VLP production is genetically tractable and requires significantly shorter processing duration for large-scale and mass production. The BSMV-VLP biotemplated metal nanomaterials present great qualities and controllable dimensions. This approach has explored the synthetic palette and opened up enormous possibilities in the bottom-up nanofabrication of versatile and tunable organic-inorganic nanoscaled complex and would facilitate future engineering industrial applications.<br></p>

Une série de composant hybride basée sur réactives polyédriques oligomères silsesquioxane (POSS) precusors et ses copolymères réactifs de PGMA ont été synthétisés et utilisés pour nanobuild en époxy. POSS réactifs et de copolymères en dispersion dans la matrice homogène dans, au délà de POSS-POSS interaction, ce qui a entraîné la séparation de phase macroscopique. Les nanocomposites obtenus ont été analysés par microscopie électronique à balayage, microscopie électronique à transmission, diffusion des rayons X et l'analyse mécanique dynamique. Un analogue de POSS (notée POSSMOCA) a été synthétisé par réaction d'addition, qui a réactive liaison groupe amino dans le réseau époxy et d'améliorer la stabilité thermique, en raison du silicium, d'azote et un atome d'halogène structurel. Époxy / polyédriques silsesquioxanes oligomères (POSS) composites hybrides ont été préparés à partir de pré-réaction entre l'éther de silanol POSS-OH et diglycidylique trifonctionnel de bisphénol A (DGEBA) par l'intermédiaire du silanol et un groupe oxiranne. Réactif POSS-PGMA a été polymérisé par polymérisation par transfert de réversible par addition-fragmentation. Il est facile à queue de la compatibilité du copolymère séquencé époxyde avec une matrice de l'étape de croissance-polymérisé, pour former par réaction avec nanostructure segements PGMA. Dans le cas d'inertes POSS-PMMA copolymères modifiés époxy, topologie de copolymère défini la morphologie finale et l'interaction entre époxy et entre eux, en raison de la liaison hydrogène directionnelle à effet de dilution. Tg de conversion époxyde différente, obéi de Gordon-Taylor équation et l'équation Kwei, k qui reflète l'interaction de modificateur et les oligomères DGEBA / MEDA et époxy / amine, était cohérente de la rhéologie et les résultats dynamiques. / A series of hybrid component based on reactive polyhedral oligomeric silsesquioxane(POSS) precusors and its reactive copolymers of PGMA were synthesized and utilized to nanobuild in epoxy. Reactive POSS and copolymer dispersed in homogenous in matrix, overcomed POSS-POSS interaction, which resulted in macroscale phase separation. The nanocomposites obtained were analyzed by Scanning electron microscopy, Transmission electron microscopy, X-ray scattering and dynamic mechanical. An analogue of POSS (denoted as POSSMOCA) was synthesized via addition reaction, which had reactive amino group bonding into epoxy network and improved the thermostability, because of the structural silicon, nitrogen and halogen. Epoxy/polyhedral oligomeric silsesquioxanes (POSS) hybrid composites were prepared from prereaction between trifunctional silanol POSS-OH and diglycidyl ether of bisphenol A (DGEBA) via silanol and the oxirane group. Reactive POSS-PGMA was polymerized via Reversible addition-fragmentation transfer polymerization. It was easy to tail the compatibility of the epoxide block copolymer with a step-growth polymerized matrix, to form nanostructure via reaction with PGMA segements. In the case of inert POSS-PMMA copolymers modified epoxy, topology of copolymer defined the final morphology and interaction between epoxy and them, because of directional hydrogen bonding and dilution effect. Tg of different epoxide conversion, obeyed of Gordon-Taylor equation and Kwei equation, k which reflected the interaction of modifier and DGEBA/MEDA and epoxy/amine oligomers, was consistent of the rheology and dynamic results.

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This study was carried out at the Department of Nanotechnology and Functional Materials,Uppsala University, one of several places where the interest of lignin in cosmetics is constantly growing. The functionalities of lignin have been studied to a great extent revealing its potential as a natural biopolymer to serve as a replacement for environmentally hazardous components in cosmetic formulations, namely UV-filters in sunscreens. Using ethnographic methods and qualitative interviews the lignin-cosmetic industry was observed and analyzed in order to discern how concerned the industry is with ecological andaesthetic value. Ecological value is a hallmark of the value proposition in the cosmetic industry, and leaders of the industry indeed share this view. The analysis further revealed that the actors of the lignin-cosmetic industry are at different stages of development and that as of this year we can expect the first product to be launched. Furthermore, the value chain of the lignin actors was identified and for the first time mapped out in detail from the qualitative analysis that was carried out targeting lignin actors within the lignin-cosmetic industry. Mapping the value chain revealed the actors included in the entire chain identified as biorefinery, manufacturer, modifier, formulator, distributor and retailer which together compose the lignin-cosmetic value chain. A qualitative, semi structured interview approach was used and adapted as we met with eleven actors interviewing them about ecological and aesthetic values in the lignin based product value proposition. The grounded theory was applied to analyze the data, generating eight categories representing the concepts comprising ecological and aesthetic values of the value proposition. The kernel category, Green Profile, explains the most important concepts valued by lignin actors in terms of what ecological and aesthetic value could be offered to be appealing to customers. The findings of this study reveals the current situation of lignin in the cosmetic market as of today, and discerns where the value of lignin lies. The understanding of lignin actors' values contributes to the current gray-area in biopolymer research, lacking information on the value chain of lignin in cosmetics. The findings therefore foster the advancement of sustainable innovative solutions for cosmetics and personal care.

Percolation theory is a relevant area of research in Nanotechnology because of its wide applications in nanoelectronics based on thin films of nanoparticles and composites, amongst others. In nanotechnology, systems are often explored through modelling and simulations. Thin films of the emerging low-dimensional nanomaterials, such as the 1D nanowires/nanotubes and 2D graphene, as well as their composites, can generally be simulated through a two dimensional percolation system of homogeneous or heterogeneous ellipses. The critical phenomena, i.e., the percolation threshold of the systems, is now obtained using the Monte Carlo simulation method, which, need extensive amounts of time. This project is an interdisciplinary one, wherein an attempt is made to use a certain amount of the data from the Monte Carlo simulations to train a machine learning model to predict the threshold of all the 2D ellipse systems with the maximum relative error &lt; 10%, thus reducing the time taken when gathering the data. This project investigates different algorithms such as Linear Regression, Polynomial Regression, Multi-layer Perceptron Neural Networks, Random Forests, Extreme Gradient Boosted Trees, Support Vector Machines and K-Nearest Neighbours. Weaknesses in the results are identified and overcome by specific additional sample generation. Finally, a comparison is made between the algorithms marking the Multi-layer Perceptron and Extreme Gradient Boosted Trees as successful, with the Multi-layer Perceptron being the clear winner. The algorithm is successful within the defined 10% relative error, performing even better with all samples having relative prediction errors less than 7%. The model can be downloaded and used from https://github.com/NiravSurajlal/ PercolationAI. / Perkolationsteori är ett relevant forskningsområde inom nanoteknik på grund av dess breda tillämpningar inom nanoelektronik, bland annat baserade på tunna filmer av nanopartiklar och kompositer. Inom nanoteknik undersöks system ofta genom modellering och simuleringar. Tunna filmer av de framväxande lågdimensionella nanomaterialen, såsom 1D-nanotrådar / nanorör och 2Dgrafen, liksom deras kompositer, kan i allmänhet simuleras genom ett tvådimensionellt perkolationssystem av homogena eller heterogena ellipser. De kritiska fenomenen, dvs. systemets perkolationströskel, erhålls nu med hjälp av Monte Carlosimuleringsmetoden, som kräver omfattande tidsperioder. Detta projekt är ett tvärvetenskapligt projekt, där man försöker använda en viss mängd data från Monte Carlo-simuleringarna för att träna en maskininlärningsmodell för att förutsäga tröskeln för alla 2D-ellipssystem med det maximala relativa felet &lt;10%vilket minskar den tid det tar att samla in data. Detta projekt undersöker olika algoritmer som linjär regression, polynomregression, flerlagers Perceptron-neuronnätverk, slumpmässiga skogar, extrema gradientförstärkta träd, stöd för vektormaskiner och K-närmaste grannar. Svagheter i resultaten identifieras och övervinns genom specifik ytterligare provgenerering. Slutligen görs en jämförelse mellan algoritmerna som markerar Multi-layer Perceptron och Extreme Gradient Boosted Trees som framgångsrika, med Multi-layer Perceptron som den tydliga vinnaren. Algoritmen är framgångsrik inom det definierade 10 % relativfelet och presterar ännu bättre med alla prover som har relativa prediktionsfel mindre än 7 %. Modellen kan laddas ner och användas från https://github.com/NiravSurajlal/PercolationAI.

Doctor of Philosophy / Department of Chemical Engineering / Larry E. Erickson / Over the past decade, nanomaterials have been the subject of enormous interest. Their defining characteristic is a very small size in the range of 1-100 nm. Due to their nanometer size, nanomaterials are known to have unique mechanical, thermal, biological, optical and chemical properties, together with the potential for wide-ranging industrial applications. Here, we synthesized nanocrystalline metal oxides through the sol-gel process and used these materials as desulfurization adsorbents and photocatalysts. Deep desulfurization of fuels has received more and more attention worldwide, not only because of health and environmental consideration but also due to the need for producing ultra-low-sulfur fuels, which can only be achieved under severe operating conditions at high cost using hydrodesulfurization (HDS). Consequently, development of new and affordable deep desulfurization processes to satisfy the decreasing limit of sulfur content in fuels is a big challenge. Sol-gel derived Cu/Al[subscript]2O[subscript]3 and Zn/Al[subscript]2O[subscript]3 adsorbents have been demonstrated to be effective in the removal of thiophene from a model solution. Results showed that Cu[superscript]+ was the active site and thermal treatment under vacuum was critical for Zn/Al[subscript]2O[subscript]3 since a defective, less crystalline spinel led to stronger interaction between zinc ions and thiophene molecules in the adsorption process. The kinetic study suggested that most of the adsorption occurred in the first 30 min, and adsorption equilibrium was attained after 1.5 h. Both adsorbents showed good regenerative property. TiO2 is considered the most promising photocatalyst due to its high efficiency, chemical stability, non-toxicity, and low cost for degradation and complete mineralization of organic pollutants. However, the use of TiO[subscript]2 is impaired because it requires ultraviolet (UV) activation ([Lambda]<387 nm). The shift of optical response of TiO[subscript]2 from the UV to the visible light region would have a profound positive effect on the efficient use of solar energy in photocatalytic reactions. We shifted the optical response of TiO[subscript]2 and improved the photocatalytic efficiency through size modification and transition metal ion and nonmetal atom doping. Experimental results showed that C and V co-doped TiO[subscript]2 catalysts had much higher activity than commercial P25 TiO[subscript]2 towards the degradation of acetaldehyde under visible light irradiation. For the first time, we reported that activities were comparable in the dark and under visible light irradiation for co-doped TiO[subscript]2 with 2.0 wt% V. C and N co-doped TiO[subscript]2 exhibited higher activity for the degradation of methylene blue than pure TiO[subscript]2 under visible light and UV irradiation. Possible mechanisms were discussed based on the experimental results.

Engineered nanomaterials (ENMs) have become ubiquitous in consumer products and industrial applications, and consequently the environment. Much of the environmentally released ENMs are expected to enter terrestrial ecosystems via land application of nano-enriched biosolids to agricultural fields. Among the organisms most likely to encounter nano-enriched biosolids are the key soil bacteria known as plant growth promoting rhizobacteria (PGPR). I reviewed what is known concerning the toxicological effects of ENMs to PGPR and observed the need for high-throughput methods to evaluate lethal and sublethal toxic responses of aerobic microbes. I addressed this issue by developing high-throughput microplate assays which allowed me to normalize oxygen consumption responses to viable cell estimates. Oxygen consumption is a crucial step in cellular respiration which may be examined relatively easily along with viability and may provide insight into the metabolic/physiological response of bacteria to toxic substances. Because many of the most toxic nanomaterials (i.e. metal containing materials) exhibit some level of ionic dissolution, I first developed my methods by examining metal ion responses in the PGPR, Bacillus amyloliquefaciens GB03. I found this bacterium exhibits differential oxygen consumption responses to Ag+, Zn2+, and Ni2+. Exposure to Ag+ elicited pronounced increases in O2 consumption, particularly when few viable cells were observed. Also, while Ni2+ and Zn2+ are generally thought to induce similar toxic responses, I found O2 consumption per viable cell was much more variable during Ni2+ exposure and that Zn2+ induced increased O2 utilization to a lesser extent than Ag+. Additionally, I showed my method is useful for probing toxicity of traditional antibiotics by observing large increases in O2 utilization in response to streptomycin, which was used as a positive control due to its known effects on bacterial respiration. After showing the utility of my method for examining metal ion responses in a single species of PGPR, I investigated the toxicity of silver ENMs (AgENMs) and ions to three PGPR, B. amyloliquefaciens GB03, Sinorhizobium meliloti 2011, and Pseudomonas putida UW4. The ENM exposures consisted of untransformed, polyvinylpyrrolidone coated silver ENMs (PVP-AgENMs) and 100% sulfidized silver ENMs (sAgENMs), which are representative of environmentally transformed AgENMs. I observed species specific O2 consumption responses to silver ions and PVP-AgENMs. Specifically, P. putida exhibited increased O2 consumption across the observed range of viable cells, while B. amyloliquefaciens exhibited responses similar to those found in my first study. Additionally, S. meliloti exhibited more complex responses to Ag+ and PVP-AgENMs, with decreased O2 consumption when cell viability was ~50-75% of no metal controls and increased O2 consumption when cell viability was <50%. I also found the abiotically dissolved fraction of the PVP-AgENMs was likely responsible for most of the toxic response, while abiotic dissolution did not explain the toxicity of sAgENMs. My work has yielded a straightforward, cost-effective, and high-throughput method of evaluating viability and oxygen consumption in aerobic bacteria. I have used this method to test a broad range of toxic substances, including, metal ions, antibiotics, and untransformed and transformed ENMs. I observed species specific toxic responses to Ag+, PVP-AgENMs, and sAgENMs in PGPR. These results not only show the clear utility of the methodology, but also that it will be crucial to continue examining the responses of specific bacterial strains even as nanotoxicology, as a field, must move toward more complex and environmentally relevant systems.

Three-dimensional porous single crystals (PSCs) are a recent development in the growing world of mesoporous material. The mesoporosity allows for the material to retain their nanoproperties whilst being bulk in size. The current work concentrates on chromium oxide and cobalt oxide PSCs formed in the templates SBA-15 and KIT-6. HRTEM is the main technique used in this investigation, looking at the morphology and single crystallinity of these materials. A growth mechanism for the PSC material is proposed based on HRTEM observations. XRD studies revealed that the confinement effect, caused by the mesopores, reduces the temperature for both cobalt and chromium oxide crystallisation, as well as a different intermediate route from the metal nitrates. The properties of chromium oxide PSC are also investigated magnetically and catalytically. Some metal oxides in different templates are also presented, despite no PSC forming. HRTEM work on other nanomaterials, based on collaboration, is also presented.

Ce travail porte sur la synthèse de couches minces de nanoparticules de silicium (np-Si) encapsulées dans une matrice diélectrique en vue d’une application en tant que couche active pour les cellules solaires de 3ème génération. La technique utilisée pour la synthèse des np-Si est la pyrolyse laser. Cette technique nous a permis d’obtenir des np-Si cristallines d’environ 5 nm de diamètre avec une distribution en taille étroite. Par ailleurs, l’utilisation de gaz précurseurs spécifiques (PH₃, B₂H₆) dans le mélange réactionnel a rendu possible le dopage (type n ou p) des np-Si. Le dopage effectif des np-Si a pu être mis en évidence par des mesures de résonance paramagnétique électronique (RPE). Des films de np-Si seules ont pu être déposés in-situ via la création d’un jet supersonique de gaz contenant les particules de silicium. Les caractérisations optoélectroniques de ces couches ont montré un effet de confinement quantique fort au sein de films, garantissant ainsi un élargissement important du gap du silicium de 1.12 eV (pour le silicium massif) à environ 2 eV (pour les np-Si) ; prérequis indispensable pour réaliser une cellule tandem tout silicium. Des mesures de résistivité sur ces films ont permis de confirmer l’activité des dopants au sein des np-Si. Pour les np-Si dopées au phosphore une diminution de la résistivité de plus de 5 ordres de grandeurs par rapport au np-Si intrinsèques a été observée. Le couplage entre la pyrolyse laser et la pulvérisation magnétron via notre dispositif original de synthèse s’est révélé parfaitement adapté à l’élaboration de couches minces nanocomposites np-Si/SiO₂. Un comportement de type diode a pu être mis en évidence sur une jonction constituée par la superposition d’une couche nanocomposites (type n) sur un substrat de silicium massif (type p). Au-delà de la simple application au photovoltaïque, le procédé couplé, largement éprouvé et optimisé au cours de ce travail de thèse, pourrait permettre la réalisation d’une multitude de couches nanocomposites différentes, puisque la nature chimique des particules et de la matrice peuvent être choisies indépendamment. / This work focuses on the synthesis of thin films composed of silicon nanoparticles (np- Si) embedded in a dielectric matrix for application as an active layer for the third generation solar cells. The technique used for the synthesis of np-Si is the laser pyrolysis. This technique allowed us to obtain 5 nm cristalline np -Si with a narrow size distribution. Furthermore, the use of specific precursor gases (PH₃, B₂H₆) in the reaction mixture enables doping (n or p -type) of np -Si. Effective np -Si doping has been demonstrated by measurements of electron paramagnetic resonance (EPR). Films made of np-Si only, have been deposited in situ by creating a supersonic jet of gas containing the silicon particles. Optoelectronic characterization of these layers showed a strong quantum confinement effect in films, thus ensuring a significant widening of the gap of 1.12 eV silicon (for bulk silicon) to about 2 eV (np -Si); which is an essential prerequisite to achieve a silicon tandem cell. Resistivity measurements on these films have confirmed the dopants activity in the np -Si. For np -Si doped with phosphorus, a significant decrease of the resistivity of more than five orders of magnitude compared to the intrinsic np -Si was observed. Coupling between laser pyrolysis and magnetron sputtering through our original synthesis device proved to be perfectly suited for the elaboration of nanocomposite thin films np-Si/SiO₂. A diode-type behavior has been highlighted on a junction formed by the superposition of a nanocomposite layer (n-type) on a bulk silicon substrate (p-type ). Beyond the simple application to photovoltaics , the coupled process, widely used and optimized during this work could allow the production of a multitude of different nanostructured layers , since the chemical nature of the particles and the matrix can be chosen independently.