En esta tesis se estudian la electrocatálisis de algunas reacciones involucradas en las pilas de combustible. Se utilizan electrodos monocristalinos de oro y platino para analizar, a nivel fundamental, los procesos que tienen lugar en la interfase entre electrodo y la disolución. En una primera parte se analiza la oxidación de ácido fórmico e hidracina que son dos combustibles empleados en las celdas de combustible. Posteriormente se estudian reacciones secundarias a las mismas como es la oxidación de CO o la oxidación y reducción de peróxido de hidrógeno.

Traditionally, when debugging a software system, developers rely on having access to the input data that caused the error. However, with data privacy concerns on the rise, it is becoming increasingly challenging to rely on input data as it might be sensitive or even classified. Telemetry is a method of collecting information about a system that can offer assistance. This thesis proposes a telemetry solution for debugging systems where input data is sensitive. The telemetry solution was implemented in a geographical 3D visualization system and evaluated based on two aspects: its effectiveness in assisting the developers working on the system to locate if and where a problem has occurred, and its ability to deduce the input data that generated the output. The results indicate that the telemetry solution is successful in helping developers identify system errors. Additionally, the system's privacy is maintained, as it is not feasible to directly ascertain the input data responsible from the output. However, no proof is presented and as such, no guarantee can be made. We conclude that telemetry can be a useful tool for developers, making the debugging process more effective while protecting sensitive input data. However, this might not be the case for different customers or systems. The thesis demonstrates the potential of using telemetry for debugging privacy-sensitive systems, with a proof-of-concept solution that can be improved upon in the future.

The Yellow Rail (Coturnicops noveboracensis) is a migratory nongame bird of high conservation priority throughout its entire range. The objectives of this study were: (1) assess Yellow Rail occupancy in the context of prescribed fire regime in pine savanna habitats of Mississippi and Alabama and (2) assess Yellow Rail habitat use in pine savanna habitats of coastal Mississippi. Yellow Rail occupancy decreased significantly with time since fire and increased with grassland patch size. Throughout the study area Yellow Rail maintained small (mean = 3.37 ha) home ranges aggregated within study areas, indicating suitable habitat may be limited. Yellow Rail used areas dominated by Aristida stricta and Carex spp. They used locations with lower woody percent cover, greater herbaceous height structure and lower frequency of trees than locations outside their home range. This research highlights the continued need to prioritize conservation and management of open grasslands and pine savanna habitats.

This thesis investigates the effect of reaction media on the efficiency of grafting hydrophobic polymers from cellulose nanocrystals (CNCs) via surface-initiated atom transfer radical polymerization (SI-ATRP), with the goal of producing highly-modified CNCs for incorporation into latex-based pressure sensitive adhesives (PSAs). A latex is a dispersion of polymer particles in water made by emulsion polymerization; latexes are commonly used in paints, coatings, elastomers, inks/toners, household products, cosmetics, and adhesives. However, latex-based PSAs often underperform compared to their organic solvent-polymerized counterparts due to a lack of cohesive strength in the cast latex films. The environmental benefit of using latex-based PSAs synthesized in water is significant, but the development of strategies to improve their performance are required. CNCs are hydrophilic rod-shaped nanoparticles with high mechanical strength. Adding CNCs to latex-based PSAs has been shown to improve both adhesive (i.e., tack and peel strength) and cohesive (i.e., shear strength) properties and offers a degree of sustainability because CNCs are derived from natural cellulose sources such as wood pulp. However, their hydrophilicity, particularly relative to the hydrophobic polymers used in PSAs, has constrained CNCs to the continuous (i.e., water) phase of the latex. To improve CNC compatibility with the dispersed (i.e., polymer) phase and improve their distribution in cast latex films, hydrophobic polymers can be grafted from CNCs. However, CNCs with a high polymer graft density are required to ensure their compatibility with monomers/polymers during latex synthesis. To begin, grafting poly(butyl acrylate) (PBA) from CNCs using SI-ATRP in polar dimethylformamide (DMF) versus non-polar toluene was directly compared. The enhanced colloidal stability of initiator-modified CNCs in DMF led to improved accessibility to surface initiator groups during polymer grafting. As such, PBA-grafted CNCs produced in DMF had up to 30 times more grafted polymer chains than PBA-grafted CNCs produced in toluene. The PBA-grafted CNCs produced in DMF showed high contact angles when cast in a film and formed stable suspensions in toluene. This work highlights that optimizing CNC colloidal stability in a given solvent prior to polymer grafting is a more crucial consideration than solvent–polymer compatibility in the context of obtaining high graft densities and thus hydrophobic CNCs via SI-ATRP. The improved polymer grafting method in DMF was then used to produce PBA and poly(methyl methacrylate) (PMMA)-grafted CNCs at two polymer chain lengths. Polymer grafted CNCs were incorporated in situ during a seeded semi-batch emulsion polymerization to produce PBA latex nanocomposite PSAs. Viscosity measurements revealed significant differences between latexes prepared with CNCs versus polymer-grafted CNCs, with the lower viscosities of the latter suggesting their incorporation inside the polymer particles. When CNCs with short polymer grafts were introduced into PSAs at 1 wt. % loading, they exhibited comparable tack and improved peel strength compared to unmodified CNCs (and all properties improved relative to the base latex without any CNCs). This is attributed to their improved distribution throughout the PSA, the enhanced wettability of the substrate with the CNC containing latex, and the increased polymer chain mobility achieved based on the low molecular weight of the grafts. CNCs with long polymer grafts aggregated in the latex and did not improve PSA properties. PMMA-grafted CNCs slightly outperformed PBA-grafted CNCs likely due to the higher glass transition temperature of PMMA. These results provide insight into future optimization of more sustainable latex-based PSA formulations as well as new commercial CNC-latex products, where the presence of low molecular weight grafts on CNC surfaces could improve polymer mobility and tack and peel strength. / Thesis / Master of Applied Science (MASc) / When the adhesives used in tapes, labels or sticky notes are produced using water-based reactions, they normally underperform compared to conventional adhesives produced using toxic solvents. To improve such water-based adhesives, adding nanocellulose (tiny particles derived from wood pulp) during synthesis has been shown to be an asset. Nanocellulose can be chemically modified to improve its compatibility with adhesive ingredients, and thus change the role of nanocellulose during adhesive manufacturing. In this thesis, modified nanocelluloses were added to water-based adhesives to evaluate their effect on performance (i.e., strength and stickiness). It was found that the reaction conditions during nanocellulose modification were crucial for obtaining highly modified particles that are compatible with adhesive ingredients. This work aims to provide insight for future production of less environmentally taxing adhesives made in water and expand the use of nanocellulose in new commercial products.

In this study, novel lamination techniques are introduced for the coating of fabrics in order to enhance their ballistic/needle penetration resistance properties. Pressure sensitive adhesive (PSA) was used to create flexible ballistic composite panels with ultra-high molecular weight polyethylene (UHMWPE) fabric. An increase in processing pressure from 0.1 to 8 MPa significantly improved the ballistic performance against 9 mm FMJ ammunition of UHMWPE composite. The number of layers required to stop the bullet were reduced from 45 to 22 layers after lamination without a significant increase in stiffness. The backface signature (BFS) was reduced from 19.2 mm for the 45 layer neat samples to 11.7 mm for the 25 layer laminated samples pressed at 8 MPa. The second lamination technique used patterned thermoplastic hot film to create flexible UHMWPE composite laminates. Hexagonal patterns were cut through a heat transfer vinyl carrier sheet using a vinyl cutter and was used as a mask between the UHMWPE fabric and hot film during heat treatment in order to have the fabric coated only on those regions. The patterns had a nominal diameter of 27.9 mm with a 1 mm gap between each region. A significant improvement in the ballistic performance of UHMWPE fabric is observed after coating each individual layer with patterned hot film and 25 layers of laminated fabric were sufficient to stop a .357 magnum FMJ ammunition compared to unlaminated neat fabric which required 45 layers to stop the bullet. Patterning of the hot film did not negatively affect the ballistic performance of the composite laminates whilst increasing their flexibility in relation to using plain hot film with no patterning involved. It resulted in a 21% increase in bending angle of the 25 layer samples v and 9.5% reduction in bending length of the single plies which both relate to greater flexibility because a higher bending angle and lower bending length correlates to more flexibility. The same technique of patterning of hot film is used in the lamination of woven cotton fabric to enhance needle penetration resistance properties whilst maintaining the flexibility. Patterns used in this study were either hexagonal or a combination of hexagons and triangles and the nominal diameter ranged from 2.6-13.5 mm. The lamination significantly improved the 25G hypodermic needle penetration resistance of the fabric. By increasing the number of laminated fabric plies from 1 to 2, the needle resistance force increased by up to 150%. However, in comparison to just one layer, the flexibility decreased by about 12% to 26% for two and three layers, respectively. It was observed that reducing the sizes of the patterns improved the flexibility of the samples by up to 30% without compromising the needle penetration resistance. / Thesis / Master of Applied Science (MASc)

The regulation of pH is a critical homeostatic function of plant cells. In addition to acting as the primary cationic species responsible for energizing the plasma membrane, protons likely act as an important regulator and messenger. Despite this importance, few studies have thoroughly described cytosolic pH patterns as the plant cell progresses through the cell cycle. To investigate pH in plant cells, I chose Nicotiana tabacum (tobacco) Bright Yellow-2 (BY-2) cells as a model system. My research has two aims. First, I will measure and report the interphase cytosolic pH of BY-2 cells. Next, I will assay the cytosolic pH as BY-2 cells progress through mitosis and cytokinesis. I hypothesize that pH patterns are be temporally or spatially associated with structures such as the mitotic spindle or the phragmoplast. To investigate cytosolic pH in BY-2 cells, I will develop a cytosolic pH reporter based on a pH sensitive ratiometric fluorescent dye. This dye will be able to resolve both temporal and spatial changes in pH throughout the cytosol while imposing a minimal amount of stress on BY-2 cells. I found that pH-GFP, a variant of eGFP, had qualities of a robust pH reporter. To introduce the dye, explored biolistic bombardment, Agrobacterium mediated transient transformation, and polyethylene glycol mediated transformation as methods for introducing the pH-GFP gene into BY-2 cells. I observed very few transformation events using these methods and my observations did not support these approaches as suitable for introducing pH-GFP into BY-2 cells.

In today's interconnected digital landscape, the protection of sensitive information is of great importance. As a result, the field of cryptography plays a vital role in ensuring individuals' anonymity and data integrity. In this context, this thesis presents a comprehensive analysis of symmetric encryption algorithms, specifically focusing on the Advanced Encryption Standard (AES) and Camellia. By investigating the performance aspects of these algorithms, including encryption time, decryption time, and ciphertext size, the goal is to provide valuable insights for selecting suitable cryptographic solutions. The findings indicate that while there is a difference in performance between the algorithms, the disparity is not substantial in practical terms. Both AES and Camellia, as well as their larger key-size alternatives, demonstrated comparable performance, with AES128 showing marginally faster encryption time. The study's implementation also involves encrypting a data set with sensitive information on students. It encrypts the school classes with separate keys and assigns roles to users, enabling access control based on user roles. The implemented solution successfully addressed the problem of role-based access control and encryption of unique identifiers, as verified through the verification and validation method. The implications of this study extend to industries and society, where cryptography plays a vital role in protecting individuals' anonymity and data integrity. The results presented in this paper can serve as a valuable reference for selecting suitable cryptographic algorithms for various systems and applications, particularly for anonymization of usernames or short, unique identifiers. However, it is important to note that the experiment primarily focused on small data sets, and further investigations may yield different results for larger data sets.

Pressure sensitive insoles are an emerging and promising technology that has always been interesting for gait and planar pressure related applications. This technology can be especially valuable for monitoring, movement, and rehabilitation purposes where the pressure sensing insoles could be utilized to assess for abnormalities in order to treat or prevent complications. This thesis project explores the use of graphene coated resistive textiles based smart insoles with the purpose of constructing a functional, easy to fabricate prototype that is viable for plantar pressure and gait cycle applications. This project follows a double diamond, co-productive approach with multiple stakeholders involved during the discovery, definition, development, and delivery of the project to co-create knowledge of value for society. The results of the thesis project present three functional prototypes with 3, 4 and 6 pressure sensors with the 4-sensor prototype indicating to be the most feasible out of the three. The highlight of the prototypes features is that it is capable of detecting and measuring pressure, operates with durable and thin properties and low accuracy. Through proper calibration with an ADC tool, the prototype was able to detect and measure movement during testing. Furthermore, several areas with a room for improvement have been identified with potential for further automating the production process as well as unlocking barriers for certain applications with a cost effective approach. In conclusion, this thesis project contributes to the advancement of smart insoles by presenting a functional, easy to fabricate method for the production of smart insoles for low accuracy gait cycle and plantar pressure applications.

京都大学 / 新制・課程博士 / 博士(医学) / 甲第24786号 / 医博第4978号 / 新制||医||1066(附属図書館) / 京都大学大学院医学研究科医学専攻 / (主査)教授 花川 隆, 教授 村井 俊哉, 教授 高橋 淳 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DFAM

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