京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18982号 / 工博第4024号 / 新制||工||1620(附属図書館) / 31933 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 田中 功, 教授 酒井 明, 教授 邑瀬 邦明 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(薬科学) / 甲第18918号 / 薬科博第32号 / 新制||薬||4(附属図書館) / 31869 / 京都大学大学院薬学研究科薬科学専攻 / (主査)教授 松﨑 勝巳, 教授 加藤 博章, 教授 石濱 泰 / 学位規則第4条第1項該当 / Doctor of Pharmaceutical Sciences / Kyoto University / DGAM

We propose a lattice model for three stochastically interacting components that mimicsthe formation of the internal structure of adhesive bands via evaporating one component(the solvent) by thermal gradient. We use high-performance computing resources toinvestigate the formation of rubber-acrylate morphologies. We pay special attentionto the role of varying temperature as well as of the changing the solvent interaction inconnection to the shape of the obtained rubber morphologies.In the lattice model, we start with microscopic spins of three particles in the latticewith short-range interactions between them. This microscopic model is approximatednumerically via a Monte Carlo Metropolis-based algorithm. High-performancecomputing resources and Python-based implementations have been used for thenumerical simulation of the lattice model. The numerical implementation highlights theeffect of the model parameters (volatility of the Solvent, temperature, and interactionbetween the particles) on the structure of the obtained morphologies. We demonstratethat one can utilize a reasonably simple model to explain the impact of parameters onthe creation of morphology in ternary systems when one component evaporates.

The purpose of this dissertation is to investigate the thermochemical properties of nonelectrolyte solutes dissolved in ternary solvent mixtures, and to develop mathematical expressions for predicting and describing behavior in the solvent mixtures. Forty-five ternary solvent systems were studied containing an ether (Methyl tert-butyl ether, Dibutyl ether, or 1,4-Dioxane), an alcohol (1-Propanol, 2-Propanol, 1-Butanol, 2-Butanol, or 2-Methyl-1-propanol), and an alkane (Cyclohexane, Heptane, or 2,2,4-Trimethylpentane) cosolvents. The Combined NIBS (Nearly Ideal Binary Solvent)/Redlich-Kister equation was used to assess the experimental data. The average percent deviation between predicted and observed values was less than ± 2 per cent error, documenting that this model provides a fairly accurate description of the observed solubility behavior. In addition, Mobile Order theory, the Kretschmer-Wiebe model, and the Mecke-Kempter model were extended to ternary solvent mixtures containing an alcohol (or an alkoxyalcohol) and alkane cosolvents. Expressions derived from Mobile Order theory predicted the experimental mole fraction solubility of anthracene in ternary alcohol + alkane + alkane mixtures to within ± 5.8%, in ternary alcohol + alcohol + alkane mixtures to within ± 4.0%, and in ternary alcohol + alcohol + alcohol mixtures to within ± 3.6%. In comparison, expressions derived from the Kretschmer-Wiebe model and the Mecke-Kempter model predicted the anthracene solubility in ternary alcohol + alkane + alkane mixtures to within ± 8.2% and ± 8.8%, respectively. The Kretschmer-Wiebe model and the Mecke-Kempter model could not be extended easily to systems containing two or more alcohol cosolvents.

The mining industry is a major economic driver and job creator for many countries. However, mining is associated with geo-hazards and environmental issues, such as the disposal of large volumes of waste, acid mine drainage, and ground subsidence. As a result, efficient mining waste management is crucial for sustainable development. The geotechnical, economic, and environmental benefits of cemented paste backfill (CPB) have piqued the interest of researchers and academicians worldwide, making it an essential aspect of underground mining management. CPB is a thickened cementitious combination of dewatered tailings (70 - 85 wt.%), binders (usually 3 to 8% wt.%), and water used to backfill mine waste into underground mining stopes. Despite being used in small amounts, the cost of cement makes up to 80% of the cost of backfilling operations. In addition, clinker production accounts for 5-8% of global human created carbon dioxide (CO₂) emissions. This predicament necessitates the development of a viable alternative to cement. Partially substituting cement with supplementary cementitious materials like fly ash, blast furnace slag, natural pozzolans, and other materials has been increasingly prevalent in CPB. It is evident that the addition of slag to cement can increase the mechanical strength of CPB at the advanced ages but decreases the strength and suction development due to the slow reaction kinetics in the CPB at the early ages, which may negatively affect the mechanical stability of the CPB, mining cycle, and safety of mineworkers. Moreover, the supply of these materials is limited and may not be enough for the future needs of the industry. Furthermore, there has been a surge in interest in using limestone powder (LS) owing to its abundance, low cost, and lack of environmental costs which are associated with Portland cement - Type 1 (PCI). The addition of LS accelerates hydration at the early ages, thus resulting in high early strength, but the dilution effect can reduce the late strength. The combination of LS and slag in a ternary blended cement can be potentially used as a binder for CPB with acceptable strength development at the early and advanced ages while lowering the cost of the CPB and the carbon footprint of the mining industry. Nevertheless, the rheology, mechanical strength, and stability are important key performance quality criteria for CPB; however, the effect of ternary cement blends on these parameters is not well known. In this research program, the impact of the binary and ternary cement blends on (i) the fresh properties of CPB, such as the rheological properties (yield stress, viscosity) and setting time, and (ii) the strength and suction development of CPB are investigated. To understand the effect of substituting slag with LS in the binary binder in the first phase of the study, binary binders with two differ-ent PCI: Slag proportions of 50/50 and 80/20 are examined with no limestone, followed by replacing slag with an increasing amount of LS from 0 to 20 wt. % of the total binder, with a constant cement content, over a period of 4 hrs (0, 0.25, 1, 2, and 4 hrs) of curing at room temperature. In the second phase, the effect of a ternary binder (PCI-Slag- LS) with varying proportions on the suction development and the mechanical behavior of hardened CPB is investigated over a curing period of up to 90 days. The changes in strength of these binary and ternary binders on the CPB sample are tested for 1, 3, 7, 28, 60, and 90 days. An unconfined compression test (UCS) is conducted to evaluate the strength development. The microstructure of the mixes is examined through mercury intrusion porosimetry (MIP) for changes are validated through monitoring for the development of hydration and suction, electrical conductivity (EC), and temperature, which is carried out for up to 30 days. This is followed by a microstructure analysis with a thermogravimetric/differential thermogravimetric test on fresh and hardened samples. The results of the first phase show that an increase in the percentage of substituted cement in the binary binder (from PCI/Slag 80/20 to 50/50) increases the yield stress of the CPB but decreases the viscosity of the mix. However, the addition of LS as a substitution for slag shows a considerable decrease in the yield stress of the control mix with an increase in viscosity with increasing dosages of LS, thus indicating an improvement in the flowability of CPB. The second phase results indicate that the slow hydration kinetics of slag influences early age suction and strength changes in the binary sample with a high slag content (50/50); however, its latent hydraulic and pozzolanic properties enhance strength gain after 28 days. The addition of 5% limestone to the ternary blend increases the strength gain by up to 7 days compared to the binary control samples. Indeed, the presence of LS influences the rate of hydration of cement and slag through both physical (filler, nucleation, dilution) and chemical (hydrate) effects. However, substituting more than 10% LS for slag affects the mechanical performance at all ages. Overall, up to 50 wt.% slag and 10 wt.% limestone with cement as a ternary binder can be used without significant compressive strength loss. This study demonstrates that the partial substitution of ordinary Portland cement (OPC) with varying percentages of slag and LS is complementary, and overall, the interaction of slag and LS is observed. The optimal use of LS and slag in a ternary system may serve as a sustainable alternative to the commonly used OPC and PCI/Slag binders, thereby reducing the energy consumption and carbon footprint associated with cement. The findings of this study will ultimately help to develop a better understanding of the impact of ternary blends with increasing percentages of LS on the rheology and setting time of CPB mixes and mechanical strength changes in designing an efficient mixing plant, particularly its transport system.

<p>  </p> <p>From applications in nanoscale electronics to regenerative medicine, there is a strong need for control assembly processes at nanometer length scales.1,2 In this work, we investigate the application of microscale droplet delivery as a rapid and scalable approach to pattern the molecular assembly of nanoscale chemical patterns on highly oriented pyrolytic graphite (HOPG). Furthermore, it was also observed that variations in the blend of alkyl impurities present in technical-grade OLAm reagents influenced the temperature-dependent assembly behavior.13 This suggests a likely role of alkyl chain phase transitions in the ligand shell, particularly in more complex mixtures and for anisotropic nanocrystals.</p> <p>Oleylamine (OLAm) is a common technical-grade reagent used in nanocrystal synthesis. Most nanocrystal synthesis is done using technical grade Oleylamine (70% purity). Higher purity reagents are not readily available because in certain instances, technical grades are obtained from natural substances, resulting in differing impurities compared to those generated during preparative reactions using pure raw materials.3 Technical grade reagents of OLAm contain 70% of the cis chain OLAm and 30% of an unspecified mixture of Elaidylamine (ELAm) , Octadecylamine (ODAm) and segments of various lengths and saturated alkyl chains.4,5 Here, we use Differential Scanning Calorimetry thermograms to investigate the miscibility of binary mixtures of OLAm/ELAm, OLAm/ODAm, and ELAm/ODAm. Ternary mixtures of the lipids showed clear peaks for the trans and saturated impurities.</p> <p>We patterned graphite surfaces with amphiphiles via inkjet printing to quickly generate 1-nm-wide functional patterns. Inkjet printing allowed for long-scale hierarchical patterning. We investigated various ink formulations and the resulting printing quality of functional monolayers on 2D crystalline materials. </p>

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<p>The growth of ternary InGaP nanowires (NWs) is explored. Free-standing NWs are grown with the Au nanoparticle-assisted method using a gas source molecular beam epitaxy (GS-MBE) system. The grown samples were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive x-ray spectroscopy (EDX). These characterization techniques were employed to examine the composition of the InGaP NWs, the morphology and the crystal structure. With varying the growth conditions, such as temperature, growth rate and V/III flux, a dependence of the NWs' composition, morphology and crystal structure were observed. In addition, the characteristics of the NWs showed great dependence on the diameter of the Au seed particle responsible for the NW growth.</p> <p>A physical-based growth model is developed to understand the NW growth results. The model deals with each of the group-III growth species differently and splits the group-V into two components, with each component associated with one of the group-III species. The model is able to match composition and morphology results obtained from the experimental data.</p> <p>Furthermore, a nucleation-based model is employed and integrated with the growth model to predict the crystal structure of the NWs. Based on this model, the operating regions for all out samples were illustrated. In addition, the dependence of the crystal structure of the NWs on the Au seed diameter, in our samples, was attributed to the change in the surface energies of the formed nucleus as the Au seed diameter change.</p> / Doctor of Engineering (DEng)

JLP (JNK associated Leucine zipper protein) is a scaffolding protein that has been shown to interact with and activate the JNK/p38MAPK pathway. Its interaction with various signaling proteins is associated with coordinated regulation of cellular processes such as endocytosis, motility, neurite outgrowth, cell proliferation and apoptosis. Here, we undertook a mass spectrometric approach to identify novel interaction partners of JLP and identified the mitotic Ser/Thr kinase, Polo like Kinase 1 (PLK1) and the Fox transcription factor, Forkhead box protein K1 (FoxK1), as proteins that interact with and form a ternary complex with JLP during mitosis. Domain mapping studies showed that the N-terminal domain of JLP interacts with the polo-box domain (PBD) of PLK1 in a phosphorylation-dependent manner. Our results indicate that, JLP is phospho-primed on Thr351, which is recognized by the PBD of PLK1 and leads to phosphorylation of JLP at additional sites. Moreover, treatment of cells with the PLK1 inhibitor BI2536 affects this interaction, demonstrating the importance of PLK1 kinase activity in this process. Because JLP is a scaffolding protein that recruits proteins to mediate specific cell signaling events, the interaction of JLP with PLK1 likely results in the recruitment of other proteins to this complex. To test this hypothesis, we carried out SILAC labeling of proteins in mitotic cells in the presence or absence of BI2536. Through mass-spectrometry, we identified the FoxK1 transcription factor as a PLK1-dependent JLP-interacting protein. Furthermore, we show that JLP, PLK1 and FoxK1 form a ternary complex that is present only during mitosis. Knockdown of PLK1 and not JLP affected the interaction between JLP and FoxK1, indicating that the formation of the ternary complex is PLK1-dependent. FoxK1 is a known transcriptional repressor of the cyclin dependent kinase inhibitor, p21/WAF1. Knockdown of JLP in U2OS cells resulted in increased FoxK1 protein levels and a reduction of p21 expression. Moreover, immunofluorescence studies in asynchronous cells showed that FoxK1 is excluded from the nucleus during mitosis and that a fraction of FoxK1 localizes to the midbody region during cytokinesis. Analysis of FoxK1 protein in cells exiting S-phase suggests that FoxK1 is post-translationally modified during mitosis. In this study we characterized the ternary complex formed between JLP, PLK1 and FoxK1 during mitosis. Based on our observations, we propose that formation of the JLP/PLK1/FoxK1 ternary complex regulates the stability and/or transcriptional activity of FoxK1. / Molecular Biology and Genetics