Dental secondary caries is the carious lesion developed around existing restoration margins. Many new technologies have been developed for caries detection purposes, but their performance is unsatisfactory for the specific purpose of secondary caries diagnosis. Therefore, the development of a novel technology to detect secondary caries has been highly necessary. The objective of this research was to investigate the ability of photothermal radiometry and modulated luminescence to detect secondary caries: wall lesions and outer lesions. Changes in experimental PTR-LUM signals due to sequential demineralization on vertical walls of sectioned tooth samples were investigated. Another study was conducted to investigate how two different types of secondary caries, wall lesions and outer lesions, affect the PTR-LUM signals. The studies demonstrated that PTR-LUM is sensitive to progressive demineralization and remineralization on vertical walls of sectioned tooth samples, as well as to the presence of wall lesions and outer lesions developed around composite restorations.

Only 2.5% of the water on Earth is fresh water and only less than 1% is accessible to human consumption. Landlocked and desert communities and communities that are not wealthy enough to provide clean drinking water via conventional water treatment technologies are facing severe water shortages and tend to rely on long distance transportation to supply fresh water for their daily use. As a lot of the water-scarce countries have abundant annual solar irradiation and relatively high humidity, this project proposes a technology that harvests water from ambient air using an anhydrate salt and releases it for collection using sunlight. This technology is designed to be potentially deployed in night-day cycles, as the humidity at night is at its peak, and solar irradiation during the day is also at its peak. In this work, a mesoporous silica powder filled with CuCl2 and coated with carbon nanotubes is used. The water capture performance of this material was investigated with different relative humidity environments. Furthermore, the powder agglomeration sizes of this material were also investigated for each relative humidity environment. Water release was investigated under 1 kW/m2 simulated solar light in an in-lab ~60% relative humidity environment. The results show that this mesoporous material was able to capture water at 12% relative humidity conditions, low enough to capture water from the air in the Sahara Desert. At relative humidity of 15% and 35%, the material was able to absorb 0.12 and 0.25 kg/kg of water, respectively, within 100 minutes, which indicates its fast water harvesting kinetics. A fully hydrated sample released 0.26 kg/kg of water in almost half an hour under 1 kW/m2 simulated sunlight. This project sheds more light on utilizing the atmosphere as an alternative water source.

Multifunctional theranostic nanoparticles hold promise for enabling non-invasive image guided cancer therapy such as photothermal therapy. Human breast tumor models in which response to image guided therapy can quickly and non-invasively be determined are needed to facilitate translation and application of these technologies. We hypothesize that a system utilizing a murine light-reporter mammary tumor cell line and near-infrared nanoparticles (NIR-NP) can be used to quantify response to therapy and determine fate of nanoparticles following photothermal ablation.

Water scarcity has caused severe impact on the entire ecosphere while the climate change is resulting in high frequency of extreme weather conditions, especially extended period of drought. Due to the even increasing world’s population and the continued societal modernization, water scarcity is now one of the leading global challenges towards the development of human society. On the other hand, atmospheric water, accounting for 6 times the water in all rivers on Earth, is emerging as an alternative water resource. This dissertation thoroughly investigated the fully solar energy driven atmospheric water harvesting (AWH) process in a broad scientific and application context. The light-to-heat conversion process of solar photothermal materials was investigated first with a rationally designed droplet-laser system, which in combination with the calculation of heat of absorption of water vapor for various application scenarios, formed a theoretical basis of this dissertation research. As a result, a series of commonly used hydrated salts and their anhydrous counterparts were judiciously selected and successfully proven to be low-cost AWH materials to generate clean fresh water for arid regions. A hydrogel-deliquescent salt composite was further developed as AWH material with a significantly enhanced fresh water production capacity. A new design of nano-capsule encapsulated deliquescent salt was further put forward to enhance water vapor sorption/desorption kinetics, which enabled, for the first time, multiple sorption/desorption cycles within one day and thus multiplied water production capacity. The first-ever continuous AWH device, as opposed to batch-type one, was rationally designed, fabricated, and successfully tested in field conditions outdoors. At last, the dissertation pioneered a novel concept of atmospheric water sorption and desorption cycle for photovoltaic (PV) panel cooling. This dissertation shines significant light on sorption based atmospheric water harvesting and inspires more research efforts on this important research topic.

Accurate temperature and thermal property measurements are critical for the modeling and prediction of heat transfer. In many industries thermal management is a limiting factor of performance, and rely on advanced modeling techniques to develop and design methods to better manage thermal energy. This study expands the thermal property and pyrometry measurement capabilities by developing three new techniques based on thermal emission’s nonlinear dependence on temperature.

Graphene is a form of carbon with unique thermal and structural properties, giving it high potential in many applications, from electronics to driveway heating. Advanced fabrication techniques putting small, graphene-like structures in a polymer matrix could allow for incorporation of some of the benefits of graphene into very lightweight materials, and allow for broader commercialization. Measuring the thermal properties of these thin-film samples is a technical capability in need of development for use with the specific specimens used in this study. Relating those thermal properties to the microstructural composition was the focus of this work. Several conclusions could be drawn from this study which will help guide future development efforts. Among these findings, it was found that increasing carbon content only improves thermal and electrical conductivity if the samples were of low porosity. Samples of approximately identical overall carbon content and void content had higher thermal conductivity if some carbon nanotubes were added in place of graphite. Nanotubes also appeared to reduce variability in thermal conductivity between pressed and unpressed samples, allowing for more predictable properties in fabrication.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18979号 / 工博第4021号 / 新制||工||1619(附属図書館) / 31930 / 京都大学大学院工学研究科マイクロエンジニアリング専攻 / (主査)教授 鈴木 基史, 教授 木村 健二, 教授 蓮尾 昌裕 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

The continued development of integrated photonic devices requires low-power, small volume all-optical modulators. The weak nonlinear optical response of conventional optical materials requires the use of high intensities and large interaction volumes in order to achieve significant light modulation, hindering the miniaturization of all-optical switches and the development of lightweight transmission optics with nonlinear optical response. These challenges may be addressed using plasmonic nanostructures due to their unique ability to confine and enhance electric fields in sub-wavelength volumes. The ultrafast nonlinear response of free electrons in such plasmonic structures and the fast thermal nonlinear optical response of metal nanoparticles, as well as the plasmon enhanced nonlinear Kerr-type response of the host material surrounding the nanostructures could allow ultrafast all-optical modulation with low modulation energy. In this thesis, we investigate the linear and nonlinear optical response of engineered effective media containing coupled metallic nanoparticles. The fundamental interactions in systems containing coupled nanoparticles with size, shape, and composition dissimilarity, are evaluated analytically and numerically, and it is demonstrated that under certain conditions the achieved field enhancement factors can exceed the single-particle result by orders of magnitude in a process called cascaded plasmon resonance. It is demonstrated that these conditions can be met in systems containing coupled nanospheres, and in systems containing non-spherical metal nanoparticles that are compatible with common top-down nanofabrication methods such as electron beam lithography and nano-imprint lithography. We show that metamaterials based on such cascaded plasmon resonance structures can produce enhanced nonlinear optical refraction and absorption compared to that of conventional plasmonic nanostructures. Finally, it is demonstrated that the thermal nonlinear optical response of metal nanoparticles can be enhanced in carefully engineered heterogeneous nanoparticle clusters, potentially enabling strong and fast thermal nonlinear optical response in system that can be produced in bulk through chemical synthesis.

Gold nanoparticles (AuNPs) with their unique sizes, shapes, and properties have generated much enthusiasm over the last two decades, and have been explored for many potential applications. The successful application of AuNPs depends critically on the ability to modify and functionalize their surface to provide stability, compatibility, and special chemical functionality. This dissertation is aimed at exploring the chemical synthesis and surface modification of AuNPs with the effort to (1) control the number of functional groups on the particle surface, and to (2) increase the colloidal stability at the physiological conditions. To control the functionality on the particle surface, a solid phase place exchange reaction strategy was developed to synthesize the 2 nm AuNPs with a single carboxylic acid group attached on the particle surface. Such monofunctional AuNPs can be treated and used as molecular nanobuilding blocks to form more complex nanomaterials with controllable structures. A "necklace"-like AuNP/polymer assembly was obtained by conjugating covalently the monofunctional AuNPs with polylysine template, and exhibited an enhanced optical limiting property due to strong electromagnetic interaction between the nanoparticles in close proximity. To improve the colloidal stability in the psychological condition, biocompatible polymers, polyacrylic acid (PAA), and polyethylene glycol (PEG) were used to surface modify the 30 nm citrate-stabilized AuNPs. These polymer-modified AuNPs are able to disperse individually in the high ionic strength solution, and offer as the promising optical probes for bioassay applications. The Prostate specific antigen (PSA) and target DNA can be detected in the low pM range by taking advantages of the large scattering cross section of AuNPs and the high sensitivity of dynamic light scattering (DLS) measurement. In addition to the large scattering cross section, AuNPs can absorb strongly the photon energy at the surface plasmon resonance wavelength and then transform efficiently to the heat energy. The efficient photon-thermal energy conversion property of AuNPs has been used to thermal ablate the Aβ peptide aggregates under laser irradiation toward Alzheimer's disease therapy.

Plasmonic photothermal therapy (PPTT) has a rising promise for treating different cancer cells such as lymphoma or stomach cancer. Technique development of PPTT using metallic nanoparticles is developed upon a modification of the irradiation therapy using two major changes: using a less harmful visible amber light (excluding blue light) and using gold-loaded biocompatible nanoparticles. Acrylate nanoparticles were loaded with desired types of gold nanoparticles at different sizes. The gold-loaded gold nanoparticles were conjugated to cancer cells. By selectively delivering the gold nanoparticles into cancer cells, irradiating a harmless amber visible light will achieve thermal ablation of the cancer cells. Based on imaging spectroscopy, flow cytometry, and cell viability assays, results showed reduction of gold-loaded viable cancer cells upon irradiating with amber visible light, no change in the number of cancer cells with irradiating with light only. On the other hand, DNA intercalation of a trinuclear gold(I), [Au(3-CH3,5-COOH)Pz]3 (Au3) is contrasted with the standard organic intercalators ethidium and ellipticine, as investigated computationally. Frontier molecular orbital energies of intercalators and DNA base pairs were determined and found that all intercalators are good electron acceptors with Au3 being the best electron acceptor having the lowest LUMO. DNA base pairs are better electron donors having the lowest HOMO values, and from the intercalators and base pairs' HOMO/LUMO energies, it is evident the intercalators will overlap with the HOMO of DNA stabilizing the intercalators. Interaction energies (kcal/mol) were obtained as a function of distance, r (angstroms). Results show that the theoretical treatment SDD-WB97XD outperforms SDD-LSDA in both adenine-thymine (AT) systems with ethidium and Au3 intercalators. In both guanine-cytosine (GC) and AT pairs, the Au3 has the lowest interaction energies among these common intercalators, suggesting a potential intercalating drug. Experimental DNA intercalation studies were attempted and methods of finding intercalation binding constants were established, showing gold complexes have better binding constants to DNA than common intercalators to support the computational results.