<div> As hybrid 2D materials are incorporated into next-generation device designs, it becomes more and more pertinent that methods are being developed which can facilitate large-area structural control of noncovalent monolayers assembled at 2D material interfaces. Noncovalent functionalization is often leveraged to modulate the physical properties of the underlying 2D material without disrupting the extended electronic delocalization networks intrinsic to its basal plane. The bottom-up nanofabrication technique of self-assembly permits sub-10-nm chemical patterning with low operational costs and relatively simple experimental designs.</div><div> The Claridge Group is interested in leveraging the unique chemical orthogonality intrinsic to the cellular membrane as a means of creating sub-10-nm hydrophilic-hydrophobic striped patterns across 2D material interfaces for applications ranging from interfacial wetting to large-area molecular templates to guide heterogeneous nanoparticle assembly. Using Langmuir–Schaefer conversion, standing phases of polymerizable amphiphiles at the air-water interfaces of a Langmuir trough are converted (through rotation) to lying-down phases on 2D material substrates. Using room temperature substrates, transfer of amphiphiles to a lowered substrate results in small domains and incomplete surface coverage.</div><div> Recognizing that heating the substrate during the LS conversion process may lower the energy barriers to molecular reorientation, and promote better molecular domain assembly, we developed a thermally controlled heated transfer stage that can maintain the surface temperature of the substrate throughout the deposition process. We found that heating during transfer results in the assembly of domains with edge lengths routinely an order of magnitude larger than transfer using room temperature substrates that are more stable towards rigorous repeat washing cycles with both polar and nonpolar solvents.</div><div> To promote the effectiveness of the LS conversion technique beyond academic environments for the noncovalent functionalization 2D material substrates for next-generation device designs, we designed and built a thermally controlled rotary stage to address the longstanding scaling demerit of LS conversion. First, we report the development of a flexible HOPG substrate film that can wrap around the perimeter of the heated disk and can be continuously cycled through the Langmuir film. We found that thermally controlled rotary (TCR) LS conversion can achieve nearly complete surface coverage at the slowest translation speed tested (0.14 mm/s). TCR–LS facilitates the assembly of domains nearly 10,000 μm² which were subsequently used as molecular templates to guide the assembly of ultranarrow AuNWs from solution in a non-heated rotary transfer step. Together, these findings provide the foundation for the use of roll-to-roll protocols to leverage LS conversion for noncovalent functionalization of 2D materials. A true roll-to-roll thermally controlled LS conversion system may prove to be advantageous and a cost-efficient process in applications that require large areas of functional surface, or benefit from long-range ordering within the functional film.</div>

Localized structures of the magnetic field strength depression are often observed in the interplanetarymedium, and they are called ‘magnetic holes’ after the original work of Turner et al. 1977. A numberof observations of similar features have been reported, while the mechanisms of their origin have notfully understood yet. The scale size of their structures varies from several to a few thousand of the protongyro radii, and their characteristic orientations of the magnetic field also vary, and therefore differenttypes of the magnetic holes have been suggested. To date, the magnetic holes are classified into Mirrormode and magnetic decreases (Tsurutani et al. 2011). Despite a large number of papers that report theobservational characteristics of the magnetic holes, many identify the feature using only the magneticfield data. This is due to the scale size of the structure at a large speed of the solar wind medium, thespatial resolution of the plasma instruments is often insufficient while the magnetic field instrument canusually obtain the data in high enough time resolution.The Cassini spacecraft orbited Saturn for almost 17 years and obtained a large amount of data in/near theKronian magnetosphere, where the series of the magnetic depletions have been also observed (Smith et al.1980). The Langmuir Probe (LP) onboard Cassini measures the spacecraft potential and, in turn, measuresthe electron density in in-situ in the outer magnetosphere and solar wind region. This measurement hasbeen done using the LP sweep mode which samples the current-voltage curve of the probe every 10 minin the outer magnetosphere. The LP has also been operated in the continuous mode that measures theprobe current at a fixed bias potential every 16 s allowing to calculate the electron density in a smallerscale that is required for the studies magnetic holes. However, there is no general calibration so far inorder to conduct a statistical study in the outer magnetosphere region. The goal of this project is toinvestigate the possibility to use the LP data for the magnetic hole study, calibrate the LP continuousmode to derive the plasma density near the magnetospheric of Saturn, and investigate the scale size of theplasma density structure in the magnetic holes, i. e. plasma β, the field strength and density.The calibration of the continuous data was done by finding a relation between the current at 11 V, whichis a typical bias voltage of continuous mode, and the spacecraft potential obtained by the LP the sweepmode data. Is is expected that the current at 11V is linearly proportional to the floating potential andtherefore can be used to derive the electron density with the potential and density relationship presentedby Morooka et al. 2009. I found that the spacecraft attitude against the sun has a strong effect on therelation, and derived 11V current-floating potential relationship depending on the different spacecraftattitude.Using the LP continuous data calibration above, I investigated the electron density characteristics aroundthe magnetic hold structure, and confirmed that they are generally in anticorrelation relationship. I estim-ated also the plasma β assuming a constant temperature of 100 eV and investigated their characteristicsfor the different types of magnetic holes (linear and rotational holes) both in the magnetosheath and theholes in the solar wind for the year 2011. For the Cassini dataset during 2011, various different shapeand sizes of magnetic hole events have been found. Most (80%) of the MHs appeared within a groupedstructure, while the rest (20%) are found as isolated type holes in the magnetosheath. Among the isolatedMHs, about 30% had "Gaussian shape" and about 40% had a substructure. The scale size for the electrondensity for the isolated holes were on average 50 s in the solar wind, and 75 s (the rotational holes) and120 s (the linear holes) in the magnetosheath. Therefore, I confirmed that the LP can obtain enough datapoints to resolve the magnetic holes structure in the magnetosheath. The Cassini LP data resolution isalso capable to resolve some of the magnetic hole structure in the solar wind.In summary, I confirmed that the Cassini LP continuous data calibrated in this study is capable toinvestigate the different types of magnetic hole structures. Using this calibrated electron data statisticallyfor the large number of Cassini orbit would helpful to further identify the MHs structures in the solar wind and the magnetosheath that can be a key to understand the generation mechanisms of the magneticholes. / Lokaliserade strukturer med låg magnetfältstyrkan ses ofta i interplanetära mediet och de kallas ’mag-netiska hål’ (MH) (Turner et al. 1977). Trots et antal observationer av sådana strukturer har observeratsär deras generationsmekanism ännu förstådd. Storleken av strukturerna varierar från ett fåtal till någratusen protongyroradier och även deras kännetecknande inriktningar i magnetfältet varierar. På grund avdetta har olika typer av MH förslagits. Idag klassificerar man MH som ’mirror mode’ och magnetiskaminskningar (Tsurutani et al. 2011). Många studier har undersökt de magnetiska hålens egenskaper,men tyvärr oftast baserats endast på magnetfältsdata. Detta kan bero på strukturernas storlek vid en storsolvindshastighet, där plasmainstrumenten oftast inte har tillräckligt hög tidsupplösning för mätningar,medan magnetfältsinstrumenten kan oftast tillhandahålla data i hög tidsupplösning.Cassini-rymdfarkosten kretsade runt Saturnus i nästan 17 år och erhöll stora mängder data i och näraSaturnus magnetosfär. Langmuir-sonden (LP) ombord Cassini mäter rymdfarkostens potential ochdärmed mäter den elektrontätheten i rymden. Instrumentet fungerar som en slags väderstation för rym-dplasma och möjliggör mätningen av fundamentala plasmaparametrar såsom elektrontäthet, jontäthet,elektrontemperatur och jonmassa i en tät plasmaområdet av nära Saturnus. I den yttre magnetosfären därden plasmatätheten är låg, kan LP mäta rymdfarkosts potential och plasmatätheten. Mätningen, så kallade’sweep mode’ kan skaffades var 10:e minuter. LP:en mäter också i ’kontinuerlig mode’ som möjligenkan mäta plasmatätheten i mer frekventa men den behöver allmän kalibrering. I detta projekt undersökerjag möjligheten att använda LP kontinuerlig data för att studera MH, skapa kalibraring funktion för’kontinuerlig mode’ för att uppskatta plasmatätheten i Saturnus magnetosfär, och även att undersökastorleken och karaktär av plasmatäthetenstrukturen i MH.Jag undersökte först relationen mellan LP ström vid 11V och rymdfarkostens potential i sweep mode data.De härledda funktionerna användes vidare för att uppskatta densiteten med användning av relationenmellan rymdfarkostens potential och elektrontätheten (Morooka et al. 2009). Jag upptäckte också attden kontinuerlig mode funktionen är olika beroende på LP sensors läge i förhållande till solen ochrymdfarkosten. Hur Cassini är inriktad har en stor effekt på relationen och därför beskriva jag fyra olikarelationer för olika inriktningsregioner. Med den kontinuerlig mode funktionen jag härlett, undersöktejag struktur av magnetiska hålen som har listats av Tomas Karlsson på KTH. År 2011 innehåller MH medmycket olika former och storlekar. Den mest (80%) MH identifierades som grupp och resten (20%) varsom isolerade MH i magnetosheath. Av dessa isolerande hål har ca. 30% en Gauss-form och nästan 40%av MH verkar ha en understruktur. Genom att jämföra magfältdatan med elektrontätheten bekräftadejag den allmänna antikorrelationen mellan magnetfältstyrkan och elektrontätheten i MH-strukturerna.Dessutom hittar jag en ökning av elektron β som beräknas med en temperatur av 100 eV för linjära ochroterade MH i den magnetosheath samt MH i solvinden under 2011. Storleken av de isolerade magnetiskahålen är i genomsnitt 50 s i solvinden, 75 s (roterade magnetiska hål) och 120 s (linjära magnetiska hålen)i magnetosheath:en. Därför kan Cassini LP ha tillräcklig många datapoäng för att upplösa struktur avMH i magnetosheath. I solvinden kan LP upplösa en del av relativt stora MH.Sammanfattningsvis kan LP:s kontinuerlig kalibreringen från detta projekt användas för att analyserade olika strukturerna och storlekar av MH. Med denna kalibrerade plasmatäthet data är det möjligt attidentifiera olika MH karaktär i statistiskt för det stora antalet Cassini data. Det skulle vara en stor hjälpför att förstå genereringsmekanismerna av de magnetiska hålen.

This thesis deals with the synthesis and characterization ofnovel polyhydroxyl surfactants. The first part describes thesynthesis of a number of stereoisomers of a polyhydroxylsurfactant, and the second part concerns surface chemicalcharacterization. A stereodivergent route for preparation of the hydrophilichead group was developed, featuring consecutive stereoselectivedihydroxylations of a diene. This afforded in total fourdifferent polyhydroxyl head groups. These surfactant headgroups were natural and unnatural sugar analogues, and wereused for the coupling with two different hydrophobic tailgroups. Three of these surfactants were used to investigate thechiral discrimination in Langmuir monolayers at an air-waterinterface. The isotherms showed a remarkable difference incompressibility between surfactants of diastereomericrelationship and also a pronounced chiral discriminationbetween racemic and enantiomerically pure surfactants favoringheterochiral discrimination. / <p>NR 20140805</p>

Partitioning of poly(ethyleneglycol) (PEG) molecules in 2-D and 3-D systems is presented as a self-assembly approach for controlling non-specific adsorption of proteins at interfaces. Lateral restructuring of multi-component Langmuir monolayers to accommodate adsorbing proteins was investigated as a model 2-D system. Ferritin adsorption to monolayers containing cationic, nonionic, and PEG bearing phospholipids induced protein sized binding pockets surrounded by PEG rich regions. The number, size, and distribution of protein imprint sites were controlled by the molar ratios, miscibility, and lateral mobility of the lipids. The influence of PEG chain length on the ternary monolayer restructuring and protein distribution was also investigated using DSPE-PEGx (x= 7, 16, 22). Monolayer miscibility analysis demonstrated that longer PEG chains diminished the condensed phase formation for a fixed ratio of lipids. Thus, incorporation of longer PEG chains, intended to diminish protein adsorption outside of the imprint sites of cationic / non-ionic lipids, leads to dramatic changes in monolayer phase behavior and protein distribution in this 2-D system. The assembly of PEG-amphiphiles at elastomer surfaces and subsequent protein adsorption was investigated as a model 3-D system. Polydimethylsiloxane (PDMS) substrates were modified with block copolymers comprised of PEG and PDMS segments by two methods: (1) the block copolymer was mixed with PDMS during polymerization; (2) the block copolymer diffused into solvent swollen PDMS monoliths. Hydrophilic surfaces resulted for both approaches that, for 600 D block copolymer, exhibited up to 85% reduction in fibrinogen adsorption as compared to native PDMS. Higher MW block copolymers (up to 3000 D) resulted in less hydrophilic surfaces and greater protein adsorption, presumably due to diffusion limitations of copolymer in the PDMS monolith. All modified PDMS surfaces were dynamic and restructured when cycled between air and water. PDMS transparency also decreased with increase in block copolymer concentration for both methods, limiting this modification protocol for applications requiring high polymer transparency. The 2-D system presents a bottom-up approach, where adsorbing protein constructs the binding site, while the 3-D system presents a top down approach, where protein-binding elements may be introduced into the PEG-bearing polymer for fabrication of surfaces with controlled protein adsorption.

Langmuir probes are extensively employed to study the plasmas in space and laboratory environments. Successful measurements require a comprehensive modeling of both the plasma environment and the probe conditions in the form of current collection models. In this thesis, the surface morphology implications on the probe current collection are investigated. This problem is applied and solved in the context of a CubeSat regime. The first problem that is investigated is the consequence of surface structural variability on the current measurements. A new model for dealing with non-uniformity of the probe surface structure is developed in this paper. This model is applied to analyze the Langmuir probe data from a sounding rocket mission that was subjected to surface structural non-homogeneities. This model would be particularly useful for CubeSat platforms where elaborate probe design procedures are not feasible. The second problem that is investigated is the surface area implications on Langmuir probe measurements. It has been established that surface area ratio of the spacecraft to that of the probe needs to be sufficiently large to make successful plasma measurements. CubeSats would therefore pose a challenge for employing Langmuir-type instruments to study the space plasma. We inspect the feasibility of making plasma measurements using Langmuir probes subjected to CubeSat area constraints. This analysis is done for a forthcoming Utah State University (USU)/Space Dynamics Lab (SDL) CubeSat mission.

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第18385号 / エネ博第297号 / 新制||エネ||61(附属図書館) / 31243 / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 水内 亨, 教授 前川 孝, 教授 佐野 史道 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第19193号 / 農博第2132号 / 新制||農||1034(附属図書館) / 学位論文||H27||N4939(農学部図書室) / 32185 / 京都大学大学院農学研究科森林科学専攻 / (主査)教授 髙野 俊幸, 教授 西尾 嘉之, 教授 木村 恒久 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DGAM

The plasma environment of an active comet provides a unique setting for plasma physics research. The complex interaction of newly created cometary ions with the flowing plasma of the solar wind gives rise to a plethora of plasma physics phenomena, that can be studied over a large range of activity levels as the distance to the sun, and hence the influx of solar energy, varies. In this thesis, we have used measurements of the spacecraft potential by the Rosetta Langmuir probe instrument (LAP) to study the evolution of activity of comet 67P/Churyumov-Gerasimenko as it approached the sun from 3.6 AU in August 2014 to 2.1 AU in March 2015. The measurements are validated by cross-calibration to a fully independent measurement by an electrostatic analyzer, the Ion Composition Analyzer (ICA), also on board Rosetta. The spacecraft was found to be predominantly negatively charged during the time covered by our investigation, driven so by a rather high electron temperature of ~5 eV resulting from the low collision rate between electrons and the tenuous neutral gas. The spacecraft potential exhibited a clear covariation with the neutral density as measured by the ROSINA Comet Pressure Sensor (COPS) on board Rosetta. As the spacecraft potential depends on plasma density and electron temperature, this shows that the neutral gas and the plasma are closely coupled. The neutral density and negative spacecraft potential were higher in the northern hemisphere, which experienced summer conditions during the investigated period due to the nucleus spin axis being tilted toward the sun. In this hemisphere, we found a clear variation of spacecraft potential with comet longitude, exactly as seen for the neutral gas, with coincident peaks in neutral density and spacecraft potential magnitude roughly every 6 h, when sunlit parts of the neck region of the bi- lobed nucleus were in view of the spacecraft. The plasma density was estimated to have increased during the investigated time period by a factor of 8-12 in the northern hemisphere and possibly as much as a factor of 20-44 in the southern hemisphere, due to the combined effects of seasonal changes and decreasing heliocentric distance. The spacecraft potential measurements obtained by LAP generally exhibited good correlation with the estimates from ICA, confirming the accuracy of both of these instruments for measurements of the spacecraft potential. / <p>QC 20200602</p>

Botulinum Neurotoxin (BoNT) is one of the most potent toxins known to human kind. The Atomic Force Microscope (AFM) was employed to investigate the conditions under which BoNT type A heavy chain would bind and/or insert into mica supported dipalmitoylphosphatidylcholine (DPPC) lipid bilayers. As an alternate technique, DPPC/GT1b or total ganglioside extract (80:20) monolayers of a Langmuir Blodgett (LB) Trough were adapted to be artificial membrane models for toxin insertion studies. We conclude that LB monolayer studies are a promising candidate for BoNT/A membrane insertion investigation. Botulinum neurotoxin serotype A insertions into the LB monolayers in the presence of BoNT/A low affinity ganglioside receptor alone, independent of pH. This thermodynamic evidence indicates that BoNT/A may begin its heavy chain insertion into the cholinergic nerve ending before endocytosis and acidification.

No description available.