Aqueous industrial effluents containing organic pollutants, such as textile dyes and crude oil, represent environmental and human health concerns due to their toxicity and possible carcinogenic effects. Adsorption is the most promising wastewater treatment method due to its efficiency, ease of operation, and low cost. However, currently used adsorbents have either high regeneration costs or low adsorption capacities. In this work, new organic/inorganic hybrids based on hollow silica microspheres were successfully synthesized, and their ability to remove Methylene Blue from wastewater and crude oil from simulated produced water was evaluated. By employing four different silanes, namely triethoxy (octyl) silane, triethoxy (dodecyl) silane, trichloro (octadecyl) silane, and triethoxy (pentafluorophenyl) silane, hydro and fluorocarbons were grafted onto the surface of commercially available silica microspheres. These silica derivatives were tested as adsorbents by exposing them to Methylene Blue aqueous solutions and synthetic produced water. Absorbance and oil concentration were measured via a UV/Vis Spectrophotometer and an HD-1000 Oil-in-Water Analyzer respectively. Methylene Blue uptake experiments showed that increasing the adsorbent dosage and decreasing initial dye concentration might increase adsorption percentage. On the other hand, adsorption capacities were improved with lower adsorbent dosages and higher initial dye concentrations. Varying the initial solution pH, from pH 5 to pH 9, and increasing ionic strength did not seem to have a significant impact on the extent of adsorption of Methylene Blue. Overall, the silica derivative containing aromatic functional groups, Caro, was proven to be the most effective adsorbent due to the presence of π-π and cation-π interactions in addition to the van der Waals and hydrophobic interactions occurring with all four adsorbents. Although the Langmuir Model did not accurately represent the equilibrium data, it produced consistent maximum adsorption values and adsorption equilibrium constants. Preliminary experiments demonstrated the potential to recover and reuse the silica microspheres by washing with NaOH and organic solvents. The preferential adsorption of oil micro-droplets onto the surface of functionalized hollow silica microspheres was evidenced. However, preparing synthetic produced water that was stable enough to carry out kinetics experiments remained a challenge.

xi, 125 p. : ill. (some col.) A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / This dissertation presents experimental and theoretical studies of radiation pressure cooling in silica optomechanical microresonators where whispering gallery modes (WGMs) are coupled to thermal mechanical vibrations. In an optomechanical system, circulating optical fields couple to mechanical vibrations via radiation pressure, inducing Stokes and anti-Stokes scattering of photons. In analogy to laser cooling of trapped ions, the mechanical motion can in principle be cooled to its ground state via the anti-Stokes process in the resolved-sideband limit, in which the cavity photon lifetime far exceeds the mechanical oscillation period. Our optomechanical system is a slightly deformed silica microsphere (with a diameter 25-30 μm ), featuring extremely high Q -factors for both optical ( Q o ∼ 10 8 ) and mechanical ( Q m ∼ 10 4 ) systems. Exploiting the unique property of directional evanescent escape in the deformed resonator, we have developed a free-space configuration for the excitation of WGMs and for the interferometric detection of mechanical displacement, for which the part of input laser that is not coupled into the microsphere serves as a local oscillator. Measurement sensitivity better than 5 × 10 -18 m /[Special characters omitted.] has been achieved. The three optically active mechanical modes observed in the displacement power spectrum are well described by finite element analysis. Both radiation pressure cooling and parametric instabilities have been observed in our experiments. The dependence of the mechanical resonator frequency and linewidth on the detuning as well as the intensity of the input laser show excellent agreement with theoretical calculations with no adjustable parameters. The free-space excitation technique has enabled us to combine resolved sideband cooling with cryogenic cooling. At a cryogenic temperature of 1.4 K, the sideband cooling leads to an effective temperature as low as 210 m K for a 110 MHz mechanical oscillator, corresponding to an average phonon occupation of 37, which is one of the three lowest phonon occupations achieved thus far for optomechanical systems. The cooling process is limited by ultrasonic attenuation in fused silica, which should diminish when bath temperature is further lowered, with a 3 He cryostat, to a few hundred millikelvin. Our experimental studies thus indicate that we are tantalizingly close to realizing the ground-state cooling for the exploration of quantum effects in an otherwise macroscopic mechanical system. / Committee in charge: Michael Raymer, Chairperson, Physics; Jens Noeckel, Member, Physics; Hailin Wang, Member, Physics; Paul Csonka, Member, Physics; Jeffrey Cina, Outside Member, Chemistry

xii, 138 p. : ill. (some col.) A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / Controlling colloidal interactions continues to receive a great deal of attention due both to basic scientific interests as well as industrial applications. However, many aspects of interactions between microparticles remain poorly understood, including the attraction observed between particles with the same kind of charge (like-charge attraction). This situation hinders progress in the generation of colloidal self-assembled structures. This thesis focuses on measurements of pair interactions of functionalized silica microspheres and the resulting insights into colloidal interactions. Silica microparticles were functionalized in two ways. For one method, each particle was coated with a lipid inlayer membrane. The charge density of the particle surface can thereby be easily tuned by controlling the type or amount of charged lipids. For the other method, the cholera toxin subunit B protein (CTB) was bound to lipid-functionalized microparticles. To measure pair interactions, we invented a line optical trap that enables nearly free one-dimensional Brownian motion of particles. Pair interaction energies of functionalized particles above the bottom of the experimental chamber can be extracted via a Boltzmann relationship. Both lipid-only and lipid-plus-protein functionalized microparticles show tunable, attractive pair interactions. For lipid-only coatings, the attraction becomes stronger by increasing the fraction of positively charged lipids. There is a linear relationship between pair potential and molar percentage of positively charged lipids. For lipid-plus-protein coatings, attractive potentials were weakened monotonically by binding more CTB. Decompositions of potential curves allow identification of directly charge-dependent and charge-independent contributions to colloidal like-charge attraction. Analysis shows that the correlations between attraction strength and range are opposite in these two sets of particles. Moreover, the correlations between particle-wall separation and attraction strength in lipid-only and lipid-plus-protein functionalized particles are also opposite. These comparisons show that like-charge attraction may result from more than one mechanism. Finally, we measured pair potential energies of lipid functionalized silica particles above a lipid functionalized glass chamber bottom, which exhibit a quadratic relationship between the attraction strength and the fraction of positively charged lipids. Compared with the situation of particle functionalization only, this relation indicates that confinement-induced like-charge attraction can be modulated by altering electrostatic properties of the confining wall. / Committee in charge: Dr. Stephen D. Kevan, Chair; Dr. Raghuveer Parthasarathy, Advisor; Dr. Hailin Wang; Dr. Miriam Deutsch; Dr. Marina G. Guenza

L’Annexine A5 (AnxA5) est une protéine soluble se liant aux membranes contenant de la phosphatidylsérine (PS) en présence de calcium (Ca2+). Le rôle central joué par l’AnxA5 dans les processus de réparation membranaire a été récemment mis en évidence. L’AnxA5 possède une très forte affinité pour les membranes biologiques contenant de la PS, cependant son mode de liaison aux membranes n’est pas encore élucidé.La première partie de mon travail de thèse a concerné le développement d’une approche originale d’étude de la liaison de l’AnxA5 à des microsphères de silice fonctionnalisées par une bicouche lipidique (µPSiO2@SLB pour supported lipid bilayer), par cytométrie en flux (FCM). Cette approche m’a permis d’étudier la liaison à l’équilibre et en cinétique à très faible concentration en AnxA5, de l’ordre du picomolaire. Cette approche représente une des méthodes les plus sensibles d’étude de liaison à l’équilibre et la première permettant d’accéder aux constantes cinétiques d’interaction pour l’AnxA5. Cette étude m’a également permis de mettre au point une stratégie de dosage indirect de liposomes contenant de la PS avec une sensibilité de l’ordre du nanogramme de lipides par millilitre.La seconde partie de ma thèse a concerné l’étude de microparticules (MP), fragments de membranes cellulaires présents dans les fluides biologiques. Dans le plasma sanguin la majorité des MP sont d’origine plaquettaire et exposent de la PS. Il existe une corrélation entre la concentration en MP plasmatiques exposant de la PS et le développement de pathologies thrombotiques. La FCM est la méthode de référence dans l’étude des MP cependant leur détection est rendue difficile par leur petite taille. J’ai appliqué aux MP plasmatiques le test de dosage développé pour les liposomes. Les résultats obtenus sont prometteurs et permettent d’envisager le développement d’un test de dosage de l’ensemble des MP exposant de la PS. / Annexin-A5 (AnxA5) is a soluble membrane binding protein that binds to phosphatidylserine (PS) containing membranes in a calcium dependent manner and plays a central role in cell membrane repair processes. AnxA5 has a remarkably high affinity for PS containing membranes, but its binding mechanism remains unclear.The first part of my PhD work was to develop a new method for studying AnxA5 binding using supported lipid bilayer functionalized silica microspheres (µPSiO2@SLB) and Flow Cytometry (FCM). This approach allowed me to describe in details both equilibrium and kinetics of AnxA5 binding at picomolar concentrations in AnxA5. This study is one of the most sensitive for equilibrium binding studies and the first allowing to measure binding kinetics constants for AnxA5. This study also led to the development of a new strategy for determination of liposome concentration with sensitivity in the range of one nanogram of lipid per milliliter. The second part of my work focused on microparticles (MP) that are cell membrane fragments found in biological fluids. In plasma, the vast majority of MP originates from platelets and expresses PS at their surface. There is a correlation between MP concentration in plasma and thrombotic risk. FCM is the “golden standard” of hæmatologic analysis but the majority of MPs are too small to be detected. I have applied the test developed with liposomes for the quantification of MP. The results are promising and allow foreseeing the development of a test able to give the absolute quantity of PS exposing MPs in plasma samples.