by Raymon, Wai-man Chan. / "March 1999." / Thesis (Ph.D.)--Chinese University of Hong Kong, 1999. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / Abstracts in English and Chinese. / by Raymon, Wai-man Chan.

In this dissertation, I report my thesis work on studying surface electron dynamics for intercalated graphene on a metal template using both experimental and theoretical methods. A general description of the research motivation is summarized in the first Chapter. The experimental and theoretical techniques involved in this thesis research are introduced in Chapter 2. In Chapter 3 and Chapter 4, the key findings of this thesis work are reported. These findings concern two novel surface electronic phenomena in oxygen intercalated-graphene on Ir(111) interface. The first phenomenon was the observation of strongly excited image potential states (IPS) in a well-defined quasi-free-standing graphene (QFG) at an oxygen-intercalated Gr/Ir interface. Specifically, the interfaces were synthesized to form Gr/Ir and QFG (Gr/O/Ir) by oxygen intercalation. The syntheses were monitored by low-energy-electron-diffraction (LEED). Our research succeeded in exciting and measuring IPSs on both interfaces by angle-resolved two-photon-photoemission (AR-2PPE) and then the increasing of the IPS binding energy of 0.17 eV following the oxygen intercalation. Finally, our work proposed a theoretical model based on density-functional-theory (DFT) calculations and effective potential models to simulate the surface potential variations in the presence of the intercalated oxygen and its influence on IPSs. The energy shift could be understood by an approximation considering only the out-of-plane chemical and structural modulations. In addition, the results of the model are in strong agreement with the measured IPS band structures. The agreement enables us to attribute the IPS binding energy shift to two potential modulations: a deepened and widened interfacial potential well due to the presence of oxygen intercalants and an increased graphene-Ir interlayer distance. The second phenomenon investigated was a non-dispersive unoccupied band at the Brillouin Zone (BZ) center, which was observed only for Gr/O/Ir but not for Gr/Ir interface. The unoccupied state is approximately 2.6 eV above Fermi energy and was discovered by AR-2PPE. The existence of the non-dispersive band inspired us to undertake a careful examination of the in-plane structural modulation induced by oxygen intercalants. LEED measurements confirm the presence of an in-plane 2$\times$2 periodicity of the intercalated oxygen in QFG. This periodicity can provide periodic perturbation to QFG and can generate the flat unoccupied state due to zone-folding effects from the BZ edge. Angle-resolved photoemission measurements and DFT-based calculations were used to compare the measured Gr/O/Ir states to that of Gr/Ir and O/Ir, providing solid evidence for this zone-folding interpretation. The realization of mixing bands between high symmetry points in BZ by zone-folding in Gr/O/Ir demonstrates a pathway for engineering the graphene electronic structure and its two-photon optical excitation via other ordered intercalants. In addition, a separate but related collaboration work on the phase-transition and electronic-structure evolution in W-doped \ce{MoTe2} is documented in Chapter 5. In this work, I contributed expertise in photoemission to study the critical dopant stoichiometry responsible for the phase transition.

Hydrogen desorption mechanisms on hydrogenated silicon surface such as H/Si(1 00)-1x1, H/Si(l00)-2xl and H/Si(100)-3x1 surfaces have been explored by theoretical calculations with slab models. Similar desorption mechanisms have been identified for three hydrogenated surfaces and the calculated barriers were in agreement with experimental values. More interestingly, a common bridge structure has been identified as an intermediate. Its unique electronic structure is analyzed in detail. The identification of such a structure provides an alternative account for previous experimental results on STM tip-induced desorption. / Metal atom clusters are nanoscale intermediates between metal atoms and the bulk metal. Al13- can be regarded as a cluster model for Al(111) due to its special electronic and geometric structures. The reaction between Al13- and O2 was explored by various DFT methods such as BLYP, PW91, PBE, B3LYP and BHHLYP and post-HF methods such as CCSD and QCISD(T). The calculation results demonstrated that the reaction was exothermic and thermodynamically quite favorable, and the reason for the stability of Al13- towards oxygen exposure was kinetic, due to the presence of a reaction barrier. True to the expectation of Al13- as a molecular model for the Al surface, the identification of this barrier resolved a long standing puzzle in the initial chemisorption of O2 on Al(111): a barrier was identified in experiment but not in any theoretical calculations on the ground state potential surface. / Reactions on solid surfaces play a crucial role in many technologically important areas such as corrosion, adhesion, synthesis of new materials and heterogeneous catalysis. Theoretical studies on chemical reactions at surfaces can provide much useful information to understand and control these chemical processes. The present project is devoted to explore chemical reactions occurred on the aluminum cluster of Al13- and on the Si(100) surface by first principle calculations, using Gaussian 03 and Vienna Ab Initio Simulation Package (VASP). / The Al13-+HX reactions, with HX being either HCl or HI, are explored by first principle calculations and two importance dynamic factors are identified. Firstly, there was a barrier to the dissociative adsorption of FIX on the surface of an Al13- cluster, which involved charge transfer from Al13-. Secondly, the H atom could be bonded to the cluster in multiple ways, similar to the top, bridge and hollow adsorption sites on Al(111) surface. With a large amount of energy (>40 kcal/mol) deposited during the formation of Al13 -HX-, the H atom could easily migrate among these sites, similar to the diffusion of H on metal surfaces. The two dynamic factors were therefore important considerations in the formation and dissociation of Al 13-HX- And moreover, these dynamic factors make Al13- a fascinating model to probe the dynamic aspect of surface reactions, which should be an important consideration in the reactivity of other metal clusters. / Yuan, Qinghong. / "October 2009." / Source: Dissertation Abstracts International, Volume: 72-01, Section: B, page: . / Thesis (Ph.D.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. Ann Arbor, MI : ProQuest Information and Learning Company, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.

Xing, Xiaochen. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references. / Abstract also in Chinese. / Abstract (Chinese) --- p.i / Abstract --- p.iii / Contents --- p.v / Acknowledgement --- p.ix / Chapter Chapter1 --- Introduction and background / Chapter 1.1 --- Overview of Studies in Colloid-Polymer mixture --- p.1 / Chapter 1.2 --- Depletion Force in Colloid-Polymer Mixture --- p.1 / Chapter 1.2.1. --- Depletion Interaction in Monodisperse and Neutral Polymer-Colloid Mixtures: Theory --- p.3 / Chapter 1.2.1.1. --- An Exact Result: the Interaction between Parallel Plates due to Ideal Polymer Chains --- p.3 / Chapter 1.2.1.2. --- Penetrable Hard Sphere (PHS) Approach --- p.4 / Chapter 1.2.2. --- Early Experimental Findings of Depletion Interaction --- p.6 / Chapter 1.3 --- References and Notes --- p.8 / Chapter Chapter2 --- Principle of Total Internal Reflection Microscopy (TIRM) and Instrumentation / Chapter 2.1 --- Introduction of Total Internal Reflection Microscopy (TIRM) --- p.10 / Chapter 2.2 --- The Principle of TIRM Technique --- p.11 / Chapter 2.2.1 --- Total Internal Reflection --- p.11 / Chapter 2.2.2 --- Details on Scattering of the Evanescent Wave --- p.13 / Chapter 2.2.3 --- Data Analysis --- p.16 / Chapter 2.3 --- Instrumentation --- p.20 / Chapter 2.3.1 --- Apparatus --- p.20 / Chapter 2.3.2 --- Optical Tweezer --- p.23 / Chapter 2.3.3 --- Cleaning of the Slide Surface --- p.24 / Chapter 2.3.4 --- A Typical Potential Energy Profile --- p.25 / Chapter 2.4 --- Laser Light Scattering (LLS) --- p.26 / Chapter 2.5 --- Zeta-potential Measurements --- p.27 / Chapter 2.6 --- References and Notes --- p.28 / Chapter Chapter3 --- Depletion Attraction between a Polystyrene Sphere and a Hydrophilic Surface in a Pluronic Aqueous Solution / Chapter 3.1 --- Introduction --- p.30 / Chapter 3.2 --- Experimental Section --- p.34 / Chapter 3.2.1 --- Sample Preparation --- p.34 / Chapter 3.2.2 --- Total Internal Reflection Microscopy --- p.35 / Chapter 3.2.3 --- Laser Light Scattering --- p.36 / Chapter 3.3 --- Results and Discussion --- p.37 / Chapter 3.4 --- Conclusion --- p.48 / Chapter 3.5 --- References and Notes --- p.50 / Chapter Chapter4 --- pH-Controllable Depletion Attraction Induced by Microgel Particles / Chapter 4.1 --- Introduction --- p.53 / Chapter 4.2 --- Experimental Section --- p.54 / Chapter 4.2.1 --- Sample Preparation --- p.54 / Chapter 4.2.2 --- Total Internal Reflection Microscopy --- p.56 / Chapter 4.3 --- Results and Discussion --- p.58 / Chapter 4.4 --- Conclusion --- p.63 / Chapter 4.5 --- References and Notes --- p.64 / Publication List --- p.65

Emulsions are commonly found both in nature and industry. Due to the complex nature of emulsion systems, their interfacial properties and stability are poorly understood, particularly the influence of droplet deformability on the colloid and interfacial behaviour. This study has highlighted the role of emulsion droplet cross-linking (deformability and penetrability) on droplet surface chemistry, droplet colloidal stability and adsorption at the droplet-water interface and provides insight into methods for enhancing the performance of emulsion formulations.

In this thesis, we investigated the surface composition and orientation of both pure room-temperature ionic liquids (Ils) and binary mixtures of the ILs of the type consisting of the 1-alkyl-3-methylimidazolium ([C[subscropt n]mim]���, n=4, 8, and 12) cation coupled with either [PF���]���, [BF���]���, [Cl]���, or [Br]���. The surfaces of the ILs were examined using both direct recoil spectrometry (DRS) and surface tension measurements. With DRS, a spectral signal produced by a recoiled surface atom indicates the existence of a particular molecular or ionic species at the interface. Derived from the signal are the atomic ratios, which are strongly dependent on the surface orientation of the surface species. The DRS findings are complimented with surface tension measurements, and the thermodynamics properties (surface enthalpy and entropy) derived from such measurements are related to the surface composition and orientation. From the experiments on the neat ILs, the surface compositions of the imidazolium-based ILs were determined. Furthermore, the effects of systematic variations of the cation size (the length of the 1-alkyl chain) and anion identity on the surface orientation of the organic cation were also examined. The surfaces of binary mixtures containing ~25 mol % of [C������mim][PF���] or [C������mim][BF���] in [C���mim}[BF���] were also investigated. The DRS and surface tension data of the mixtures were compared to those of the pure components to determine the composition and any changes in the orientations of the cations upon mixing. / Graduation date: 2004

This thesis aimed to give more insight in the dynamics of enzymes at interfaces. The adsorption and mobility of adsorbed proteins can e.g. give a better understanding of structure-function properties of interfacially active enzymes. Studied enzyme was the lipase from Thermomyces lanuginosus (TLL). Adsorption of TLL to surfaces of different hydrophobicity was studied by Dual Polarization Interferometry (DPI), Surface Plasmon Resonance (SPR) and ellipsometry. It was found that TLL had highest affinity and adsorbed to largest adsorbed amount on a hydrophobic, C18 terminated surface. Moreover, activity studies of adsorbed TLL suggested that a larger fraction of the lipases were orientated with the active site facing the surface on hydrophobic surfaces. Mobility of adsorbed enzymes was studied by means of Fluorescence Recovery After Photobleaching (FRAP) with Confocal Laser Scanning Microscopy (CLSM). CLSM was also used as a tool to image the role of TLL in the detergency of lipids from single cotton fibers. The TLL surface mobility was measured on model surfaces of different hydrophobicity. The rate of TLL surface diffusion was strongly dependent on the surface density of lipase, which was explained by sterical hindrance and intermolecular repulsion. The diffusion was both lowest and decreased as a function of time after adsorption on the most hydrophobic surface. This was thought to be due to a larger fraction of adsorbed TLL oriented with the active site towards the hydrophobic surface and that this fraction increased as a function of time. The presence of surfactants affected the TLL mobility on hydrophobic surfaces. The diffusion increased more than tenfold when TLL was coadsorbed with C12E6/LAS above the critical micellar concentration (cmc) of the surfactant. This was thought to be due to a surfactant induced desorption-rebinding mechanism of TLL. Total Internal Reflection Fluorescence Correlation Spectroscopy (TIR-FCS) supported this theory and was implemented as a technique to quantify kinetic processes of protein-surfactant interactions at surfaces. The surface mobility of TLL was higher on a trimyristin substrate surface compared to the model hydrophobic surface. Single particle tracing of lipases could be performed by conjugation of TLL to Quantum Dots (QDs). The microscopic behavior of QD-lipases on trimyristin suggested that the enzyme operated in two different modes on the surface, which gave the trajectories of single lipase molecules a “bead on a string” appearance. / QC 20100818

Phosphate is one of the essential minerals for all living organisms. It has to be supplied to the soil in order for plant growth. In Turkey, most of the soils lack phosphate mineral. Although this can be overcome by the use of phosphate fertilizers, in Turkey there are no phosphate mines being utilized / and this brings about the need to import phosphate rock and phosphate fertilizers. The estimated phosphate rock reserve of Turkey is around 300 million tons, but it cannot be utilized since no economical method of upgrading has been proved to work yet. The aim of this study has been two-fold / to determine the effects of several parameters on the cell flotation of Mardin-Mazidagi phosphate rock and to increase the grade of the product above 30% P2O5 content with a reasonable recovery rate, so that it could be used commercially. Phosphate rock upgrading was made by using flotation in a cell. There are many factors affecting the recovery and grade of the product such as, particle size, pulp pH, collector volume, acid and collector conditioning times and temperature. Phosphate rock samples used contained 14% P2O5, 43% CaCO3 and 1% SiO2 with a CaO/P2O5 ratio of 3.1. Due to the low silica content, one-stage flotation was made. In the experiments, effects of the important parameters were tested at constant pulp density (10% solids by weight). Particle sizes were between 53 m and 150 m, while the pH values were kept between 5,0 - 6,5 using amounts of acid within the range of 6 - 19 kg H3PO4/ton of rock. The collector (mixture of kerosene and oleic acid in 1:3 volumetric ratio) was used in the range of 0,6 ml (0,96 kg collector/ton rock) and 5,4 ml (8,64 kg collector/ton rock). Acid and collector conditioning times were changed between 10-110 s and 10-80 s, respectively. The temperature range was between 15-35 &deg / C. At the end of the parametric studies a grade of 36% P2O5 with a recovery of 93% could be obtained.

No description available.

Cell adhesion to proteins adsorbed onto implanted surfaces is particularly important to host responses in biomedical and tissue engineering applications. Biomaterial surface properties influence the type, quantity and functional presentation (activity) of proteins adsorbed upon contact with physiological fluids, and modulate subsequent cell response. Cell adhesion to extracellular matrix proteins (e.g. fibronectin) is primarily mediated by the integrin family of cell-surface receptors. Integrins not only anchor cells, supporting cell spreading and migration, but also trigger signals that regulate survival, proliferation and differentiation. A fundamental understanding of the adhesive interactions at the biomaterial interface is critical to the rational design of biomaterial surfaces. Using model surfaces of self-assembled monolayers of alkanethiols on gold presenting well-defined surface chemistries (CH3, OH, COOH, NH2), we investigated the effects of surface chemistry on osteoblastic differentiation. We report that surface chemistry effectively modulates fibronectin adsorption, integrin binding, focal adhesion assembly and signaling to direct the osteoblast cellular functions of adhesion strength, gene expression and matrix mineralization. Specifically, surfaces presenting OH and NH2 functionalities provide enhanced functional presentation of adsorbed fibronectin, promoting specificity of integrin binding as well as elevating focal adhesion assembly and signaling. Furthermore, the OH and NH2 surfaces supported elevated levels of osteoblast differentiation as evidenced by osteoblast-specific gene expression and matrix mineralization. These results contribute to the development of design principles for the engineering of surfaces that direct cell adhesion for biomedical and tissue engineering applications. In particular, the understanding provided by this analysis may be useful in the engineering of surface properties for bone tissue repair and regeneration.