Nanophotonics, especially plasmonics is a kind of very active research area, which deals with the interaction behavior between electromagnetic radiation and metallic nanostructures. It has attracted enormous attention over recent decades due to its great potential of ripple effects on electronics, energy, environmental, and medical industries as well as scientific interests. In particular, noble metal nanoparticles exhibit localized surface plasmon resonance (LSPR), which is the collective oscillating excitation of the free electrons on the surface of metal nanoparticles when light is incident on the particle. The LSPR extinction peak is very sensitive to the dielectric environment near the particle surface and can be tailored by the particle's sizes and shapes. These properties allow LSPR-active substrate using plasmonic gold nanoparticles to be a great transducer for biosensing with real-time and label-free measurement. In addition, the plasmonic gold nanoparticles such as gold nanorod and bipyramid are prepared by the seed-mediated and surfactant-directed method based on the cetyltrimethylammonium bromide (CTAB), which has a great influence on the synthesis. In the growth mechanism, it is believed that CTAB interacts with different facet and defects on the growing nanoparticles to produce different rate of gold ion reduction onto the nanoparticles to generate anisotropic growth. Therefore, CTAB layer is greatly interesting because the modification of nanoparticles surface chemistry is essential to biological targeting, film formation, and assembly of complex structures. Surface enhanced Raman spectroscopy (SERS) of gold nanorods in CTAB solution has been used to analyze a surfactant structural transition based on the distance dependent electromagnetic enhancement. As the surfactant concentration in the gold nanorod solution was reduced, a structural transition in the surfactant layer between 2 mM and 5 mM CTAB solution was observed through a sudden increase in the signal from the alkane chains. A structural transition in the CTAB layer that stabilizes gold nanorods was identified by comparing the intensities of different bands within the CTAB molecule. Therefore, the surface manipulation and analysis of the nanostructures and their interface with controlled environment provide important insight into their structural function and interpretation, and many opportunities for biomedical applications.

Colloidal particles are ideal models for studying the behavior of atomic and molecular systems. They resemble their atomic and molecular analogues in that their dynamics are driven by thermal energy and their equilibrium properties are controlled by inter-particle interactions. Based on this analogy, it is reasonable to construct colloidal chains, where each particle represents a repeat unit, as models for polymers. The advantages of this system over molecular systems are its controllable rigidity, contour length and diameter, as well as the convenience to capture its instantaneous shape and position via video microscopy, which are not trivial to realize in molecular systems. By utilizing the dipolar properties of magnetic colloids, a number of groups have assembled semiflexible and rigid colloidal chains by cross-linking magnetic beads under a magnetic field using polymer linkers. Recently, efforts in constructing colloidal chains led even to anisotropic magnetic colloidal chains that mimic the detailed atomic arrangements of polymers. These properties make colloidal chains possible candidates for the classic bead-spring or bead-rod model systems for semiflexible and rigid polymers. In my thesis, I present a method for generating linear colloidal chain structures by linking surface functionalized paramagnetic particles using DNA. First, I investigate the force interactions between individual magnetic particles under different conditions to optimize the resulting chain stability. A systematic study the bending and rotational diffusion dynamics of the chains and their relationship with the DNA linking chemistry is presented. I then demonstrate their use as a ideal model system to study polymer dynamics In addition, a technique to measure short-range repulsive surface forces between these colloids with high precision was developed. Building on these repulsive force studies, a colloidal system to study 2-D phase transitions was created. This thesis provides insights into understanding and engineering the directed-assembly of magnetic colloids with specific surface interactions, as well as using the assemblies as model systems to study molecular level phenomena.

Hemoglobin biosynthesis in erythrocyte precursors involves several steps. The correct ratios and concentrations of normal alpha (α) and beta β) globin proteins must be expressed, apoproteins must be folded correctly, heme must be synthesized and incorporated into these globins, and the resulting α and β subunits must be rapidly and correctly assembled into heterotetramers. These events occur on a large scale in vivo, and dysregulation causes serious clinical disorders such as thalassemia syndromes. Recent work has implicated a conserved erythroid protein known as Alpha-Hemoglobin Stabilizing Protein (AHSP) as a participant in these events. Current evidence suggests that AHSP enhances α subunit stability and diminishes its participation in harmful redox chemistry. There is also evidence that AHSP facilitates one or more early-stage post-translational hemoglobin biosynthetic events. In this work, the rate constants associated with AHSP binding to and dissociation from native ferric and ferrous human α subunits have been determined, along with the binding and dissociation equilibrium constants. Also, several mutant AHSP proteins were used to better define the cis-trans peptidyl-prolyl isomerization events that AHSP is known to undergo, and several naturally occurring human a subunit missense mutants were used to probe AHSP function. Additionally, several post-binding events regarding AHSP:α-subunit interactions were investigated, such as autooxidation, heme uptake, hemin loss, effects on ligand binding, and secondary structure acquisition. Finally, AHSP was co-expressed with α and β subunits in transgenic Escherichia coli as a way of probing the effects of AHSP on hemoglobin production. Collectively, these data support the model that AHSP rapidly binds α subunits, stabilizes them, and then is displaced by β subunits during hemoglobin production.

ix, 99 p. / We characterize the diagonals of four classes of self-adjoint operators on infinite dimensional Hilbert spaces. These results are motivated by the classical Schur-Horn theorem, which characterizes the diagonals of self-adjoint matrices on finite dimensional Hilbert spaces. In Chapters II and III we present some known results. First, we generalize the Schur-Horn theorem to finite rank operators. Next, we state Kadison's theorem, which gives a simple necessary and sufficient condition for a sequence to be the diagonal of a projection. We present a new constructive proof of the sufficiency direction of Kadison's theorem, which is referred to as the Carpenter's Theorem. Our first original Schur-Horn type theorem is presented in Chapter IV. We look at operators with three points in the spectrum and obtain a characterization of the diagonals analogous to Kadison's result. In the final two chapters we investigate a Schur-Horn type problem motivated by a problem in frame theory. In Chapter V we look at the connection between frames and diagonals of locally invertible operators. Finally, in Chapter VI we give a characterization of the diagonals of locally invertible operators, which in turn gives a characterization of the sequences which arise as the norms of frames with specified frame bounds. This dissertation includes previously published co-authored material. / Committee in charge: Marcin Bownik, Chair; N. Christopher Phillips, Member; Yuan Xu, Member; David Levin, Member; Dietrich Belitz, Outside Member

xii, 133 p. : ill. (some col.) / We study entanglement estimation and verification in realistic situations, taking into account experimental imperfections and statistical fluctuations due to finite data. We consider both photonic and spin-1/2 systems. We study how entanglement created with mixed photon wave packets is degraded. We apply statistical analysis to and propose criteria for reliable entanglement verification and estimation. Finally we devote some effort to making quantum state estimation efficient by applying information criteria. This dissertation includes previously published co-authored material. / Committee in charge: Michael G. Raymer, Chair; Steven J. van Enk, Advisor; Stephen Hs,u Member; Jens U. Noeckel, Member; Je rey A. Cina, Outside Member;

xvi, 143 p. : ill. (some col.) / Electron spins form a two-level quantum system in which the remarkable properties of quantum mechanics can be probed and utilized for many applications. By learning to manipulate these spins, it may be possible to construct a completely new form of technology based on the electron spin degree of freedom, known as spintronics. The most ambitious goal of spintronics is the development of quantum computing, in which electron spins are utilized as quantum bits, or qubits, with properties that are not possible with classical bits. Before these ideas can become reality, a system must be found in which spin lifetimes are long enough and in which spins can be completely controlled. Semiconductors are an excellent candidate for electron spin control since they can be integrated into on-chip devices and produced on a scalable level. The focus of this dissertation is on electron spin control in two different semiconductor systems, namely a two-dimensional electron gas in a modulation-doped quantum well and donor-bound electrons in bulk semiconductors. Both systems have been studied extensively for a variety of purposes. However, the ability to manipulate spins has been elusive. In this dissertation, the first experimentally successful demonstration of electron spin control in a two-dimensional electron gas is presented, in which ultrafast optical pulses induce spin rotations via the optical Stark effect. Donor-bound electron spin manipulation in bulk semiconductors is also investigated in this dissertation. Important information was obtained on the limiting factors that serve to prohibit spin control in this system. By taking these new factors into account, it is our hope that full electron spin control can eventually be accomplished in this system. Finally, through the course of investigating electron spin dynamics, a strange nonlinear optical behavior was observed in a bilayer system, which was determined to result from a coupling of optical interactions with tunneling rates between layers. The data suggest that there is a strong interplay between interlayer and intralayer correlations in this system. Investigations into the nature of this interaction were undertaken and are presented in the last part of this dissertation. This dissertation includes previously published and unpublished co-authored material. / Committee in charge: Dr. Daniel Steck, Chair; Dr. Hailin Wang, Advisor; Dr. Jens Nockel, Inside; Dr. John Toner, Inside; Dr. Andrew Marcus, Outside

xvii, 110 p. : ill. (some col.) / Electron spin states in semiconductors feature long coherence lifetimes, which have stimulated intense interest in the use of these spins for applications in spin based electronics and quantum information processing (QIP). A principal requirement for these spins to be viable candidates in QIP is the ability to coherently control the spins on timescales much faster than the decoherence times. The ability to optically control the spin state can meet this requirement. The spin states of electrons exhibit strong radiative coupling to negatively charged exciton (trion) states, and this radiative coupling makes coherent optical control of spin states possible. This dissertation presents experimental demonstration of coherent control of an electron spin ensemble in a two-dimensional electron gas in a CdTe quantum well. We present two complimentary techniques to optically manipulate these electron spins using a Raman transition. The first demonstration is with a single off-resonant ultrafast optical pulse. This ultrafast pulse acts like an effective magnetic field in the propagation direction of the optical pulse. The second experiment utilizes phase-locked Raman resonant pulse pairs to coherently rotate the quantum state, where the relative phase of the pulse pair sets the axis of rotation. The Raman pulse pair acts like a microwave field driving the spin states. This research demonstrates two significant contributions to the field of coherent optical interactions with semiconductors. First, we have advanced the potential use of electron spin ensembles in semiconductors for optics based quantum information processing hardware through our demonstration of coherent spin flips and complete coherent control. Second, we have experimentally realized full coherent control through the use of phase-locked Raman pulse pairs that overcomes inherent limitations of the single-pulse optical rotation technique, which is the current standard technique used in coherent control. This dissertation includes previously published and unpublished co-authored material. / Committee in charge: Dr. Miriam Deutsch, Chairperson; Dr. Hailin Wang, Advisor; Dr. Steven van Enk, Member; Dr. Raghuveer Parthasarathy, Member; Dr. Catherine Page, Outside Member

xiv, 326 p. : ill. (some col.) / Tetra-ortho -substituted aryl naphthalenes (TOANs) are a motif of great importance, being present in biologically active natural products, chiral ligands, and building blocks relevant to materials science. The synthesis of sterically demanding and enantioenriched TOANs continues to be a challenge for current synthetic methods. Herein, we describe the highly effective synthesis of a variety of sterically demanding and enantioenriched TOANs through a rearrangement-based method. Our method utilizes a cyclopropyl carbinol moiety as the key rearrangement precursor. We have demonstrated that carbon-carbon coupling through a simple nucleophilic attack on a cyclopropyl indanone allows for very large aryl substrates to be added and rearranged. We discuss in detail the following: 1) the initial substrate-scope and proof-of-concept studies, 2) our progress in building the most sterically demanding TOANs to date, and 3) the asymmetric synthesis of TOANs through chiral transfer. This dissertation includes previously published and unpublished co-authored material. / Committee in charge: Michael M. Haley, Chairperson; Shih-Yuan Liu, Advisor; Darren W. Johnson, Member; Victoria J. DeRose, Member; Paul J. Wallace, Outside Member

xx, 214 p. : ill. (some col.) / Intramolecular cascading Michael additions have the ability to transform simple, symmetric substrates into densely functionalized compounds containing new ring structures and chiral centers. The Rauhut-Currier (RC) reaction, also known as the vinylogous Morita-Baylis-Hillman reaction, utilizes this type of reactivity by cyclizing tethered, activated alkenes using phosphine or thiolate catalysis. This dissertation describes the expansion of the scope of the RC reaction, the introduction and importance of co-catalysts to cascading Michael additions, the development of the first amine-catalyzed RC reaction, and the transformation of cyclization products into fused, polycyclic aromatic compounds. Chapter I reviews the development and applications of the Rauhut-Currier reaction. Chapter II describes the regioselective synthesis of di-substituted indenes and introduces phenol as a rate- and selectivity-enhancing co-catalyst. Although tertiary amine nucleophiles were found to be inferior to phosphines as cyclization catalysts, chapter III discusses the ability of unhindered primary and secondary amines to undergo a diastereoselective, cascading aza-Michael-Michael addition to yield a wide variety of amino-indanes in the presence of an acid catalyst. Recognizing the importance of protic environments and small nucleophiles, the development of the first amine-catalyzed intramolecular RC is introduced in chapter IV. Chapter V describes the conversion of methyl ketone-substituted indenes to fluorene derivatives via an intramolecular aldol reaction. Chapter VI describes the serendipitous discovery and synthesis of indenopyrylium salts. Chapter VII details the novel production of indenopyridines from di-substituted indenes. Lastly, chapter VIII provides a summary and suggests future directions for this research. This dissertation includes previously published and unpublished co-authored material. / Committee in charge: Shih-Yuan Liu, Chairperson; Kenneth Doxsee, Advisor; David Tyler, Member; Michael Haley, Member; A. Dana Johnston, Outside Member

xvii, 189 p. ： ill. (some col.) / Low-dimensional electronic systems, systems that are restricted to single energy levels in at least one of the three spatial dimensions, have attracted considerable interest in the field of thermoelectric materials. At these scales, the ability to manipulate electronic energy levels offers a great deal of control over a device's thermopower, that is, its ability to generate a voltage due to a thermal gradient. In addition, low-dimensional devices offer increased control over phononic heat flow. Mesoscale geometry can also have a large impact on both electron and phonon dynamics. Effects such as ballistic transport in a two-dimensional electron gas structure can lead to the enhancement or attenuation of electron transmission probabilities in multi-terminal junctions. The first half of this dissertation investigates the transverse thermoelectric properties of a four-terminal ballistic junction containing a central symmetry-breaking scatterer. It is believed that the combined symmetry of the scatterer and junction is the key component to understanding non-linear and thermoelectric transport in these junctions. To this end, experimental investigations on this type of junction were carried out to demonstrate its ability to generate a transverse thermovoltage. To aid in interpreting the results, a multi-terminal scattering-matrix theory was developed that relates the junction's non-linear electronic properties to its thermoelectric properties. The possibility of a transverse thermoelectric device also motivated the first derivation of the transverse thermoelectric efficiency. This second half of this dissertation focuses on heat flow phenomena in InAs/InP heterostructure nanowires. In thermoelectric research, a phononic heat flow between thermal reservoirs is considered parasitic due to its minimal contribution to the electrical output. Recent experiments involving heterostructure nanowires have shown an unexpectedly large heat flow, which is attributed in this dissertation to an interplay between electron-phonon interaction and phononic heat flow. Using finite element modeling, the recent experimental findings have provided a means to probe the electron-phonon interaction in InAs nanowires. In the end, it is found that electron-phonon interaction is an important component in understanding heat flow at the nanoscale. This dissertation includes previously unpublished co-authored material. / Committee in charge: Dr. Richard Taylor， Chair； Dr. Heiner Linke， Advisor； Dr. David Cohen， Member； Dr. John Toner， Member； Dr. David Johnson， Outside Member