Chelation-enforced metal-arene interactions : insights into substrate binding and catalysis by late transition metal complexes

Understanding and catalyzing chemical reactions requiring multiple electron transfers is an endeavor relevant to many outstanding challenges in the field of chemistry. To study multi-electron reactions, a terphenyl diphosphine framework was designed to support one or more metals in multiple redox states via stabilizing interactions with the central arene of the terphenyl backbone. A variety of unusual compounds and reactions and their relevance toward prominent research efforts in chemistry are the subject of this dissertation.

Chapter 2 introduces the para-terphenyl diphosphine framework and its coordination chemistry with group 10 transition metal centers. Both mononuclear and dinuclear compounds are characterized. In many cases, the metal center(s) are stabilized by the terphenyl central arene. These metal–arene interactions are characterized both statically, in the solid state, and fluxionally, in solution. As a proof-of-principle, a dinickel framework is shown to span multiple redox states, showing that multielectron chemistry can be supported by the coordinatively flexible terphenyl diphosphine.

Chapter 3 presents reactivity of the terphenyl diphosphine when bound to a metal center. Because of the dearomatizing effect of the metal center, the central arene of the ligand is susceptible to reactions that do not normally affect arenes. In particular, Ni-to-arene H-transfer and arene dihydrogenation reactions are presented. Additionally, evidence for reversibility of the Ni-to-arene H-transfer is discussed.

Chapter 4 expands beyond the chelated metal-arene interactions of the previous chapters. A dipalladium(I) terphenyl diphosphine framework is used to bind a variety of exogenous organic ligands including arenes, dienes, heteroarenes, thioethers, and anionic ligands. The compounds are structurally characterized, and many ligands exhibit unprecedented bindng modes across two metal centers. The relative binding affinities are evaluated spectroscopically, and equilibrium binding constants for the examined ligands are determined to span over 13 orders of magnitude. As an application of this framework, mild hydrogenation conditions of bound thiophene are presented.

Chapter 5 studies nickel-mediated C–O bond cleavage of aryl alkyl ethers, a transformation with emerging applications in fields such as lignin biofuels and organic methodology. Other group members have shown the mechanism of C–O bond cleavage of an aryl methyl ether incorporated into a meta-terphenyl diphosphine framework to proceed through β-H elimination of an alkoxide. First, the electronic selectivity of the model system is examined computationally and compared with catalytic systems. The lessons learned from the model system are then applied to isotopic labeling studies for catalytic aryl alkyl ether cleavage under dihydrogen. Results from selective deuteration experiments and mass spectrometry draw a clear analogy between the mechanisms of the model and catalytic systems that does not require dihydrogen for C–O bond cleavage, although dihydrogen is proposed to play a role in catalyst activation and catalytic turnover.

Appendix A presents initial efforts toward heterodinuclear complexes as models for CO dehydrogenase and Fischer Tropsch chemistry. A catechol-incorporating terphenyl diphosphine is reported, and metal complexes thereof are discussed.

Appendix B highlights some structurally characterized terphenyl diphosphine complexes that either do not thematically belong in the research chapters or proved to be difficult to reproduce. These compounds show unusual coordination modes of the terphenyl diphosphine from which other researchers may glean insights.

Gamma-ray induced color centers in Yb : YAG crystals grown by Czochralski method

20 at.% Yb:YAG single crystals have been grown by the CZ method and gamma-ray irradiation induced color centers and valence change of Fe3+ and Yb3+ ions in Yb:YAG have been studied. One significant 255 nm absorption band was observed in as-grown crystals and was attributed to Fe3+ ions. Two additional absorption (AA) bands located at 255 nm and 345 nm, respectively, were produced after gamma irradiation. The changes in the AA spectra after gamma irradiation and air annealing are mainly related to the charge exchange of the Fe3+, Fe2+, oxygen vacancies and F-type color centers. Analysis shows that the broad AA band is associated with Fe2+ ions and F-type color centers. The transition Yb3+ Yb2+ takes place as an effect of recharging of one of the Yb3+ ions from a pair in the process of gamma irradiation. (C) 2006 Elsevier Ltd. All rights reserved.

Effects of Carbon Dioxide Capture and Storage in Germany on European Electricity Exchange and Welfare

28 p.

Evaluation of Two Alternative Carbon Capture and Storage Technologies: A Stochastic Model

30 p.

An integrated design approach to power systems : from power flows to electricity markets

Power system is at the brink of change. Engineering needs, economic forces and environmental factors are the main drivers of this change. The vision is to build a smart electrical grid and a smarter market mechanism around it to fulfill mandates on clean energy. Looking at engineering and economic issues in isolation is no longer an option today; it needs an integrated design approach. In this thesis, I shall revisit some of the classical questions on the engineering operation of power systems that deals with the nonconvexity of power flow equations. Then I shall explore some issues of the interaction of these power flow equations on the electricity markets to address the fundamental issue of market power in a deregulated market environment. Finally, motivated by the emergence of new storage technologies, I present an interesting result on the investment decision problem of placing storage over a power network. The goal of this study is to demonstrate that modern optimization and game theory can provide unique insights into this complex system. Some of the ideas carry over to applications beyond power systems.

Effect of pressure on mechanical behavior of filled elastomers

The Young's modulus, stress-strain curves, and failure properties of glass bead-filled EPDM vulcanizates were studied under superposed hydrostatic pressure. The glass bead-filled EPDM was employed as a representation of composite systems, and the hydrostatic pressure controls the filler-elastomer separation under deformation. This separation shows up as a volume change of the system, and its infuence is reflected in the mechanical behavior as a reinforcing effect of variable degree.

The strain energy stored in the composite system in simple tension was calculated by introducing a model which is described as a cylindrical block of elastomer with two half spheres of filler on each end with their centers on the axis of the cylinder. In the derivation of the strain energy, assumptions were made to obtain the strain distribution in the model, and strain energy-strain relation for the elastomer was also assumed. The derivation was carried out for the case of no filler-elastomer separation and was modified to include the case of filler-elastomer separation.

The resulting strain energy, as a function of stretch ratio and volume of the system, was used to obtain stress-strain curves and volume change-strain curves of composite systems under superposed hydrostatic pressure.

Changes in the force and the lateral dimension of a ring specimen were measured as it was stretched axially under a superposed hydrostatic pressure in order to calculate the mechanical properties mentioned above. A tensile tester was used which is capable of sealing the whole system to carry out a measurement under pressure. A thickness measuring device, based on the Hall effect, was built for the measurement of changes in the lateral dimension of a specimen.

The theoretical and experimental results of Young's modulus and stress-strain curves were compared and showed fairly good agreement.

The failure data were discussed in terms of failure surfaces, and it was concluded that a failure surface of the glass-bead-filled EPDM consists of two cones.

Electron tunneling in proteins and water

The subject of this thesis is electronic coupling in donor-bridge-acceptor systems. In Chapter 2, ET properties of cyanide-bridged dinuclear ruthenium complexes were investigated. The strong interaction between the mixed-valent ruthenium centers leads to intense metal-to-metal charge transfer bands (MMCT). Hush analysis of the MMCT absorption bands yields the electronic-coupling strength between the metal centers (H_(AB)) and the total reorganization energy (λ). Comparison of ET kinetics to calculated rates shows that classical ET models fail to account for the observed kinetics and nuclear tunneling must be considered.

In Chapter 3, ET rates were measured in four ruthenium-modified highpotential iron-sulfur proteins (HiPIP), which were modified at position His50, His81, His42 and His18, respectively. ET kinetics for the His50 and His81 mutants are a factor of 300 different, while the donor-acceptor separation is nearly identical. PATHWAY calculations corroborate these measurements and highlight the importance of structural detail of the intervening protein matrix.

In Chapter 4, the distance dependence of ET through water bridges was measured. Photoinduced ET measurements in aqueous glasses at 77 K show that water is a poor medium for ET. Luminescence decay and quantum yield data were analyzed in the context of a quenching model that accounts for the exponential distance dependence of ET, the distance distribution of donors and acceptors embedded in the glass and the excluded volumes generated by the finite sizes of the donors and acceptors.

In Chapter 5, the pH-dependent excited state dynamics of ruthenium-modified amino acids were measured. The [Ru(bpy)_(3)] ^(2+) chromophore was linked to amino acids via an amide linkage. Protonation of the amide oxygen effectively quenches the excited state. In addition. time-resolved and steady-state luminescence data reveal that nonradiative rates are very sensitive to the protonation state and the structure of the amino acid moiety.

Measurement of the galactic cosmic ray antiproton flux from 0.25 gev to 3.11 gev with the isotope matter antimatter experiment (imax)

The intensities and relative abundances of galactic cosmic ray protons and antiprotons have been measured with the Isotope Matter Antimatter Experiment (IMAX), a balloon-borne magnet spectrometer. The IMAX payload had a successful flight from Lynn Lake, Manitoba, Canada on July 16, 1992. Particles detected by IMAX were identified by mass and charge via the Cherenkov-Rigidity and TOP-Rigidity techniques, with measured rms mass resolution ≤0.2 amu for Z=1 particles.

Cosmic ray antiprotons are of interest because they can be produced by the interactions of high energy protons and heavier nuclei with the interstellar medium as well as by more exotic sources. Previous cosmic ray antiproton experiments have reported an excess of antiprotons over that expected solely from cosmic ray interactions.

Analysis of the flight data has yielded 124405 protons and 3 antiprotons in the energy range 0.19-0.97 GeV at the instrument, 140617 protons and 8 antiprotons in the energy range 0.97-2.58 GeV, and 22524 protons and 5 antiprotons in the energy range 2.58-3.08 GeV. These measurements are a statistical improvement over previous antiproton measurements, and they demonstrate improved separation of antiprotons from the more abundant fluxes of protons, electrons, and other cosmic ray species.

When these results are corrected for instrumental and atmospheric background and losses, the ratios at the top of the atmosphere are p/p=3.21(+3.49, -1.97)x10^(-5) in the energy range 0.25-1.00 GeV, p/p=5.38(+3.48, -2.45) x10^(-5) in the energy range 1.00-2.61 GeV, and p/p=2.05(+1.79, -1.15) x10^(-4) in the energy range 2.61-3.11 GeV. The corresponding antiproton intensities, also corrected to the top of the atmosphere, are 2.3(+2.5, -1.4) x10^(-2) (m^2 s sr GeV)^(-1), 2.1(+1.4, -1.0) x10^(-2) (m^2 s sr GeV)^(-1), and 4.3(+3.7, -2.4) x10^(-2) (m^2 s sr GeV)^(-1) for the same energy ranges.

The IMAX antiproton fluxes and antiproton/proton ratios are compared with recent Standard Leaky Box Model (SLBM) calculations of the cosmic ray antiproton abundance. According to this model, cosmic ray antiprotons are secondary cosmic rays arising solely from the interaction of high energy cosmic rays with the interstellar medium. The effects of solar modulation of protons and antiprotons are also calculated, showing that the antiproton/proton ratio can vary by as much as an order of magnitude over the solar cycle. When solar modulation is taken into account, the IMAX antiproton measurements are found to be consistent with the most recent calculations of the SLBM. No evidence is found in the IMAX data for excess antiprotons arising from the decay of galactic dark matter, which had been suggested as an interpretation of earlier measurements. Furthermore, the consistency of the current results with the SLBM calculations suggests that the mean antiproton lifetime is at least as large as the cosmic ray storage time in the galaxy (~10^7 yr, based on measurements of cosmic ray ^(10)Be). Recent measurements by two other experiments are consistent with this interpretation of the IMAX antiproton results.

Dendrites Inhibition in Rechargeable Lithium Metal Batteries

The specific high energy and power capacities of rechargeable lithium metal (Li⁰) batteries are ideally suited to portable devices and are valuable as storage units for intermittent renewable energy sources. Lithium, the lightest and most electropositive metal, would be the optimal anode material for rechargeable batteries if it were not for the fact that such devices fail unexpectedly by short-circuiting via the dendrites that grow across electrodes upon recharging. This phenomenon poses a major safety issue because it triggers a series of adverse events that start with overheating, potentially followed by the thermal decomposition and ultimately the ignition of the organic solvents used in such devices.

In this thesis, we developed experimental platform for monitoring and quantifying the dendrite populations grown in a Li battery prototype upon charging under various conditions. We explored the effects of pulse charging in the kHz range and temperature on dendrite growth, and also on loss capacity into detached “dead” lithium particles.

Simultaneously, we developed a computational framework for understanding the dynamics of dendrite propagation. The coarse-grained Monte Carlo model assisted us in the interpretation of pulsing experiments, whereas MD calculations provided insights into the mechanism of dendrites thermal relaxation. We also developed a computational framework for measuring the dead lithium crystals from the experimental images.

Phase shift caused by microwave field based on light storage

We have theoretically investigated the phase shift of a probe field for a four-level atomic system interacting successively with two fields tuned near an EIT resonance of an atom, a microwave field, and a coupling field. It has been found that the phase of retrieved signal has been shifted due to the cross-phase modulation when the stored spin wave was disturbed by a microwave. Because of the low relaxation rates of the ground hyperfine state, our proposed technique can impart a large phase rotation onto the probe field with low absorption of retrieved field and very low intensity of the microwave field.

A measurement of B0-B0 mixing in e+e- annihilation at 29 GeV

This thesis describes a measurement of B⁰- B⁰ mixing in events produced by electron-positron annihilation at a center of mass energy of 29 GeV. The data were taken by the Mark II detector in the PEP storage ring at the Stanford Linear Accelerator Center between 1981 and 1987, and correspond to a total integrated luminosity of 224pb^-1.

We used a new method, based on the kinematics of hadronic events containing two leptons, to provide a measurement of the probability, x, that a hadron, initially containing a b (b) quark decays to a positive (negative) lepton to be X = 0.17^+0.15_-0.08, with 90% confidence level upper and lower limits of 0.38 and 0.06, respectively, including all estimated systematic errors. Because of the good separation of signal and background, this result is relatively insensitive to various systematic effects which have complicated previous measurements.

We interpret this result as evidence for the mixing of neutral B mesons. Based on existing B⁰_d mixing rate measurements, and some assumptions about the fractions of B⁰_d and B⁰_s mesons present in the data, this result favors maximal mixing of B⁰_s mesons, although it cannot rule out zero B⁰_s mixing at the 90% confidence level.

Rewriting Schemes for Flash Memory

Flash memory is a leading storage media with excellent features such as random access and high storage density. However, it also faces significant reliability and endurance challenges. In flash memory, the charge level in the cells can be easily increased, but removing charge requires an expensive erasure operation. In this thesis we study rewriting schemes that enable the data stored in a set of cells to be rewritten by only increasing the charge level in the cells. We consider two types of modulation scheme; a convectional modulation based on the absolute levels of the cells, and a recently-proposed scheme based on the relative cell levels, called rank modulation. The contributions of this thesis to the study of rewriting schemes for rank modulation include the following: we

•propose a new method of rewriting in rank modulation, beyond the previously proposed method of “push-to-the-top”;

•study the limits of rewriting with the newly proposed method, and derive a tight upper bound of 1 bit per cell;

•extend the rank-modulation scheme to support rankings with repetitions, in order to improve the storage density;

•derive a tight upper bound of 2 bits per cell for rewriting in rank modulation with repetitions;

•construct an efficient rewriting scheme that asymptotically approaches the upper bound of 2 bit per cell.

The next part of this thesis studies rewriting schemes for a conventional absolute-levels modulation. The considered model is called “write-once memory” (WOM). We focus on WOM schemes that achieve the capacity of the model. In recent years several capacity-achieving WOM schemes were proposed, based on polar codes and randomness extractors. The contributions of this thesis to the study of WOM scheme include the following: we

•propose a new capacity-achievingWOM scheme based on sparse-graph codes, and show its attractive properties for practical implementation;

•improve the design of polarWOMschemes to remove the reliance on shared randomness and include an error-correction capability.

The last part of the thesis studies the local rank-modulation (LRM) scheme, in which a sliding window going over a sequence of real-valued variables induces a sequence of permutations. The LRM scheme is used to simulate a single conventional multi-level flash cell. The simulated cell is realized by a Gray code traversing all the relative-value states where, physically, the transition between two adjacent states in the Gray code is achieved by using a single “push-to-the-top” operation. The main results of the last part of the thesis are two constructions of Gray codes with asymptotically-optimal rate.

The Mechanical Genome in Regulation and Infection

Biological information storage and retrieval is a dynamic process that requires the genome to undergo dramatic structural rearrangements. Recent advances in single-molecule techniques have allowed precise quantification of the nano-mechanical properties of DNA [1, 2], and direct in vivo observation of molecules in action [3]. In this work, we will examine elasticity in protein-mediated DNA looping, whose structural rearrangement is essential for transcriptional regulation in both prokaryotes and eukaryotes. We will look at hydrodynamics in the process of viral DNA ejection, which mediates information transfer and exchange and has prominent implications in evolution. As in the case of Kepler's laws of planetary motion leading to Newton's gravitational theory, and the allometric scaling laws in biology revealing the organizing principles of complex networks [4], experimental data collapse in these biological phenomena has guided much of our studies and urged us to find the underlying physical principles.

Sistemas fotovoltaicos integrados ao perfil de uso da edificação

Nos últimos anos, o consumo de energia vem crescendo mundialmente nos grandes centros urbanos, e esforços na área de eficiência energética estão sendo implantados, a fim de reduzir o consumo no horário da ponta e interrupções da rede. O aproveitamento das fontes renováveis, como o fotovoltaico em uma edificação se torna um atrativo a mais para a matriz energética num momento em que o país prima pela universalização dos serviços de energia e a classificação de edifícios comerciais, de serviço e públicos, além dos residenciais quanto à eficiência energética através do Procel Edifica (RTQ-C e RTQ-R). Os sistemas fotovoltaicos podem configurar perfis de uso nas edificações de modo a gerar energia para consumo próprio ou ligado à rede e ainda ter influência na arquitetura do prédio com revestimento: os perfis podem está em telhados, fachadas ou janelas, amenizando em alguns casos a carga térmica no prédio com sombreamento arquitetônico. Hoje, com o avanço da tecnologia no setor de armazenagem é possível, o atendimento com segurança e eficiência a uma edificação ou direcionar esta armazenagem a uma demanda específica como o atendimento à demanda de ciclo profundo, tais como, iluminação externa e recarga de veículos elétricos. Partindo da premissa de sistemas interruptos de energia, UPS, uso de fonte secundária como FV, baterias e Flywheel é apresentado uma forma de melhor gerenciar a energia armazenada, podendo estender a vida útil da bateria e conseqüentemente de todo o sistema fotovoltaico na edificação. Esta forma de armazenar energia proporciona um serviço de uso contínuo sem percepção das interrupções da rede com garantia de 20 anos, tal qual o módulo fotovoltaico, com esta proposta as perdas de energia elétrica na edificação serão atenuadas, pois a eletricidade será utilizada de forma eficiente e inteligente. O ponto de partida do estudo de caso no prédio do IBAM são os sistemas fotovoltaicos com geração distribuída (mini-redes) conectados à rede que são instalados para fornecer energia ao consumidor, complementando a quantidade de energia demandada, caso haja algum aumento do consumo de energia na edificação, ou ainda utilizar o sistema fotovoltaico na hora da ponta e interrupções do sistema da rede no período fora da ponta. A estocagem inercial por meio do Flywheel tem um papel fundamental nesta mini-rede (Flywheel, bateria VRLA, UPS, inversor e STS), pois a sua utilização pode ser apontada como uma inovação tecnológica quanto à regulação de tensão no sistema de energia elétrica, além de preparar a edificação para o smart-grid. Esta configuração de acumulação de energia permitiu a analise do deslocamento desta energia armazenada para o consumo no horário de ponta, mudando o conceito de sistemas fotovoltaicos autônomos no meio urbano e rural no país. Este conceito de armazenagem se confirma então como um aporte na eficiência de energia na edificação, podendo carrear economia de energia substancial, além de proporcionar uma confiabilidade no serviço de energia, com um baixo retorno do investimento e com uma garantia de funcionamento com pequena ou nenhuma manutenção durante o período de vida de 20 anos.