Fundamental Studies of Carbon Oxygen Bond Activation in Nickel Diphosphine Ether Complexes. And, Metallomacrocycles as Ligands: Synthesis and Characterization of Aluminum-Bridged Bisglyoximato Complexes of Iron and Cobalt

In order to develop better catalysts for the cleavage of aryl-X bonds fundamental studies of the mechanism and individual steps of the mechanism have been investigated in detail. As the described studies are difficult at best in catalytic systems, model systems are frequently used. To study aryl-oxygen bond activation, a terphenyl diphosphine scaffold containing an ether moiety in the central arene was designed. The first three chapters of this dissertation focus on the studies of the nickel complexes supported by this diphosphine backbone and the research efforts in regards to aryl-oxygen bond activation.

Chapter 2 outlines the synthesis of a variety of diphosphine terphenyl ether ligand scaffolds. The metallation of these scaffolds with nickel is described. The reactivity of these nickel(0) systems is also outlined. The systems were found to typically undergo a reductive cleavage of the aryl oxygen bond. The mechanism was found to be a subsequent oxidative addition, β-H elimination, reductive elimination and (or) decarbonylation.

Chapter 3 presents kinetic studies of the aryl oxygen bond in the systems outlined in Chapter 2. Using a series of nickel(0) diphosphine terphenyl ether complexes the kinetics of aryl oxygen bond activation was studied. The activation parameters of oxidative addition for the model systems were determined. Little variation was observed in the rate and activation parameters of oxidative addition with varying electronics in the model system. The cause of the lack of variation is due to the ground state and oxidative addition transition state being affected similarly. Attempts were made to extend this study to catalytic systems.

Chapter 4 investigates aryl oxygen bond activation in the presence of additives. It was found that the addition of certain metal alkyls to the nickel(0) model system lead to an increase in the rate of aryl oxygen bond activation. The addition of excess Grignard reagent led to an order of magnitude increase in the rate of aryl oxygen bond activation. Similarly the addition of AlMe3 led to a three order of magnitude rate increase. Addition of AlMe₃ at -80 °C led to the formation of an intermediate which was identified by NOESY correlations as a system in which the AlMe3 is coordinated to the ether moiety of the backbone. The rates and activation parameters of aryl oxygen bond activation in the presence of AlMe3 were investigated.

The last two chapters involve the study of metalla-macrocycles as ligands. Chapter 5 details the synthesis of a variety of glyoxime backbones and diphenol precursors and their metallation with aluminum. The coordination chemistry of iron on the aluminum scaffolds was investigated. Varying the electronics of the aluminum macrocycle was found to affect the observed electrochemistry of the iron center.

Chapter 6 extends the studies of chapter 5 to cobalt complexes. The synthesis of cobalt dialuminum glyoxime metal complexes is described. The electrochemistry of the cobalt complexes was investigated. The electrochemistry was compared to the observed electrochemistry of a zinc analog to identify the redox activity of the ligand. In the presence of acid the cobalt complexes were found to electrochemically reduce protons to dihydrogen. The electronics of the ancillary aluminum ligands were found to affect the potential of proton reduction in the cobalt complexes. These potentials were compared to other diglyoximate complexes.

Models of the Oxygen-Evolving Complex of Photosystem II

In the five chapters that follow, I delineate my efforts over the last five years to synthesize structurally and chemically relevant models of the Oxygen Evolving Complex (OEC) of Photosystem II. The OEC is nature’s only water oxidation catalyst, in that it forms the dioxygen in our atmosphere necessary for oxygenic life. Therefore understanding its structure and function is of deep fundamental interest and could provide design elements for artificial photosynthesis and manmade water oxidation catalysts. Synthetic endeavors towards OEC mimics have been an active area of research since the mid 1970s and have mutually evolved alongside biochemical and spectroscopic studies, affording ever-refined proposals for the structure of the OEC and the mechanism of water oxidation. This research has culminated in the most recent proposal: a low symmetry Mn₄CaO₅ cluster with a distorted Mn₃CaO₄ cubane bridged to a fourth, dangling Mn. To give context for how my graduate work fits into this rich history of OEC research, Chapter 1 provides a historical timeline of proposals for OEC structure, emphasizing the role that synthetic Mn and MnCa clusters have played, and ending with our Mn₃CaO₄ heterometallic cubane complexes.

In Chapter 2, the triarylbenzene ligand framework used throughout my work is introduced, and trinuclear clusters of Mn, Co, and Ni are discussed. The ligand scaffold consistently coordinates three metals in close proximity while leaving coordination sites open for further modification through ancillary ligand binding. The ligands coordinated could be varied, with a range of carboxylates and some less coordinating anions studied. These complexes’ structures, magnetic behavior, and redox properties are discussed.

Chapter 3 explores the redox chemistry of the trimanganese system more thoroughly in the presence of a fourth Mn equivalent, finding a range of oxidation states and oxide incorporation dependent on oxidant, solvent, and Mn salt. Oxidation states from Mn^II₄ to Mn^IIIMn^IV₃ were observed, with 1-4 O^2– ligands incorporated, modeling the photoactivation of the OEC. These complexes were studied by X-ray diffraction, EPR, XAS, magnetometry, and CV.

As Ca²⁺ is a necessary component of the OEC, Chapter 4 discusses synthetic strategies for making highly structurally accurate models of the OEC containing both Mn and Ca in the Mn₃CaO₄ cubane + dangling Mn geometry. Structural and electrochemical characterization of the first Mn₃CaO₄ heterometallic cubane complex— and comparison to an all-Mn Mn₄O₄ analog—suggests a role for Ca²⁺ in the OEC. Modification of the Mn₃CaO₄ system by ligand substitution affords low symmetry Mn₃CaO₄ complexes that are the most accurate models of the OEC to date.

Finally, in Chapter 5 the reactivity of the Mn₃CaO₄ cubane complexes toward O- atom transfer is discussed. The metal M strongly affects the reactivity. The mechanisms of O-atom transfer and water incorporation from and into Mn₄O₄ and Mn₄O₃ clusters, respectively, are studied through computation and ¹⁸O-labeling studies. The μ3-oxos of the Mn₄O₄ system prove fluxional, lending support for proposals of O^2– fluxionality within the OEC.

Embedding quantum simulators

79 p.

The Forbidden Quantum Adder

Quantum information provides fundamentally different computational resources than classical information. We prove that there is no unitary protocol able to add unknown quantum states belonging to different Hilbert spaces. This is an inherent restriction of quantum physics that is related to the impossibility of copying an arbitrary quantum state, i.e., the no-cloning theorem. Moreover, we demonstrate that a quantum adder, in absence of an ancillary system, is also forbidden for a known orthonormal basis. This allows us to propose an approximate quantum adder that could be implemented in the lab. Finally, we discuss the distinct character of the forbidden quantum adder for quantum states and the allowed quantum adder for density matrices.

Parity-dependent State Engineering and Tomography in the ultrastrong coupling regime

Reaching the strong coupling regime of light-matter interaction has led to an impressive development in fundamental quantum physics and applications to quantum information processing. Latests advances in different quantum technologies, like superconducting circuits or semiconductor quantum wells, show that the ultrastrong coupling regime (USC) can also be achieved, where novel physical phenomena and potential computational benefits have been predicted. Nevertheless, the lack of effective decoupling mechanism in this regime has so far hindered control and measurement processes. Here, we propose a method based on parity symmetry conservation that allows for the generation and reconstruction of arbitrary states in the ultrastrong coupling regime of light-matter interactions. Our protocol requires minimal external resources by making use of the coupling between the USC system and an ancillary two-level quantum system.

Commercial Whaling, Especially for Gray Whales, Eschrichtius robustus, and Humpback Whales, Megaptera novaeangliae, at California and Baja California Shore Stations in the 19th Century (1854–1899)

Shore whaling along North America’s California and Baja California coasts during 1854–99 was ancillary to the offshore and alongshore American whale fishery, which had begun in the North Pacific in the early 1800’s and was flourishing by the 1840’s. From its inception at Monterey, Calif., in the mid 1850’s, the shore fishery, involving open boats deployed from land to catch and tow whales for processing, eventually spread from Monterey south to San Diego and Baja California and north to Crescent City near the California–Oregon border. It had declined to a relict industry by the 1880’s, although sporadic efforts continued into the early 20th century. The main target species were gray whales, Eschrichtius robustus, and humpback whales, Megaptera novaeangliae, with the valuable North Pacific right whale, Eubalaena japonica, also pursued opportunistically. Catch data are grossly incomplete for most stations; no logbooks were kept for these operations as they were for high-seas whaling voyages. Even when good information is available on catch levels, usually as number of whales landed or quantity of oil produced, it is rarely broken down by species. Therefore, we devised methods for extrapolation, interpolation, pro rationing, correction, and informed judgment to produce time series of catches. The resulting estimates of landings from 1854 to 1899 are 3,150 (SE = 112) gray whales and 1,637 (SE = 62) humpback whales. The numbers landed should be multiplied by 1.2 to account for hunting loss (i.e. whales harpooned or shot but not recovered and processed).

Improving aquaculture feed in Bangladesh: From feed ingredients to farmer profit to safe consumption

Use of manufactured feeds in aquaculture in Bangladesh has grown rapidly over the last five years. More than 1 million tonnes of commercially formulated feeds and 0.3-0.4 million tonnes of farm-made feeds were produced in 2012, and sectoral growth is projected to increase substantially over the medium term. This working paper summarizes findings from a study, conducted as part of the WorldFish/USAID “Feed the Future-Aquaculture” project in 2012, assessing the current status of the aquaculture feed sector in Bangladesh. Fish feed value chains, market trends, ingredients and formulation systems, farm feeding practices, ancillary services and feed regulations were investigated. The study identifies a number of entry points for interventions in the sector, and investments which would improve feed quality and farmer access to better feeds and support the growth of sustainable aquaculture.

Major and trace element analytical methods of the National Status and Trends Program: 2000-2006

This document contains analytical methods that detail the procedures for determining major and trace element concentrations in bivalve tissue and sediment samples collected as part of the National Status and Trends Program (NS&T) for the years 2000-2006. Previously published NOAA Technical Memoranda NOS ORCA 71 and 130 (Lauenstein and Cantillo, 1993; Lauenstein and Cantillo, 1998) detail trace element analyses for the years 1984-1992 and 1993-1996, respectively, and include ancillary, histopathology, and contaminant (organic and trace element) analytical methods. The methods presented in this document for trace element analysis were utilized by the NS&T Mussel Watch and Bioeffects Projects. The Mussel Watch Project has been monitoring contaminants in bivalves and sediment for over 20 years, and is the longest active contaminant monitoring program operating in U.S. costal waters. Approximately 280 Mussel Watch sites are monitored on biennial and decadal timescales using bivalve tissue and sediment, respectively. The Bioeffects Project applies the sediment quality approach, which uses sediment contamination measurements, toxicity tests and benthic macroinfauna quantification to characterize pollution in selected estuaries and coastal embayments. Contaminant assessment is a core function of both projects. Although only one contract laboratory was used by the NS&T Program during the specified time period, several analytical methods and instruments were employed. The specific analytical method, including instrumentation and detection limit, is noted for each measurement taken and can be found at http://NSandT.noaa.gov. The major and trace elements measured by the NS&T Program include: Al, Si, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Sn, Sb, Ag, Cd, Hg, Tl and Pb.

Techno-economic analysis of production and marketing of marine by-products in India

Marine by-products coming under the ancillary products group found many applications in pharmaceutical and industrial sectors. Although many of these products are fetching very high price at the export market, adequate statistics regarding their current production, marketing and utilisation is lacking. The present analysis deals with the production potential, level of exploitation, uses, export growth rate and potential for the future of some of these marine by-products. The analysis revealed that an estimated quantity of 205 t. of shells, 10 t. of gastropod operculum, 4,932 t. of shark liver oil and 4,384 t. of shark cartilage could be produced annually in India with the current landings. The production potential of chitin is estimated as 3,560 t. from shrimp shell wastes and 1,354 t. from crab shell wastes. The high unit value of different products clearly indicates the scope for their development by evolving appropriate utilisation and marketing strategies.

High-resolution γ-ray spectroscopy: A versatile tool for nuclear β-decay studies at TRIUMF-ISAC

High-resolution γ-ray spectroscopy is essential to fully exploit the unique, high-quality beams available at the next generation of radioactive ion beam facilities such as the TRIUMF isotope separator and accelerator (ISAC). The 8π spectrometer, which consists of 20 Compton-suppressed HPGe detectors, has recently been reconfigured for a vigorous research programme in weak interaction and nuclear structure physics. With the addition of a variety of ancillary detectors it has become the world's most powerful device dedicated to β-decay studies. This paper provides a brief overview of the apparatus and highlights from recent experiments. © 2005 IOP Publishing Ltd.

Evaluating the impact of V2G services on the degradation of batteries in PHEV and EV

Many researchers and industry observers claim that electric vehicles (EV) and plug-in hybrid electric vehicles (PHEV) could provide vehicle-to-grid (V2G) bulk energy and ancillary services to an electricity network. This work quantified the impact on various battery characteristics whilst providing such services. The sensitivity of the impact of V2G services on battery degradation was assessed for EV and PHEV for different battery capacities, charging regimes, and battery depth of discharge. Battery degradation was found to be most dependent on energy throughput for both the EV and PHEV powertrains, but was most sensitive to charging regime (for EVs) and battery capacity (for PHEVs). When providing ancillary services, battery degradation in both powertrains was most sensitive to individual vehicle battery depth of discharge. Degradation arising from both bulk energy and ancillary services could be minimised by reducing the battery capacity of the vehicle, restricting the number of hours connected and reducing the depth of discharge of each vehicle for ancillary services. Regardless, best case minimum impacts of providing V2G services are severe such as to require multiple battery pack replacements over the vehicle lifetime. © 2013 Elsevier Ltd.

Surface modelling of soil pH

In addition to classical methods, namely kriging, Inverse Distance Weighting (IDW) and splines, which have been frequently used for interpolating the spatial patterns of soil properties, a relatively more accurate surface modelling technique is being developed in recent years, namely high accuracy surface modelling (HASM). It has been used in the numerical tests, DEM construction and the interpolation of climate and ecosystem changes. In this paper, HASM was applied to interpolate soil pH for assessing its feasibility of soil property interpolation in a red soil region of Jiangxi Province, China. Soil pH was measured on 150 samples of topsoil (0-20 cm) for the interpolation and comparing the performance of HASM, kriging. IDW and splines. The mean errors (MEs) of interpolations indicate little bias of interpolation for soil pH by the four techniques. HASM has less mean absolute error (MAE) and root mean square error (RMSE) than kriging, IDW and splines. HASM is still the most accurate one when we use the mean rank and the standard deviation of the ranks to avoid the outlier effects in assessing the prediction performance of the four methods. Therefore, HASM can be considered as an alternative and accurate method for interpolating soil properties. Further researches of HASM are needed to combine HASM with ancillary variables to improve the interpolation performance and develop a user-friendly algorithm that can be implemented in a GIS package. (C) 2009 Elsevier B.V. All rights reserved.

Manipulating charge-transfer character with electron-withdrawing main-group moieties for the color tuning of iridium electrophosphors

A new and synthetically versatile strategy has been developed for the phosphorescence color tuning of cyclometalated iridium phosphors by simple tailoring of the phenyl ring of ppy (Hppy=2-phenylpyridine) with various main-group moieties in [Ir(ppy-X)(2)(acac)] (X=B(Mes)(2), SiPh3, GePh3, NPh2, POPh2, OPh, SPh, SO2Ph). This can be achieved by shifting the charge-transfer character from the pyridyl groups in some traditional iridium ppy-type complexes to the electron-withdrawing main-group moieties and these assignments were supported by theoretical calculations.

Robust Tris-Cyclometalated Iridium(III) Phosphors with Ligands for Effective Charge Carrier Injection/Transport: Synthesis, Redox, Photophysical, and Electrophosphorescent Behavior

With the target to design and develop new functionalized green triplet light emitters that possess distinctive electronic properties for robust and highly efficient phosphorescent organic light-emitting diodes (PHOLEDs), a series of bluish-green to yellow-green phosphorescent tris-cyclometalated homoleptic iridium(III) complexes [Ir(ppy-X)(3)] (X=SiPh3, GePh3, NPh2, POPh2, OPh, SPh, SO2Ph, Hppy=2-phenylpyridine) have been synthesized and fully characterized by spectroscopic, redox, and photophysical methods

New Efficiency Records for Stable Dye-Sensitized Solar Cells with Low-Volatility and Ionic Liquid Electrolytes

We report a high molar extinction coefficient heteroleptic polypyridyl ruthenium sensitizer, featuring an electron-rich 3,4-ethylenedioxythiophene unit in its ancillary ligand. A nanocrystalline titania film stained with this sensitizer shows an improved optical absorption, which is highly desirable for practical dye-sensitized solar cells with a thin photoactive layer, facilitating the efficient charge collection.