The Design and Synthesis of Transition Metal Complexes Supported by Non-innocent Ligand Scaffolds for Small Molecule Activation

This dissertation focuses on the incorporation of non-innocent or multifunctional moieties into different ligand scaffolds to support one or multiple metal centers in close proximity. Chapter 2 focuses on the initial efforts to synthesize hetero- or homometallic tri- or dinuclear metal carbonyl complexes supported by para-terphenyl diphosphine ligands. A series of [M₂M’(CO)₄]-type clusters (M = Ni, Pd; M’ = Fe, Co) could be accessed and used to relate the metal composition to the properties of the complexes. During these studies it was also found that non-innocent behavior was observed in dinuclear Fe complexes that result from changes in oxidation state of the cluster. These studies led to efforts to rationally incorporate central arene moieties capable managing both protons and electrons during small molecule activation.

Chapter 3 discusses the synthesis of metal complexes supported by a novel para-terphenyl diphosphine ligand containing a non-innocent 1,4-hydroquinone moiety as the central arene. A Pd⁰-hydroquinone complex was found to mediate the activation of a variety of small molecules to form the corresponding Pd⁰-quinone complexes in a formal two proton ⁄ two electron transformation. Mechanistic investigations of dioxygen activation revealed a metal-first activation process followed by subsequent proton and electron transfer from the ligand. These studies revealed the capacity of the central arene substituent to serve as a reservoir for a formal equivalent of dihydrogen, although the stability of the M-quinone compounds prevented access to the PdII-quinone oxidation state, thus hindering of small molecule transformations requiring more than two electrons per equivalent of metal complex.

Chapter 4 discusses the synthesis of metal complexes supported by a ligand containing a 3,5-substituted pyridine moiety as the linker separating the phenylene phosphine donors. Nickel and palladium complexes supported by this ligand were found to tolerate a wide variety of pyridine nitrogen-coordinated electrophiles which were found to alter central pyridine electronics, and therefore metal-pyridine π-system interactions, substantially. Furthermore, nickel complexes supported by this ligand were found to activate H-B and H-Si bonds and formally hydroborate and hydrosilylate the central pyridine ring. These systems highlight the potential use of pyridine π-system-coordinated metal complexes to reversibly store reducing equivalents within the ligand framework in a manner akin to the previously discussed 1,4-hydroquinone diphosphine ligand scaffold.

Chapter 5 departs from the phosphine-based chemistry and instead focuses on the incorporation of hydrogen bonding networks into the secondary coordination sphere of [Fe₄(μ₄-O)]-type clusters supported by various pyrazolate ligands. The aim of this project is to stabilize reactive oxygenic species, such as oxos, to study their spectroscopy and reactivity in the context of complicated multimetallic clusters. Herein is reported this synthesis and electrochemical and Mössbauer characterization of a series of chloride clusters have been synthesized using parent pyrazolate and a 3-aminophenyl substituted pyrazolate ligand. Efforts to rationally access hydroxo and oxo clusters from these chloride precursors represents ongoing work that will continue in the group.

Appendix A discusses attempts to access [Fe₃Ni]-type clusters as models of the enzymatic active site of [NiFe] carbon monoxide dehydrogenase. Efforts to construct tetranuclear clusters with an interstitial sulfide proved unsuccessful, although a (μ₃-S) ligand could be installed through non-oxidative routes into triiron clusters. While [Fe₃Ni(μ₄-O)]-type clusters could be assembled, accessing an open heterobimetallic edge site proved challenging, thus prohibiting efforts to study chemical transformations, such as hydroxide attack onto carbon monoxide or carbon dioxide coordination, relevant to the native enzyme. Appendix B discusses the attempts to synthesize models of the full H-cluster of [FeFe]-hydrogenase using a bioinorganic approach. A synthetic peptide containing three cysteine donors was successfully synthesized and found to chelate a preformed synthetic [Fe₄S₄] cluster. However, efforts to incorporate the diiron subsite model complex proved challenging as the planned thioester exchange reaction was found to non-selectively acetylate the peptide backbone, thus preventing the construction of the full six-iron cluster.

Systematic Studies on 3d- and 4f-Metal Containing Polyoxometalates Suitable for Organic Derivatization

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Processo de separação por membranas para remoção de sulfato de níquel e zinco de efluente sintético de indústrias metal-mecânicas

O objetivo do presente trabalho foi investigar o desempenho de membranas comerciais e funcionalizadas na remoção de metais pesados de efluentes sintéticos, simulando os efluentes gerados pelas indústrias metal-mecânicas. As membranas funcionalizadas foram preparadas em laboratório a partir de diferentes poli (éter imidas) sulfonadas, SPEI, que apresentavam alta hidrofilicidade e capacidade de troca iônica. As permeabilidades hidráulicas das membranas de SPEI aumentaram com o grau de sulfonação. Porém, as rejeições foram ainda muito baixas comparadas as membranas comerciais. Por esta razão, algumas membranas comerciais (NF-90, SW30, HRP98PP e BW30LE) foram investigadas e avaliadas quanto ao comportamento da permeabilidade de água e o grau de rejeição a metais pesados. Os resultados mostraram que a membrana de osmose inversa de baixa energia (BW30LE) tinha o melhor fluxo de água (48,44 L/h.m2) e grau de rejeição a cádmio (98%). Logo, ela foi selecionada para o tratamento dos efluentes sintéticos de indústrias metal-mecânicas contendo níquel e zinco. As indústrias da região de Valencia, na Espanha, forneceram amostras de seus efluentes para análise quantitativa, possibilitando o prepararo de soluções sintéticas modelos. Os resultados foram obtidos variando algumas condições de permeação, tais como a força motriz, o pH e a concentração dos metais na solução de alimentação. Os resultados indicaram que o processo de osmose inversa com a membrana BW30LE é altamente adequado para o tratamento de efluentes contendo metais pesados

Drawn to the Sea: Charles Bradford Hudson (1865-1939), Artist, Author, Army Officer, with Special Notice of His Work for the United States Fish Commission and Bureau of Fisheries

The biography of Charles Bradford Hudson that follows this preface had its seeds about 1965 when I (VGS) was casually examining the extensive files of original illustrations of fishes stored in the Division of Fishes, National Museum of Natural History, Smithsonian Institution. I happened upon the unpublished illustration of a rainbow trout by Hudson and was greatly impressed with its quality. The thought occurred to me then that the artist must have gone on to do more than just illustrate fishes. During the next 20 years I occasionally pawed through those files, which contained the work of numerous artists, who had worked from 1838 to the present. In 1985, I happened to discuss the files with my supervisor, who urged me to produce a museum exhibit of original fish illustrations. This I did, selecting 200 of the illustrations representing 21 artists, including, of course, Hudson. As part of the text for the exhibit, Drawn from the Sea, Art in the Service of Ichthyology, I prepared short biographies of each of the artists. The exhibit, with an available poster, was shown in the Museum for six months, and a reduced version was exhibited in U.S. and Canadian museums during the next 3 years.

Vitrification of Yunnan Yellow Cattle oocytes: work in progress

The objective of this study was to provide a simple cryopreservation method for oocytes from Yunnan Yellow Cattle and facilitate preservation efforts in this native Chinese breed, which is threatened by agricultural modernization. Cumulus-oocyte complexes (COCs) were collected from slaughterhouse ovaries and matured in vitro for 22-24 h, then selected for cryopreservation. Vitrification in open pulled straws (OPS) or in microdrops on a cooled metal surface (solid surface vitrification, SSV) was compared. The OPS vitrification solution consisted of 20% ethylene glycol (EG) and 20% DMSO. The SSV solution was a mixture of 35% EG, 5% polyvinyl-pyrrolidon (PVP) and 0.4 M trehalose. Vitrified and warmed oocytes were either fertilized in vitro or parthenogenetically activated. The rates of cleavage and development to blastocysts of fertilized oocytes following OPS versus SSV were not statistically different (38.3 and 12.5% versus 35.8 and 6.0%, respectively). The corresponding rates of parthenogenetic development to blastocysts were also not different (8.2 versus 3.5%, respectively). Development to blastocysts of non-vitrified controls following fertilization was significantly higher than that of the vitrified oocytes (22.6%, P < 0.05). These results demonstrate for the first time, that although both OPS and SSV procedures reduced embryonic development, Yunnan Yellow Cattle oocytes are capable of developing to blastocysts following cryopreservation. (C) 2002 Elsevier Science Inc. All rights reserved.

Bulk forming of sheet metal

Ever increasing demands on functional integration of high strength light weight products leads to the development of a new class of manufacturing processes. The application of bulk forming processes to sheet or plate semi-finished products, sometimes in combination with conventional sheet forming processes creates new products with the requested properties. The paper defines this new class of sheet-bulk metal forming processes, gives an overview of the existing processes belonging to this class, highlights the tooling aspects as well as the resulting product properties and presents a short summary of the relevant work that has been done towards modeling and simulation. © 2012 CIRP.

Characterizing the class of local metal sheet thickening processes

The need to create high-value products for specialist applications, and the search for efficient forming routes that obviate the need for some machining steps, is driving Interest In a novel class of forming processes aiming to create locally thickened features within sheet work- pieces. A number of novel forming processes have been proposed to meet this need, but it is as yet unclear which processes will be most effective in creating local thickening of various geometries, and many process configurations have yet to be tried. This paper aims to provide some basic principles for designing and characterising process behaviour. A simplified generic description of sheet thickening processes is provided, with two tools of variable operating on a sheet workpiece in plane strain, with different tool separations and motions parameterised. A comprehensive numerical study of the behaviour of this class of processes is conducted in Abaqus to predict the main characteristics of the material flow in each configuration. The results are used to classify the different basic behaviours that can be achieved by the sheet-bulk thickening processes and to give guidance on future process development, capability and applicability. © 2011 Wiley-VCH Verlag GmbH & Co. KGaA. Weinheim.

Tool-path design for metal spinning

Toolpath design in spinning is an open ended problem, with a large number of solutions, and remains an art acquired by practice. To be able to specify a toolpath without the need for experimental trials, further understanding of the process mechanics Is required. At the moment, the mechanics of the process Is not completely understood, due to the complex deformation and because long solution times required for accurate numerical modelling of the process Inhibit detailed study. This paper proposes and applies a new approach to modelling the process and aims to contribute to the understanding of process mechanics, In particular with respect to the mechanisms of failure and and to apply this understanding for toolpath design In spinning. A new approach to numerical modelling Is proposed and applied to Investigate the process. The findings suggest that there are two different causes and two different modes of wrinkling In spinning, depending on the stage In the process and direction of roller movement. A simple test Is performed to estimate the limits of wrinkling and provide a guideline for toolpath design In a typical spinning process. The results show that the required toolpath geometry in the early stages of the process is different from that In later stages. © 2011 Wiley-VCH Verlag GmbH & Co. KGaA. Weinheim.

Heavy metals in plants and phytoremediation - A state-of-the-art report with special reference to literature published in Chinese journals

Goal, Scope and Background. In some cases, soil, water and food are heavily polluted by heavy metals in China. To use plants to remediate heavy metal pollution would be an effective technique in pollution control. The accumulation of heavy metals in plants and the role of plants in removing pollutants should be understood in order to implement phytoremediation, which makes use of plants to extract, transfer and stabilize heavy metals from soil and water. Methods. The information has been compiled from Chinese publications stemming mostly from the last decade, to show the research results on heavy metals in plants and the role of plants in controlling heavy metal pollution, and to provide a general outlook of phytoremediation in China. Related references from scientific journals and university journals are searched and summarized in sections concerning the accumulation of heavy metals in plants, plants for heavy metal purification and phytoremediation techniques. Results and Discussion. Plants can take up heavy metals by their roots, or even via their stems and leaves, and accumulate them in their organs. Plants take up elements selectively. Accumulation and distribution of heavy metals in the plant depends on the plant species, element species, chemical and bioavailiability, redox, pH, cation exchange capacity, dissolved oxygen, temperature and secretion of roots. Plants are employed in the decontamination of heavy metals from polluted water and have demonstrated high performances in treating mineral tailing water and industrial effluents. The purification capacity of heavy metals by plants are affected by several factors, such as the concentration of the heavy metals, species of elements, plant species, exposure duration, temperature and pH. Conclusions. Phytoremediation, which makes use of vegetation to remove, detoxify, or stabilize persistent pollutants, is a green and environmentally-friendly tool for cleaning polluted soil and water. The advantage of high biomass productive and easy disposal makes plants most useful to remediate heavy metals on site. Recommendations and Outlook. Based on knowledge of the heavy metal accumulation in plants, it is possible to select those species of crops and pasturage herbs, which accumulate fewer heavy metals, for food cultivation and fodder for animals; and to select those hyperaccumulation species for extracting heavy metals from soil and water. Studies on the mechanisms and application of hyperaccumulation are necessary in China for developing phytoremediation.

Mode characteristics of metallically coated square microcavity connected with an output waveguide

Mode characteristics of a square microcavity with an output waveguide on the middle of one side, laterally confined by an insulating layer SiO2 and a p-electrode metal Au, are investigated by two-dimensional finite-difference time-domain technique. The mode quality (Q) factors versus the width of the output waveguide are calculated for Fabry-Peacuterot type and whispering-gallery type modes in the square cavity. Mode coupling between the confined modes in the square cavity and the guided modes in the output waveguide determines the mode Q factors, which is greatly influenced by the symmetry behaviors of the modes. Fabry-Peacuterot type modes can also have high Q factors due to the high reflectivity of the Au layer for the vertical incident mode light rays. For the square cavity with side length 4 mu m and refractive index 3.2, the mode Q factors of the Fabry-Peacuterot type modes can reach 10(4) at the mode wavelength of 1.5 mu m as the output waveguide width is 0.4 mu m.

Photoluminescence properties of tensile-strained GaAsP/GaInP single quantum wells grown by metal organic chemical vapor deposition

Tensile-strained GaAsP/GaInP single quantum well (QW) laser diode (I-D) structures have been grown by low-pressure metal organic chemical vapor deposition (LP-MOCVD) and related photoluminescence (PL) properties have been investigated in detail. The samples have the same well thickness of 16 nm but different P compositions in a GaAsP QW. Two peaks in room temperature (RT) PL spectra are observed for samples with a composition larger than 0.10. Temperature and excitation-power-dependent PL spectra have been measured for a sample with it P composition of 0.15. It is found that the two peaks have a 35 meV energy separation independent of temperature and only the low-energy peak exists below 85 K. Additionally, both peak intensities exhibit a monotonous increase as excitation power increases. Analyses indicate that the two peaks arise from the intrinsic-exciton recombination mechanisms of electron-heavy hole (e-hh) and electron-light hole (e-hh). A theoretical calculation based oil model-solid theory, taking, into account the spin-orbit splitting energy, shows good agreement with our experimental results. The temperature dependence of PL intensity ratio is well explained using the spontaneous emission theory for e-hh and e-hh transitions. front which the ratio can be characterized mainly by the energy separation between the fill and Ill states.

Multiple valley couplings in nanometer Si metal-oxide-semiconductor field-effect transistors

We investigate the couplings between different energy band valleys in a metal-oxide-semiconductor field-effect transistor (MOSFET) device using self-consistent calculations of million-atom Schrodinger-Poisson equations. Atomistic empirical pseudopotentials are used to describe the device Hamiltonian and the underlying bulk band structure. The MOSFET device is under nonequilibrium condition with a source-drain bias up to 2 V and a gate potential close to the threshold potential. We find that all the intervalley couplings are small, with the coupling constants less than 3 meV. As a result, the system eigenstates derived from different bulk valleys can be calculated separately. This will significantly reduce the simulation time because the diagonalization of the Hamiltonian matrix scales as the third power of the total number of basis functions. (C) 2008 American Institute of Physics.

First-principles study of transition metal impurities in Si

By using ab initio electronic structure calculations within density functional theory, we study the structural, electronic, and magnetic properties of Si doped with a transition metal impurity. We consider the transition metals of the 3d series V, Cr, Mn, Fe, Co, and Ni. To get insight into the level filling mechanism and the magnetization saturation, we first investigate the transition metal-Si alloys in the zinc-blende structure. Next, we investigate the doping of bulk Si with a transition metal atom, in which it occupies the substitutional site, the interstitial site with tetrahedral symmetry, and the interstitial site with hexagonal symmetry. It is found that all of these transition metal impurities prefer an interstitial position in Si. Furthermore, we show that it is possible to interpret the electronic and magnetic properties by using a simple level filling picture and a comparison is made to Ge doped with the same transition metal atoms. In order to get insight into the effect of a strained environment, we calculate the formation energy as a function of an applied homogeneous pressure and we show that an applied pressure can stabilize the substitutional position of transition metal impurities in Si. Finally, the energies of the ferromagnetic states are compared to those of the antiferromagnetic states. It is shown that the interstitial site of the Mn dopant helps us to stabilize the nearest neighbor substitutional site to realize the ferromagnetic state. For doping of Si with Cr, a ferrimagnetic behavior is predicted.

The effect of growth temperature on structural quality of GaN/AlN quantum wells by metal-organic chemical vapour deposition

The effect of the growth temperature on the surface and interface quality for the GaN/AlN multiquantum well (MQW) layer grown by metal-organic vapour chemical deposition is investigated. The obtained GaN/AlN MQW structure is almost coherent to the underlying AlGaN layer at improved growth conditions. With a relatively low growth temperature, the GaN/AlN MQW growth rate increases, the surface roughness reduces considerably and no macro steps are observed, resulting in a better periodicity of MQW.

Analytical model of spin filtering effect and its experimental verification in a forward-biased iron-metal-Al2O3-n-type GaAs tunneling structure under optical spin orientation

An analytical model for the spin filtering transport in a ferromagnetic-metal - Al2O3 - n-type semiconductor tunneling structure has been developed, and demonstrated that the ratio of the helicity-modulated photo-response to the chopped one is proportional to the sum of the relative asymmetry in conductance of two opposite spin-polarized tunneling channels and the MCD effect of the ferromagnetic metal film. The performed measurement in an iron-metal/Al2O3/n-type GaAs tunneling structure under the optical spin orientation has verified that all the aspects of the experimental results are very well in accordance with our model in the regime of the spin filtering. After the MCD effect of the iron film is calibrated by an independent measurement, the physical quantity of Delta G(t)/G(t) (Delta G(t) = G(t)(up arrow) - G(t)(down arrow) is the difference of the conductance between two opposite spin tunneling channels, G(t) =( G(t)(up arrow) + G(t)(down arrow))/2 the averaged tunneling conductance), which concerns us most, can be determined quantitatively with a high sensitivity in the framework of our analytical model. Copyright (c) EPLA, 2008.