Global ETD Search
Search theses and dissertations gathered from participating repositories worldwide. Every result links back to the library that holds it. No account is needed.
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Showing 1 to 18 of 18 for “"Secondary Coordination Sphere"”.
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Fine���tuning the reduction potential of Cupredoxin proteins by altering secondary coordination sphere interactions
… bonding and hydrophobic interactions in the secondary coordination sphere of the copper site. Surprisingly, this large range of achievable Em values was attained with only two to three mutations to the protein. It is also shown that the effects on the Em of certain individual mutations is …
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Biomimetic carboxylate-bridged diiron complexes : from solution behavior to modeling the secondary coordination sphere
… the Utility of Hydrogen Bonding Donors in the Secondary Coordination Sphere of Non-heme Metal Complexes Chapter 1 is a mini-review that covers systematic studies on the effect of hydrogen bonding donors on the properties of metal complexes. Generalizing across different metals studied in …
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Bio-inspired iron complexes featuring secondary coordination sphere interactions: Ligand design strategies and dioxygen reactivity
… on well-place hydrogen bonding networks in the secondary coordination sphere and protein superstructure to facilitate favorable reactivity at the metal center. These non-covalent interactions can contribute to the overall reactivity in a number ways including fine-tuning metal ligand …
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The Effect of the Secondary Coordination Sphere on the Stabilities of Cerium(III) and Cerium(IV) Coordination Complexes
… of the lanthanide bonds, the use of the secondary coordination sphere about lanthanide complexes, including alkali metal cations lithium, sodium, and potassium, as well as hydrogen bonding guanidinium cations, as a framework to guide lanthanide-ligand bonding interactions was studied. …
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Investigating the role of secondary coordination sphere in designed metalloenzymes and engineering protein interactions for enhanced electron transfer
Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2024-05-01
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Bio-inspired iron and cobalt complexes featuring a secondary coordination sphere: ligand design, complexation, and modeling of enzymatic processes
The activation of small molecules is crucial to the function of biological systems’ metabolic processes, detoxification, and cellular signaling. Metallocofactors and protein scaffolds often work in conjunction to attract and bind the small molecules, stabilize reactive intermediates, and shuttle …
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Bio-inspired first-row transition metal complexes for small molecule activation
Secondary coordination spheres play many important roles in the activity and function of metalloenzymes: they can help stabilize reactive intermediates and shuttle protons or electrons over the course of enzymatic transformations. Accordingly, there have been numerous efforts to mimic these …
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Oxyanion reduction in a non-heme iron system
The secondary coordination sphere of metalloenzymes is implicated in controlling nuclearity, enhancing substrate selectivity, and stabilizing reactive intermediates, and is thus essential in promoting the reactivity of the metal center in the active site. Inspired by the small molecule activation …
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Small molecule activation and reduction using non-heme iron complexes
… out a vast array of different reactions. The secondary coordination sphere of these play an intricate role in controlling nuclearity, enhancing substrate selectivity, stabilizing reactive intermediates, and controlling the redox potential of the active site metal. Many of these secondary …
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Developing Structure-Activity-Relationships for Metal-Ligand-Cooperative (MLC) Complexes using PR2NR′2 Ligands
… and steric properties of the primary and secondary coordination sphere, respectively. Metalation of PR2NR′2 ligands with Ru gave a series of MLC proton shuttling complexes for catalytic testing. From catalytic performance, structure-activity relationships were extracted for two types of …
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The Interplay Between Anions And Radicals In Synthesis, Spectroscopy, And Catalysis
… Either the presence of CuI cations in the secondary coordination sphere or the use of sulfur donor atoms in the primary coordination sphere resulted in unusual architectures in the Shibasaki rare earth alkali metal BINOLate (REMB) framework. In CuI containing REMBs an atypical 2 coordinate …
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Distal hydrogen-bonding effects and cofacial bimetallic salen architectures for oxygen activation chemistry
… studies elucidated the key redox, steric, and secondary coordination sphere effects for optimal catalytic ability. The incorporation a chiral backbone into the macrocycle led to catalysts that perform enantioselective epoxidation of unfunctionalized olefins. A macrocycle with an amide, imine, …
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Characterization and catalytic application of an engineered cupredoxin possessing a potential in excess of 1 volt
… in an attempt to demonstrate the power of the secondary coordination sphere constituents in determining the redox potential of a metal center. This new variant, M44F/N47S/F114N/G116F/M121L (henceforth referred to as 5mAz, for brevity’s sake), is an amalgamation of previously characterized …
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ZnSe Quantum Dots as a platform for solar fuels synthesis
… capping ligands as a powerful tool to modify the secondary coordination sphere and therefore the product selectivity of colloidal photocatalysts. Furthermore, dithiols, a class of capping ligands not examined in the context of CO2 reduction previously, were found to enhance CO2 reduction on ZnSe …
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Isolating, characterizing, and engineering novel Cu-proteins and peroxidases
… on the role of subtle changes of residues in the secondary coordination sphere of the metal ion, an underexplored area of study. I use protein engineering techniques not only to shed light on the mechanisms underlying such changes, but also to design new functionalities within our scaffold …
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Characterizing a structural and functional model of nitric oxide reductase performing NO and O2 reduction in engineered myoglobin
… and each metal contains a different primary and secondary coordination sphere.1 NOR and HCO also have cross-reactivity, though they are more reactive toward their native substrate. NOR is capable of O2 reduction and some members of the HCO superfamily are capable of NO reduction.2–4 Therefore, an …
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Ligand design in nickel and cobalt complexes for homogeneous catalysis
… chemistry. Instillation of a Lewis acid secondary coordination sphere on a CCC framework was achieved via sequential metalation and hydroboration. Finally, a rhodium metalation procedure for the DippCCC ligand was achieved resulting in the isolation of (DippCCC)RhN2. This complex was …
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Development & characterization of bio-inspired earth-abundant metal systems and extreme ultraviolet spectroscopy of precious metal photocatalysts
Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2024-08-01