A5037258492- Metalloenzymes and iron-sulfur proteins
- Electrocatalysts for Energy Conversion
- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- CO2 Reduction Techniques and Catalysts
- Hydrogen Storage and Materials
- Carbon dioxide utilization in catalysis
- Metal-Catalyzed Oxygenation Mechanisms
- Cholinesterase and Neurodegenerative Diseases
- Pesticide Exposure and Toxicity
- Advanced Photocatalysis Techniques
- Catalysis and Hydrodesulfurization Studies
- Catalytic Processes in Materials Science
- Redox biology and oxidative stress
- Asymmetric Hydrogenation and Catalysis
- Advanced battery technologies research
- Ammonia Synthesis and Nitrogen Reduction
- Computational Drug Discovery Methods
The Ohio State University
2017-2024
Columbus Center
2024
Well-defined molecular systems for catalytic hydrogen production that are robust, easily generated, and active under mild aqueous conditions remain underdeveloped. Nickel-substituted rubredoxin (NiRd) is one such system, featuring a tetrathiolate coordination environment around the nickel center identical to native [NiFe] hydrogenases demonstrating hydrogenase-like proton reduction activity. However, until now, mechanism has remained elusive. In this work, we have combined quantitative...
Secondary sphere interactions are known to significantly impact catalytic rates within biological systems as well synthetic molecular catalysts. The [NiFe] hydrogenase enzymes oxidize and produce hydrogen at high turnover a complex coordination environment. Nickel-substituted rubredoxin (NiRd) has been developed functional, protein-based mimic of the hydrogenase, providing an opportunity understand influence secondary environment on proton reduction activity. In this work, rationally...
Nickel-substituted rubredoxin (NiRd) is a functional enzyme mimic of hydrogenase, highly active for electrocatalytic and solution-phase hydrogen generation. Spectroscopic methods can provide valuable insight into the catalytic mechanism, provided appropriate technique used. In this study, we have employed multiwavelength resonance Raman spectroscopy coupled with DFT calculations on an extended active-site model NiRd to probe electronic geometric structures resting state system. Excellent...
Abstract An enzymatic system for light‐driven hydrogen generation has been developed through covalent attachment of a ruthenium chromophore to nickel‐substituted rubredoxin (NiRd). The photoinduced activity the hybrid enzyme is significantly greater than that two‐component and strongly dependent on position phototrigger relative active site, indicating role intramolecular electron transfer in catalysis. Steady‐state time‐resolved emission spectra reveal pathway rapid, direct quenching...
The field of solar fuels is a rapidly growing area research, though low overall efficiencies continue to preclude large-scale implementation. To resolve the elementary processes involved in light-driven energy storage and identify key factors contributing efficiency losses, systematic investigation optimization are necessary. In this work, ruthenium chromophore directly attached model hydrogenase enzyme, nickel-substituted rubredoxin, construct molecular system capable photoinduced hydrogen...
The life-sustaining reduction of N2 to NH3 is thermoneutral yet kinetically challenged by high-energy intermediates such as N2H2. Exploring intramolecular H-bonding a potential strategy stabilize diazene intermediates, we employ series [xHetTpCu]2(μ-N2H2) complexes that exhibit between pendant aromatic N-heterocycles (xHet) pyridine and bridging trans-N2H2 ligand at copper(I) centers. X-ray crystallography IR spectroscopy clearly reveal in [pyMeTpCu]2(μ-N2H2) while low-temperature 1H NMR...
Light-driven hydrogen evolution is a promising means of sustainable energy production to meet global demand. This study investigates the photocatalytic activity nickel-substituted rubredoxin (NiRd), an artificial hydrogenase mimic, covalently attached ruthenium phototrigger (RuNiRd). By systematically modifying para-substituents on Ru(II) polypyridyl complexes, we sought optimize intramolecular electron transfer processes within RuNiRd system. A series electron-donating and...
Chemical warfare nerve agents (CWNAs) present a global threat to both military and civilian populations. The acute toxicity of CWNAs stems from their ability effectively inhibit acetylcholinesterase (AChE). This inhibition can lead uncontrolled cholinergic cellular signaling, resulting in crisis and, ultimately, death. Although the current FDA-approved standard care is moderately effective when administered early, development novel treatment strategies necessary. Butyrylcholinesterase (BChE)...
Nickel‐substituted rubredoxin (NiRd) has been shown to serve as a functional mimic of nickel‐containing hydrogenases, able produce hydrogen gas with high catalytic rates. In the native enzyme, nickel center is coordinated by four cysteine thiolates. A similar environment seen in NiRd, which represents first model reproduce this coordination motif. This 52‐residue protein stable under wide range conditions, making it well‐suited for production or future fuel cells. Although much known about...
The life-sustaining reduction of N 2 to NH 3 is thermoneutral yet kinetically challenged by high energy intermediates such as H . Exploring intramolecular H-bonding a potential strategy stabilize diazene intermediates, we employ series [ xHet TpCu] (𝜇-N ) complexes that exhibit between pendant aromatic N-heterocycles ( X Het) pyridine and bridging trans -N ligand at copper(I) centers. X-ray crystallography IR spectroscopy clearly reveal in pyMe while low temperature 1 NMR studies coupled...
<div><p>The life-sustaining reduction of N<sub>2</sub> to NH<sub>3</sub> is thermoneutral yet kinetically challenged by high energy intermediates such as N<sub>2</sub>H<sub>2</sub>. Exploring intramolecular H-bonding a potential strategy stabilize diazene intermediates, we employ series [<sup>xHet</sup>TpCu]<sub>2</sub>(𝜇-N<sub>2</sub>H<sub>2</sub>) complexes that exhibit between...