Professor Mirica's research interests include Inorganic Chemistry, Bioinorganic Chemistry, Organometallic Chemistry, Organic Chemistry, Biological Chemistry, Biomimetic Oxidations, Renewable Energy Catalysis, Oxygen-Activating Metalloenzymes, Role of Transition Metal Ions in Neurodegenerative Diseases
Our research program uses inorganic chemistry, organic chemistry, and biological chemistry to address important metal-mediated processes with energy, biological, and medical relevance. An interdisciplinary, problem-based approach will be employed to synthesize and characterize new organic molecules and inorganic complexes, with the ultimate goal to tackle unsolved problems with broad implications to our society. Several research areas will be pursued, which are expected to attract students and postdocs with different research interests and to provide them with a broad knowledge base applicable in most chemistry careers.
Catalysis of Energy-Related Processes. The global energy consumption is expected to at least double in the next fifty years and development of efficient chemical transformations for efficient fossil fuel utilization and energy production from renewable sources will be greatly needed. Methane – the main constituent of natural gas, is found in large quantities on earth and could become a significant source of energy as petroleum reserves diminish. The conversion of methane into liquid fuels (e.g., higher alkanes) would allow for a more efficient use of natural gas reserves as an inexpensive energy resource. In this regard, we are interesting in the development of novel catalysts for the oxidative oligomerization of methane using green oxidants such as O2 that should have a major impact on our society and the environment. In addition, we are also interested in developing catalytic systems for CO2 reduction, which would constitute an important step in employing CO2 as a renewable source for the generation of liquid fuels and thus potentially impact the global carbon balance. In our catalyst development we aim to combine successful approaches from organometallic chemistry for the functionalization of unactivated organic molecules with strategies from bioinorganic chemistry for the activation of small molecules (i.e., O2 and CO2). While initial studies have focused on Pd complexes – given their extensive use in catalysis, current research efforts focus on earth abundant Ni complexes. The proposed research will take advantage of our ability to judiciously design ligands that tune the electronic properties and catalytic reactivity of metal ions in various oxidation states. We are also uniquely equipped to study the electronic properties and reactivity of both paramagnetic and diamagnetic systems through an extensive series of spectroscopic, mechanistic, and computational approaches to characterize in detail the electronic properties and reactivity of the investigated systems.
Another approach for the production of carbon-neutral energy production is to use sunlight, the largest exploitable renewable energy resource. In this context, there is a large interest in developing molecular systems that can capture solar energy and used it to produce oxygen and hydrogen from water. We are interested in the design, synthesis, and characterization of polymetallic complexes as potential catalysts for water oxidation. If successful, the developed catalysts capable of water oxidation can potentially be used in tandem with photovoltaic cells to construct artificial photosynthetic centers.
In addition, we have recently been able to isolate and characterize in detail organometallic NiIII complexes containing various organic ligands. These are the first isolated NiIII species that undergo transmetallation and/or reductive elimination reactions to form new C-C or C-heteroatom bonds, and are also competent catalysts for Kumada and Negishi cross-coupling reactions, providing strong evidence for the direct involvement of organometallic NiIII species in cross-coupling reactions and oxidatively-induced C-heteroatom bond formation reactions. Importantly, successful development of earth abundant Ni-based catalysts for such key chemical transformations would replace the currently used precious metal catalysts employing Pd, Rh, Ir, and Ru systems.
Metal-Amyloid β Peptide Interactions in Alzheimer’s Disease. Alzheimer’s Disease (AD) is the most common neurodegenerative disease. Presently around five million people are diagnosed with AD in the US and the number is expected to reach fourteen million by 2050. The brains of patients with AD are characterized by the deposition of amyloid β (Aβ) peptide plaques, which accumulate unusually high concentrations of copper, iron, and zinc. This project aims to investigate the interaction of transition metal ions with Aβ peptides and the study of the role of metal ions in Aβ oligomerization and amyloid plaque formation. In addition, we are developing novel metal-binding bifunctional compounds as potential therapeutic and diagnostic agents for AD.