Overview
Recent advancements in molecular and structural biology have greatly improved our understanding of the molecular intricacies of life processes. These developments provide new opportunities for chemists to explore the molecular perspective of life. The Kim research group draws on insights from biology to develop fresh frameworks that enhance our understanding of life processes or create artificial systems that mimic nature. Our synthetic modeling approach is based on the belief that the innate properties of atoms and molecules do not change. Our research aims to establish broad chemical principles of reactivity that can ultimately be used to improve human health or to solve environmental problems.
Area 1: Chemistry of Iron-Sulfur Clusters in Redox Signaling
Proteins that incorporate [Fe-S] clusters perform crucial roles in various biological functions, including gene regulation. Organisms have evolved to utilize the innate reactivity of [Fe-S] clusters with small molecule oxidants, such as NO, O2, H2O2, etc., that are produced during oxidative or nitrosative stress, to monitor the cellular environment. When these small molecule oxidants disrupt [Fe-S] clusters in regulatory proteins, this directly links to the activation of the protein’s defensive functions or gene transcription/translation. However, there is limited understanding of the structural changes that occur in proteins after cluster modifications and the potential mechanisms involved in sensing processes. Our research aims to uncover the interconnection of critical redox components, including [Fe-S] clusters, nitric oxide, molecular oxygen (O2), hydrogen sulfide (H2S), and thiols, in propagating their signals. Through synthetic modeling chemistry, we identify novel chemical reactivities unique to [Fe-S] clusters that can offer insights into the redox signaling processes facilitated by [Fe-S] clusters.
- Oakley, K.M.; Lehane, R.L; Zhao, Z.; Kim E. “Dioxygen reactivity of a biomimetic [4Fe-4S] compound exhibits [4Fe-4S] to [2Fe-2S] cluster conversion” J. Inorg. Biochem. 2022, 111714
- Oakley, K. M.; Sterling, K.; Shearer, J.; Kim, E. “Controlled Protonation of [2Fe-2S] Leading to MitoNEET Analogues and Concurrent Cluster Modification.” Inorg. Chem. 2021, 21, 16074–16078.
- Oakley, K. M.; Zhao, Z.; Lehane, R. L.; Ma, J.; Kim E. “Generation of H2S from Thiol-Dependent NO Reactivity of Model [4Fe-4S] Cluster and Roussin’s Black Anion.” Inorg. Chem. 2021, 21, 15910–15917.
Area 2: Biomimetic Catalysts for Energy and Environmental Applications
Human activity is having a devastating impact on our environment. When we burn fossil fuels like gasoline and diesel, we release carbon dioxide (CO2), a greenhouse gas that contributes to climate change. These fuels also contain impurities like N- or S-containing molecules, which, when burned, produce harmful air pollutants such as nitrous oxide (N2O) and sulfur dioxide (SO2). Meanwhile, agricultural activities and improper disposal of rocket fuels have led to nitrate (NO3–) and perchlorate (ClO4–) contamination in groundwater.
Despite this dire situation, some microorganisms have evolved enzymes containing molybdenum (Mo) or tungsten (W) that can efficiently break down these stable molecules through an oxygen atom transfer (OAT) reaction. Inspired by this, our research group aims to develop molecular OAT catalysts that use discrete Mo and W complexes to facilitate important O- and S-atom transfer reactions.
- Seo, J.; Shearer, J.; Williard, P. G.; Kim, E. “Reactivity of a biomimetic W(IV) bis-dithiolene complex with CO2 leading to formate production and structural rearrangement” Dalton Trans, 2019, 48, pp17441-17444
- Elrod, L. T. and Kim, E. “Lewis Acid Assisted Nitrate Reduction with Biomimetic Molybdenum Oxotransferase Complex” Inorg. Chem, 2018, 57, pp2594-2602
Area 3: Molecular Informatics and Computing
Over the last half-century, computing has made incredible strides, bringing us many of the conveniences of modern life. However, there are concerns that these advances will slow down in the years to come. In response, the Kim research group has teamed up with experts in theoretical and physical chemistry, electrical engineering, and computer science to explore new ways of computing using molecules and chemical reactions.
Our team has made exciting progress in this field, showing that small molecules in mixtures can store information effectively and chemical reactions can be used to run parallel pattern recognition algorithms. By exploring alternative computing paradigms, we hope to overcome the challenges facing conventional computation and continue making advances that benefit society.
- Agiza, A. A.; Oakley, K.; Rosenstein, J.; Rubenstein, B. M.; Kim, E.; Riedel, M.; Reda, S. “Digital circuits and neural networks based on acid-base chemistry implemented by robotic fluid handling” Nat. Commun. 2023, 14, 496.
- Arcadia, C.E.; Dombroski, A.; Oakley, K.; Chen, S. L.; Tann, H.; Rose, C.; Kim, E.; Reda, S.; Rubenstein, B.M.; Rosenstein, J.K. “Leveraging autocatalytic reactions for chemical domain image classification” Chem. Sci. 2021, 12, 5464-5472.
- Dombroski, A.; Oakley, K.; Arcadia, C.; Nourael, F.; Ling, S.; Rose, C.; Rubenstein, R.; Rosenstein, J.; Reda, S.; Kim E. “Implementing parallel arithmetic via acetylation and its application to chemical image Processing” Proc. R. Soc. A. 2021, 477, 20200899