The Minteer Research Group is currently focused on studying bioelectrocatalysis. We have two main projects: enzyme cascades for bioelectrocatalysis and microbial bioelectrocatalysis for sensing and energy conversion applications. Our research in enzymatic bioelectrocatalysis is focused on both the bioengineering of natural enzymatic metabolic pathways for bioanodes for biofuel cells as well as enzyme discovery and enzyme engineering for non-natural complete oxidation pathways for biofuels. Recently, we have expanded these enzyme cascades for electrosynthesis. Our research in microbial-based bioelectrocatalysis is focused on the fundamental understanding of extracellular electron transfer between electrodes and microbes, as well as the application of microbial bioelectrocatalysis for biosensing, energy conversion, and electrosynthesis.
Biofuel cells are a type of fuel cell where a biocatalyst is used as the catalyst for converting the chemical energy of a fuel into electrical energy, instead of a traditional metallic catalyst. Our research group has made advances in enzymatic fuel cell lifetimes over the last decade due to the development of a novel enzyme immobilization membrane that three-dimensionally constrains the enzyme while providing a buffered pH and a hydrophobic environment that mimics the cellular environment. However, in order to effectively utilize biofuel cells as energy conversion devices, it is essential to be able to use enzyme cascades to allow for complete oxidation of complex biofuels and, thereby, high energy densities, as well as coupling to an air breathing biocathode to ensure high current densities. In a living cell, complex fuels/substrates are completely oxidized to carbon dioxide utilizing the enzymatic cascades of metabolic pathways, such as: the Kreb's cycle, glycolysis, etc. These metabolic pathways can be used to oxidize fuels in a biofuel cell, but require the immobilization of over 20 enzymes at a bioanode, whereas only 6 of these enzymes are dehydrogenase (i.e. electron producing enzymes). We have employed metabolic engineering to design and study these systems. However, we are also developing enzymatic cascades for complete oxidation of a variety of biofuels by employing non-specific PQQ-dependent dehydrogenases. We have previously shown the ability to do this for the complex alcoholic fuels: ethylene glycol and glycerol. Recently, we have been using biofuel cells as a tool for electrosynthesis of value-added products from ammonia to chiral amines and chiral amino acids.
The metabolic pathways discussed above exist within living organisms, so we also have a program looking at microbial bioelectrocatalysis for sensors, fuel cells, and the electrosynthesis of value-added compounds that focuses on using microbial metabolism and synthetic biology to use electrodes as a source or sink of electrons. This involves studying microbes that can undergo extracellular electron transfer between the microbe and the electrode.
References (Selected Publications)
- H. Chen, M. Prater, R. Cai, F. Dong, H. Chen, and S.D. Minteer, “Bioelectrocatalytic Conversion from N2 to Chiral Amino Acids in a H2/α-keto Acid Enzymatic Fuel Cell,” Journal of the American Chemical Society, 2020, 142, 4028-4036.
- H. Chen, F. Dong, and S.D. Minteer, “The progress and outlook of bioelectrocatalysis for the production of chemicals, fuels, and materials,” Nature Catalysis, 2020, 3, 225–244.
- R. Milton and S.D. Minteer, “Nitrogenase Bioelectrochemistry for Synthesis Applications,” Accounts of Chemical Research, 2019, 52, 3351-3360.
- C. Sandford, L. Fries, T. Ball, S.D. Minteer, and M.S. Sigman, “Mechanistic Studies into the Oxidative Addition of Co(I) Complexes: Combining Electroanalytical Techniques with Parameterization,” Journal of the American Chemical Society, 2019, 141, 18877-18889.
- D. Hickey, R. Cai, Z.Y. Yang, K. Grunau, O. Einsle, L. Seefeldt, and S.D. Minteer, “Establishing a Thermodynamic Landscape for the Active Site of Mo-Dependent Nitrogenase,” Journal of the American Chemical Society, 2019, 141, 17150-17157.
- M. Yuan, M. Kummer, and S.D. Minteer, “Strategies for Bioelectrochemical CO2 Reduction,” Chemistry- A European Journal, 2019, 25, 14258-14266.
- B. Bulutoglu, F. Macao, J. Bale, N. King, D. Baker, S.D. Minteer, and S. Banta, “Multimerization of an Alcohol Dehydrogenase by Fusion to a Designed Self-Assembling Protein Results in Enhanced Bioelectrocatalytic Operational Stability,” ACS Applied Materials & Interfaces, 2019, 11, 20022-20028.
- M. Yuan, M. Kummer, R. Milton, T. Quah, and S.D. Minteer, “Efficient NADH Regeneration by a Redox Polymer-Immobilized Enzymatic System,” ACS Catalysis, 2019, 9, 5486-5495.
- Y. Kawamata, J.C. Vantourout, D.P. Hickey, P. Bai, L. Chen, Q. Hou, W. Qiao, K. Barman, M. Edwards, A. Garrido-Castro, J. deGruyter, H. Nakamura, K. Knouse, C. Qin, K. Clay, D. Bao, C. Li, J. Starr, C. Garcia-Irizarry, N. Sach, H. White, M. Neurock, S.D. Minteer, and P. Baran, “Electrochemically Driven, Ni-Catalyzed Aryl Amination: Scope, Mechanism, and Applications,” Journal of the American Chemical Society, 2019, 141, 6392-6402.
- H. Chen, R. Cai, J. Patel, F. Dong, H. Chen, and S.D. Minteer, “Upgraded Bioelectrocatalytic N2 Fixation to Chiral Amine Intermediates,” Journal of the American Chemical Society, 2019, 141, 4963-4971.
- G. Pankratova, D. Pankratov, R.D. Milton, S.D. Minteer, and L. Gorton, “Following Nature: Bioinspired Mediation Strategy for Gram-positive Bacterial Cells,” Advanced Energy Materials, 2019, 1900215.
- B.K. Peters, K.X. Rodriguez, S.H. Reisberg, S.B. Beil, D.P. Hickey, Y. Kawamata, M. Collins, J. Starr, L. Chen, S. Udyavara, K. Klunder, T. Gorey, S.L. Anderson, M. Neurock, S.D. Minteer, and P.S. Baran, “Scalable and safe synthetic organic electroreduction inspired by Li-ion battery chemistry,” Science, 2019, 363, 838-845.
- D.P. Hickey, C. Sandford, Z. Rhodes, T. Gensch, L. Fries, M.S. Sigman, and S.D. Minteer, “Investigating the Role of Ligand Electronics on Stabilizing Electrocatalytically Relevant Low Valent Co(I) Intermediates,” Journal of the American Chemical Society, 2019, 141, 1382-1392.
- R.D. Milton, R. Cai, S. Sahin, S. Abdellaoui, B. Alkotaini, D. Leech, and S.D. Minteer, “The In Vivo Potential-Regulated Protective Protein of Nitrogenase in Azotobacter vinelandii Supports Aerobic Bioelectrochemical Dinitro-gen Reduction In Vitro,” Journal of the American Chemical Society, 2017, 139, 9044-9052.
- Y. Liu, D.P. Hickey, J.Y. Guo, E. Earl, S. Abdellaoui, R. Milton, M.S. Sigman, S.D. Minteer, and S. Calabrese Barton, “Substrate Channeling in an Artificial Metabolon: A Molecular Dynamics Blueprint for an Experimental Peptide Bridge,” ACS Catalysis, 2017, 7, 2486-93.
- J. Kitt, D. Bryce, S.D. Minteer, and J.M. Harris, “Raman Spectroscopy Reveals Selective Interactions of Cytochrome c with Cardiolipin that Correlate with Membrane Permeability,” Journal of the American Chemical Society, 139(10), 3851-3860.
- K. Van Nguyen and S.D. Minteer. “Investigating DNA hydrogels as a new biomaterial for enzyme immobilization in biobatteries,” Chem Commun (Camb), 2015, 51, 13071-3.
- M. Rasmussen, S. Abdellaoui, and S.D. Minteer. “Enzymatic biofuel cells: 30 years of critical advancements,” Biosens Bioelectron, 2015, 76, 91-102.
- S. Aquino Neto, D.P. Hickey, R.D. Milton, A.R. De Andrade, and S.D. Minteer. “High current density PQQ-dependent alcohol and aldehyde dehydrogenase bioanodes,” Biosens Bioelectron, 2015, 72, 247-54.
- R.D. Milton, K. Lim, D.P. Hickey, and S.D. Minteer. “Employing FAD-dependent glucose dehydrogenase within a glucose/oxygen enzymatic fuel cell operating in human serum,” Bioelectrochemistry, 2015, 106, 56-63.
- M. Rasmussen and S.D. Minteer. “Long-term arsenic monitoring with an Enterobacter cloacae microbial fuel cell,” Bioelectrochemistry, 2015, 106, 207-12.
- K. Van Nguyen and S.D. Minteer. “DNA-functionalized Pt nanoparticles as catalysts for chemically powered micromotors: toward signal-on motion-based DNA biosensor,” Chem Commun (Camb), 2015, 51, 4782-4.
- R.C. Reid, S.D. Minteer, and B.K. Gale. “Contact lens biofuel cell tested in a synthetic tear solution,” Biosens Bioelectron, 2015, 68, 142-8.
- F. Wu and S. Minteer S. “Krebs cycle metabolon: structural evidence of substrate channeling revealed by cross-linking and mass spectrometry,” Angew Chem Int Ed Engl, 2015, 54, 1851-4.
- F. Wu, L.N. Pelster, and S.D. Minteer. “Krebs cycle metabolon formation: metabolite concentration gradient enhanced compartmentation of sequential enzymes,” Chem Commun (Camb), 2015, 51, 1244-7.