Dewey Holten

Dewey Holten

​Professor of Chemistry
PhD, University of Washington, Seattle
BA, Washington University in St. Louis
research interests:
  • Physical and Biophysical Chemistry
  • Primary Reactions of Photosynthesis
  • Tetrapyrrole Photophysics
  • Ultrafast Optical Spectroscopy

contact info:

mailing address:

  • Washington University
    CB 1134
    One Brookings Dr.
    St. Louis, MO 63130-4899

Professor Holten’s research interests include the initial reactions of photosynthesis and photophysical studies of tetrapyrrole chromophores and arrays. The goals of his lab's photosynthesis research are to achieve a molecular-level understanding of charge separation in the bacterial reaction center and design of mutants that endow the reaction enter with properties not realized in nature.  The goals of the tetrapyrrole research are to elucidate the electronic properties of natural and synthetic tetrapyrroles, address fundamental questions in energy and electron transfer, and tailor systems for a range of applications. 

In the reaction center pigment-protein complex, light energy is converted into chemical potential energy by a series of fast electron transfers across the membrane from the photoexcited bacteriochlorophyll special dimer along a chain of electron acceptors on the photoactive A-branch with a quantum yield of ~1. His lab is studying mutants to (1) modulate the rate constants, yields and mechanisms of charge separation versus recombination at each step on both A and B branches, and (2) give electron transfer fully down the normally inactive B branch. The studies of tetrapyrrole chromophores (porphyrin, chlorin, bacteriochlorin) are aimed at elucidating the interplay between molecular composition, electronic structure, and photophysical properties. These properties include absorption and emission spectra and the rate constants and yields of the singlet excited-state decay pathways (fluorescence, internal conversion, intersystem crossing). Studies of multichromophore arrays probe fundamental aspects of energy and electron transfer including the potential effects of coherence phenomena.  The collective studies provide insights and design principles that for constructing chromophores and arrays for use in solar-energy and life-sciences research.

Selected Publications

Balancing Panchromatic Absorption and Multistep Charge Separation in a Compact Molecular Architecture, A. Roy, N. C. M. Magdaong, H. Jing, J. Rong, J. R. Diers, H.  S. Kang, D. M. Niedzwiedzki, M. Taniguchi, C. Kirmaier, J. S. Lindsey, D. F. Bocian, and D. Holten, J. Phys. Chem A  2022, 126, 9352-9365.

High Yield of B-side Electron Transfer at 77 K in the Photosynthetic Reaction Center Protein from Rhodobacter sphaeroides, N.C. M. Magdaong, K. M. Faries, J. C. Buhrmaster, G. A. Tira, R. M. Wyllie, C. E. Kohout, D. K. Hanson, P. D. Laible, D. Holten, and C. Kirmaier, J. Phys. Chem. B 2022, 126, 8940-8956.

Probing the Effects of Electronic-Vibrational Resonance on the Rate of Excited-State Energy Transfer in Bacteriochlorin Dyads, N. C. M. Magdaong, H. Jing, J. R. Diers, C. Kirmaier, J. S. Lindsey, D. F. Bocian, and D. Holten, J. Phys. Chem. Lett. 2022, 13, 7906-7910.                 

Perspective on the Redox Properties of Tetrapyrrole Macrocycles, J. R. Diers, C. Kirmaier, M. Taniguchi, J. S. Lindsey, D. F. Bocian, and D. Holten, Phys. Chem. Chem. Phys. 2021, 23, 19130–19140.

In Situ, Protein-Mediated Generation of a Photochemically Active Chlorophyll Analog in a Mutant Bacterial Photosynthetic Reaction Center, N. C. M. Magdaong, J. C. Buhrmaster, K. M. Faries, H. Liu, G. A. Tira, J. S. Lindsey, D. K. Hanson, D. Holten, P. D. Laible, and C. Kirmaier, Biochemistry 2021, 60, 1260-1275.

Photophysical Properties and Electronic Structure of Zinc(II) Porphyrins Bearing Zero to Four meso-Phenyl Substituents – Zinc Porphine to Zinc Tetraphenylporphyrin (ZnTPP), N. C. M. Magdaong, M. Taniguchi, J. R. Diers, D. M. Niedzwiedzki, C. Kirmaier, J. S. Lindsey, D. F. Bocian, and D. Holten, J. Phys. Chem. A. 2020, 124, 7777-7794.

Switching Sides - Re-Engineered Primary Charge Separation in the Bacterial Photosynthetic Reaction Center, P. D. Laible, D. K. Hanson, J C. Burhmaster, G. A. Tira, K. M. Faries, D. Holten, and C. Kirmaier, Proc. Nat Acad. Sci. U.S.A. 2020, 117, 865-871.

Annulated Bacteriochlorins for Near-Infrared Photophysical Studies, H. Fujita, H. Jing, M. Krayer, S. Allu, G. Veeraraghavaiah, Z. Wu, J. Jiang, J. R. Diers, N. C. M. Magdaong, A. K. Mandal, A. Roy, D. M. Niedwiedzki, C. Kirmaier, D. F. Bocian, D. Holten and J. S. Lindsey, New Journal of Chemistry 2019, 3, 7209-7232.

Origin of Panchromaticity in Multichromophore-Tetrapyrrole Arrays, J. M. Yuen, J. R. Diers, E. J. Alexy, A. Roy, A. K. Mandal, H. S. Kang, D. M. Niedzwiedzki, C. Kirmaier, J. S. Lindsey, D. F. B, and D. Holten , J. Phys. Chem. A 2018, 122, 7181-7201.122, 7181-7201.

Tailoring Panchromatic Absorption and Excited-State Dynamics of Tetrapyrrole–Chromophore (Bodipy, Rylene) Arrays. The Interplay of Orbital Mixing and Configuration Interaction, A. K. Mandal, J. R. Diers, D. M. Niedziedzki, G. Hu, R. Liu, E. J. Alexy, J. S. Lindsey, D. F. Bocian, and D. Holten, J. Am. Chem. Soc. 2017, 139, 17547-17564.

Effects of Substituents on Synthetic Analogs of Chlorophylls.  Part 4: How Formyl Group Location Dictates the Spectral

Properties of Chlorophylls b, d and f, J. M. Yuen, M. A. Harris, M. Liu, J. R. Diers, C. Kirmaier, D. F. Bocian, J. S. Lindsey and D. Holten, Photochem. Photobiol.2015, 91, 331-342.

Extending the Short and Long Wavelength Limits of Bacteriochlorin Near-Infrared Absorption via Dioxo- and Bisimide-Functionalization, P. Vairaprakash, E. Yang, T. Sahin, M. Taniguchi, M. Krayer, J. R. Diers, A. Wang, D. M. Niedzwiedzki, C. Kirmaier, J. S. Lindsey, D. F. Bocian, and D. Holten, J. Phys. Chem. B, 2015, 119, 4382-4995.

Optimizing Multi-Step B-side Charge Separation in Photosynthetic Reaction Centers from Rhodobacter capsulatus, K. M. Faries, L. Kressel, N. P. Dylla, Marc J. Wander, D. K. Hanson, D. Holten, P. D. Laible, C. Kirmaier, Biochem. Biophys Acta. 2016, 1857,150-159.

Effects of Strong Electronic Coupling in Chlorin and Bacteriochlorin Dyads, H. S. Kang, N. N. Esemoto, J. R. Diers, D. M. Niedzwiedzki, J. A. Greco, J. Akhigbe, Z. Yu, C. Pancholi, G. V. Bhagavathy, J. K. Nguyen, C. Kirmaier, R. R. Birge, M. Ptaszek, D. Holten and D. F. Bocian, J. Phys. Chem. A. 2016, 120, 379-395.

Manipulating the Energetics and Rates of Electron Transfer in R. capsulatus Reaction Centers with Asymmetric Pigment Content, K. M. Faries, N. P. Dylla, D. K. Hanson, D. Holten, P. D. Laible, C. Kirmaier, J. Phys. Chem. B., 2017, 121, 6989-7004.

Augmenting light coverage for photosynthesis through YFP-enhanced charge separation at the Rhodobacter sphaeroides reaction centre, K. J. Grayson, K. M. Faries, X. Huang, P. Qian, P. Dilbeck, E. C. Martin, A. Hitchcock, C. Vasilev, J. M. Yuen, D. M. Niedzwiedzki, G. J. Leggett, D. Holten, C. Kirmaier and C. N. Hunter, Nature Communications, 2017, 8, 1-12.

Tailoring Panchromatic Absorption and Excited-State Dynamics of Tetrapyrrole–Chromophore (Bodipy, Rylene) Arrays. The Interplay of Orbital Mixing and Configuration Interaction, A. K. Mandal, J. R. Diers, D. M. Niedziedzki, G. Hu, R. Liu, E. J. Alexy, J. S. Lindsey, D. F. Bocian, and D. Holten, J. Am. Chem. Soc. 2017, 139, 17547-17564.

Origin of Panchromaticity in Multichromophore-Tetrapyrrole Arrays, J. M. Yuen, J. R. Diers, E. J. Alexy, A. Roy, A. K. Mandal, H. S. Kang, D. M. Niedzwiedzki, C. Kirmaier, J. S. Lindsey, D. F. B, and D. Holten , J. Phys. Chem. A 2018, 122, 7181-7201.
 

in the news:

Switching tracks: Understanding photosynthesis

Back to Ampersand