Electronic Structure of the Primary Electron Donor P700+• in Photosystem I Studied by Multifrequency HYSCORE Spectroscopy at X- and Q-Band

Chestnut, Melanie M.; Milikisiyants, Sergey; Chatterjee, Ruchira; Kern, Jan; Smirnov, Alex I.

doi:10.1021/acs.jpcb.0c09000

Title: Electronic Structure of the Primary Electron Donor P₇₀₀^+• in Photosystem I Studied by Multifrequency HYSCORE Spectroscopy at X- and Q-Band

Abstract

The primary electron donor P₇₀₀ of the photosystem I (PSI) is a heterodimer consisting of two chlorophyll molecules. A series of electron-transfer events immediately following the initial light excitation leads to a stabilization of the positive charge by its cation radical form, P₇₀₀^+•. Here, the electronic structure of P₇₀₀^+• and, in particular, its asymmetry with respect to the two chlorophyll monomers is of fundamental interest and is not fully understood up to this date. Here, we apply multifrequency X- (9 GHz) and Q-band (35 GHz) hyperfine sublevel correlation (HYSCORE) spectroscopy to investigate the electron spin density distribution in the cation radical P₇₀₀^+• of PSI from a thermophilic cyanobacterium Thermosynechococcus elongatus. Six ¹⁴N and two ¹H distinct nuclei have been resolved in the HYSCORE spectra and parameters of the corresponding nuclear hyperfine and quadrupolar hyperfine interactions were obtained by combining the analysis of HYSCORE spectral features with direct numerical simulations. Based on a close similarity of the nuclear quadrupole tensor parameters, all of the resolved ¹⁴N nuclei were assigned to six out of total eight available pyrrole ring nitrogen atoms (i.e., four in each of the chlorophylls), providing direct evidence of spin density delocalization over the both monomers in the heterodimer.more »« less

Authors:

^[1]; Milikisiyants, Sergey ^[1];

^[2];

^[1]

North Carolina State Univ., Raleigh, NC (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Publication Date:: Thu Dec 24 00:00:00 EST 2020

Research Org.:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

OSTI Identifier:: 1844514

Grant/Contract Number:: AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

Additional Journal Information:: Journal Volume: 125; Journal Issue: 1; Journal ID: ISSN 1520-6106

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Magnetic properties; Electron paramagnetic resonance spectroscopy; Electron density; Quantum mechanics; Energy levels

Citation Formats


                    Chestnut, Melanie M., Milikisiyants, Sergey, Chatterjee, Ruchira, Kern, Jan, and Smirnov, Alex I. Electronic Structure of the Primary Electron Donor P700+• in Photosystem I Studied by Multifrequency HYSCORE Spectroscopy at X- and Q-Band.  United States: N. p., 2020. 
Web.  doi:10.1021/acs.jpcb.0c09000.

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                    Chestnut, Melanie M., Milikisiyants, Sergey, Chatterjee, Ruchira, Kern, Jan, & Smirnov, Alex I. Electronic Structure of the Primary Electron Donor P700+• in Photosystem I Studied by Multifrequency HYSCORE Spectroscopy at X- and Q-Band.  United States.  https://doi.org/10.1021/acs.jpcb.0c09000

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                    Chestnut, Melanie M., Milikisiyants, Sergey, Chatterjee, Ruchira, Kern, Jan, and Smirnov, Alex I. Thu .  
"Electronic Structure of the Primary Electron Donor P700+• in Photosystem I Studied by Multifrequency HYSCORE Spectroscopy at X- and Q-Band".  United States.  https://doi.org/10.1021/acs.jpcb.0c09000.  https://www.osti.gov/servlets/purl/1844514.

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@article{osti_1844514,

  title        = {Electronic Structure of the Primary Electron Donor P700+• in Photosystem I Studied by Multifrequency HYSCORE Spectroscopy at X- and Q-Band},

  author       = {Chestnut, Melanie M. and Milikisiyants, Sergey and Chatterjee, Ruchira and Kern, Jan and Smirnov, Alex I.},

  abstractNote = {The primary electron donor P700 of the photosystem I (PSI) is a heterodimer consisting of two chlorophyll molecules. A series of electron-transfer events immediately following the initial light excitation leads to a stabilization of the positive charge by its cation radical form, P700+•. Here, the electronic structure of P700+• and, in particular, its asymmetry with respect to the two chlorophyll monomers is of fundamental interest and is not fully understood up to this date. Here, we apply multifrequency X- (9 GHz) and Q-band (35 GHz) hyperfine sublevel correlation (HYSCORE) spectroscopy to investigate the electron spin density distribution in the cation radical P700+• of PSI from a thermophilic cyanobacterium Thermosynechococcus elongatus. Six 14N and two 1H distinct nuclei have been resolved in the HYSCORE spectra and parameters of the corresponding nuclear hyperfine and quadrupolar hyperfine interactions were obtained by combining the analysis of HYSCORE spectral features with direct numerical simulations. Based on a close similarity of the nuclear quadrupole tensor parameters, all of the resolved 14N nuclei were assigned to six out of total eight available pyrrole ring nitrogen atoms (i.e., four in each of the chlorophylls), providing direct evidence of spin density delocalization over the both monomers in the heterodimer. Using the obtained experimental values of the 14N electron-nuclear hyperfine interaction parameters, the upper limit of the electron spin density asymmetry parameter is estimated as RA/Bupper = 7.7 ± 0.5, while a tentative assignment of 14N observed in the HYSCORE spectra yields RB/A = 3.1 ± 0.5.},

  doi          = {10.1021/acs.jpcb.0c09000},

  journal      = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},

  number       = 1,

  volume       = 125,

  place        = {United States},

  year         = {Thu Dec 24 00:00:00 EST 2020},

  month        = {Thu Dec 24 00:00:00 EST 2020}

}

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2D ESEEM of the [sup 15]N-labeled radical cations of bacteriochlorophyll a and of the primary donor in reaction centers of Rhodobacter sphaeroides

Journal Article Kaess, H ; Rautter, J ; Boenigk, B ; ... - Journal of Physical Chemistry; (United States)

The radical cations of [[sup 15]N]bacteriochlorophyll a and of the primary donor P[sub 865] in [sup 15]N-labeled reaction centers of Rhodobacter spaeroides R-26.1 were investigated in frozen solutions using two-dimensional ESEEM methods. Both three-pulse (stimulated echo) and four-pulse (HYSCORE) sequences were employed to avoid ambiguities in data analysis. Computer simulations of the experimental powder spectra were performed, yielding a complete set of nitrogen hyperfine coupling tensors for both systems. The obtained tensor values are compared with those from ENDOR measurements and from semiempirical INDO-type MO calculations. The results obtained from 2D stimulated echo ESEEM and HYSCORE for P[sub 865][sup [centermore »« less
https://doi.org/10.1021/j100001a065

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Title: Electronic Structure of the Primary Electron Donor P₇₀₀^+• in Photosystem I Studied by Multifrequency HYSCORE Spectroscopy at X- and Q-Band

Structure and Energy Transfer in Photosystems of Oxygenic Photosynthesis
journal, June 2015

Specific Distribution of Phosphatidylglycerol to Photosystem Complexes in the Thylakoid Membrane
journal, November 2017

The g -Factor Anisotropy of Plant Chlorophyll a ^•+
journal, July 2000

Multiple quantum coherence in HYSCORE spectra
journal, June 2001

Trapping Dynamics in Photosystem I-Light Harvesting Complex I of Higher Plants Is Governed by the Competition Between Excited State Diffusion from Low Energy States and Photochemical Charge Separation
journal, October 2017

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journal, August 1996

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journal, August 2002

Submillimeter High-Field EPR Studies of the Primary Donor in Plant Photosystem I P700 ^•+
journal, November 1997

Ultrafast Transient Absorption Studies on Photosystem I Reaction Centers from Chlamydomonas reinhardtii. 1. A New Interpretation of the Energy Trapping and Early Electron Transfer Steps in Photosystem I
journal, December 2003

Independent initiation of primary electron transfer in the two branches of the photosystem I reaction center
journal, February 2010

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journal, September 2004

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journal, July 1996

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journal, May 2008

Photosystems and global effects of oxygenic photosynthesis
journal, August 2011

ESR, ENDOR and TRIPLE resonance studies of the primary donor radical cation P960+• in the photosynthetic bacterium Rhodopseudomonas viridis
journal, July 1988

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journal, June 2001

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journal, January 1996

A Structural Model for the Charge Separated State in Photosystem I from the Orientation of the Magnetic Interaction Tensors
journal, October 2000

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journal, July 2007

Analysis of ¹ ⁴ N ESEEM patterns of randomly oriented solids
journal, November 1987

Cofactors Involved in Light-Driven Charge Separation in Photosystem I Identified by Subpicosecond Infrared Spectroscopy
journal, February 2011

Mechanism of adiabatic primary electron transfer in photosystem I: Femtosecond spectroscopy upon excitation of reaction center in the far-red edge of the QY band
journal, November 2017

FTIR Study of the Primary Electron Donor of Photosystem I (P700) Revealing Delocalization of the Charge in P700 ⁺ and Localization of the Triplet Character in ³ P700
journal, September 1999

Protein–cofactor interactions in bioenergetic complexes: The role of the A1A and A1B phylloquinones in Photosystem I
journal, September 2009

The electronic structure of the primary donor cation radical in Rhodobacter sphaeroides R-26: ENDOR and TRIPLE resonance studies in single crystals of reaction centers
journal, November 1993

The chlorophyll triplet state as a probe of structure and function in photosynthesis
journal, March 1991

Photosystem I
journal, July 1996

High-Resolution Two-Dimensional ¹ H and ¹⁴ N Hyperfine Sublevel Correlation Spectroscopy of the Primary Quinone of Photosystem II
journal, February 2011

Cationic State Distribution over the P700 Chlorophyll Pair in Photosystem I
journal, October 2011

Mutation Induced Modulation of Hydrogen Bonding to P700 Studied Using FTIR Difference Spectroscopy
journal, July 2003

Computational Investigation of the Spin-Density Asymmetry in Photosynthetic Reaction Center Models from First Principles
journal, May 2020

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journal, October 1979

Purification, characterisation and crystallisation of photosystem II from Thermosynechococcus elongatus cultivated in a new type of photobioreactor
journal, January 2005

Function and organization of Photosystem I polypeptides
journal, May 1995

Nanotube Array Method for Studying Lipid-Induced Conformational Changes of a Membrane Protein by Solid-State NMR
journal, January 2015

Pulsed EPR Study of Spin-Coupled Radical Pairs in Photosynthetic Reaction Centers: Measurement of the Distance Between and in Photosystem I and between and in Bacterial Reaction Centers
journal, February 1997

Primary Donor Photo-Oxidation in Photosystem I: A Re-Evaluation of (P700 ⁺ − P700) Fourier Transform Infrared Difference Spectra ^†
journal, October 2001

Molecular orbital study of the primary electron donor P700 of photosystem I based on a recent X-ray single crystal structure analysis
journal, November 2003

P700: the primary electron donor of photosystem I
journal, October 2001

Ultrafast Transient Absorption Studies on Photosystem I Reaction Centers from Chlamydomonas reinhardtii. 2: Mutations near the P700 Reaction Center Chlorophylls Provide New Insight into the Nature of the Primary Electron Donor
journal, January 2006

Analysis of electron donors in photosystems in oxygenic photosynthesis by photo-CIDNP MAS NMR
journal, November 2015

Intensity of Cross-Peaks in Hyscore Spectra of S = 1/2, I = 1/2 Spin Systems
journal, June 2000

5- and 6-pulse electron spin echo envelope modulation (ESEEM) of multi-nuclear spin systems
journal, February 2008

High-frequency EPR studies on cofactor radicals in photosystem I
journal, December 2001

Measurement of the g-tensor of the P700+. signal from deuterated cyanobacterial photosystem I particles.
journal, October 1993

15N and 31P solid-state NMR study of transmembrane domain alignment of M2 protein of influenza A virus in hydrated cylindrical lipid bilayers confined to anodic aluminum oxide nanopores
journal, April 2005

Hyperfine sublevel correlation (hyscore) spectroscopy: a 2D ESR investigation of the squaric acid radical
journal, December 1986

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journal, July 2000

Flow-Through Lipid Nanotube Arrays for Structure-Function Studies of Membrane Proteins by Solid-State NMR Spectroscopy
journal, October 2006

Femtosecond infrared spectroscopy of chlorophyll f-containing photosystem I
journal, January 2019

A High-Field EPR Study of P ₇₀₀ ⁺ ^• in Wild-Type and Mutant Photosystem I from Chlamydomonas reinhardtii ^,
journal, January 2004

Structure and Function of Photosystem I
journal, June 1992

Photosystem I photochemistry under highly reducing conditions: Study of the P700 triplet state formation from the secondary radical pair (P700+−A−1)
journal, December 1990

Substrate-Supported Lipid Nanotube Arrays
journal, July 2003

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journal, May 1985

P HOTOSYSTEM I: Function and Physiology
journal, June 2001

Orientation and Electronic Structure of the Primary Donor Radical Cation in Photosystem I: A Single Crystals EPR and ENDOR Study
journal, February 2001

Photochemical processes in photosynthesis studied by advanced electron paramagnetic resonance techniques
journal, January 2003

EasySpin, a comprehensive software package for spectral simulation and analysis in EPR
journal, January 2006

High-resolution absorbance-difference spectra of the triplet state of the primary donor P-700 in Photosystem I subchloroplast particles measured with absorbance-detected magnetic resonance at 1.2 K. Evidence that P-700 is a dimeric chlorophyll complex
journal, July 1983