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Time-resolved FTIR difference spectroscopy for the study of photosystem I with high potential naphthoquinones incorporated into the A1 binding site 2: Identification of neutral state quinone bands

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Abstract

Time-resolved step-scan FTIR difference spectroscopy at 77 K has been used to study photosystem I (PSI) from Synechocystis sp. PCC 6803 with four high-potential, 1,4–naphthoquinones (NQs) incorporated into the A1 binding site. The incorporated quinones are 2–chloro–NQ (2ClNQ), 2–bromo–NQ (2BrNQ), 2,3–dichloro–NQ (Cl2NQ), and 2,3–dibromo–NQ (Br2NQ). For completeness 2-methyl-NQ (2MNQ) was also incorporated and studied. Previously, PSI with the same quinones incorporated were studied in the, so-called, anion spectral region between 1550 and 1400 cm−1 (Agarwala et al. in Biochim Biophys Acta 1864(1):148918, 2023). Here we focus on spectra in the previously unexplored 1400–1200 cm−1 spectral region. In this region several bands are identified and assigned to the neutral state of the incorporated quinones. This is important as identification of neutral state quinone bands in the regular 1700–1600 cm−1 region has proven difficult in the past. For neutral PhQ in PSI a broad, intense band appears at ~ 1300 cm−1. For the symmetric di-substituted NQs (Cl2NQ/Br2NQ) a single intense neutral state band is found at ~ 1280/1269 cm−1, respectively. For both mono-substituted NQs, 2ClNQ and 2BrNQ, however, two neutral state bands are observed at ~ 1280 and ~ 1250 cm−1, respectively. These observations from time-resolved spectra agree well with conclusions drawn from absorption spectra of the NQs in THF, which are also presented here. Density functional theory based vibrational frequency calculations were undertaken allowing an identification of the normal modes associated with the neutral state quinone bands.

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Abbreviations

Cl2NQ:

2,3–Dichloro–NQ

Br2NQ:

2,3–Dibromo–NQ

2ClNQ:

2–Chloro–NQ

2BrNQ:

2–Bromo–NQ

2MNQ:

2–Methyl–NQ

C=O:

Carbonyl

Chl a :

Chlorophyll a

DAS:

Decay associated spectrum

DDS:

Double difference spectrum

DFT:

Density functional theory

DS:

Difference spectra/spectrum/spectroscopy

ET:

Electron transfer

FTIR:

Fourier transform infrared

H–bond:

Hydrogen bond

NQ:

1,4–Naphthoquinone

PhQ:

Phylloquinone (2–methyl–3–phytyl–NQ)

PQ:

Plastoquinone–9

DMNQ:

2,3–Dimethyl–NQ

PSI:

Photosystem I

PSII:

Photosystem II

RC:

Reaction center

S6803:

Synechocystis Sp. PCC 6803

THF:

Tetrahydrofuran

TRSS:

Time–resolved step–scan

WT:

Wild type

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Acknowledgements

This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award Number DE−SC−0017937 to GH. The statements made herein are solely the responsibility of the authors. NA acknowledges a fellowship from the Molecular Basis of Disease Program at Georgia State University.

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Authors and Affiliations

  1. Department of Physics and Astronomy, Georgia State University, Atlanta, GA, USA

    Neva Agarwala & Gary Hastings

  2. Department of Chemistry, Georgia State University, Atlanta, GA, USA

    Neva Agarwala

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  1. Neva Agarwala
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  2. Gary Hastings
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NA: Methodology, formal analysis, data curation, writing—original draft. GH: conceptualization, formal analysis, resources, writing—review & editing, supervision, funding acquisition, project administration. All authors reviewed the manuscript.

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Correspondence to Gary Hastings.

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Agarwala, N., Hastings, G. Time-resolved FTIR difference spectroscopy for the study of photosystem I with high potential naphthoquinones incorporated into the A1 binding site 2: Identification of neutral state quinone bands. Photosynth Res 158, 1–11 (2023). https://doi.org/10.1007/s11120-023-01036-8

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