Activation energies for two steps in the S2 → S3 transition of photosynthetic water oxidation from time-resolved single-frequency infrared spectroscopy

Mäusle, Sarah M.; Abzaliyeva, Aiganym; Greife, Paul; Simon, Philipp S.; Pérez, R. Pena De; Zilliges, Yvonne; Dau, Holger

doi:10.1063/5.0027995

Cited by 25 publications

(28 citation statements)

References 94 publications

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“…Early changes (50 µs after the 2nd flash) are observed around the water network at the PsbO-D2 interface (Fig. 5a ), which may indicate a fast, long-range electrostatically triggered proton release of surface carboxylates as found in PS II membrane particles from plants 14 , 62 . The short H-bonding interaction of E65 and R334 in the open state of the gate at 150 µs may indicate that a proton is already released from the gate in line with a suggested fast refilling of the earlier deprotonated site 62 .…”

Section: Discussionmentioning

confidence: 92%

“…5a ), which may indicate a fast, long-range electrostatically triggered proton release of surface carboxylates as found in PS II membrane particles from plants 14 , 62 . The short H-bonding interaction of E65 and R334 in the open state of the gate at 150 µs may indicate that a proton is already released from the gate in line with a suggested fast refilling of the earlier deprotonated site 62 . Alternatively, the gate may stay open until the proton is released in an apparent single proton hopping event occurring with Mn oxidation 56 .…”

Section: Discussionmentioning

confidence: 99%

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Structural dynamics in the water and proton channels of photosystem II during the S2 to S3 transition

et al. 2021

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Light-driven oxidation of water to molecular oxygen is catalyzed by the oxygen-evolving complex (OEC) in Photosystem II (PS II). This multi-electron, multi-proton catalysis requires the transport of two water molecules to and four protons from the OEC. A high-resolution 1.89 Å structure obtained by averaging all the S states and refining the data of various time points during the S2 to S3 transition has provided better visualization of the potential pathways for substrate water insertion and proton release. Our results indicate that the O1 channel is the likely water intake pathway, and the Cl1 channel is the likely proton release pathway based on the structural rearrangements of water molecules and amino acid side chains along these channels. In particular in the Cl1 channel, we suggest that residue D1-E65 serves as a gate for proton transport by minimizing the back reaction. The results show that the water oxidation reaction at the OEC is well coordinated with the amino acid side chains and the H-bonding network over the entire length of the channels, which is essential in shuttling substrate waters and protons.

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Section: Discussionmentioning

confidence: 92%

Section: Discussionmentioning

confidence: 99%

Structural dynamics in the water and proton channels of photosystem II during the S2 to S3 transition

et al. 2021

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“…The S 2 → S 3 transition was studied in details [110,111], also by another research group [112]. In particular, results from the Noguchi group [107] suggested that during the S 2 → S 3 transition proton release is a rate-limiting step in the proton-coupled electron transfer.…”

Section: Photosystem II Reaction Centersmentioning

confidence: 99%

Time-resolved infrared absorption spectroscopy applied to photoinduced reactions: how and why

Mezzetti

Schnee

Lapini³

et al. 2022

Photochem Photobiol Sci

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Time-resolved infrared (IR) spectroscopy is a widely used technique in the investigation of photoinduced reactions, given its capabilities of providing structural information about the presence of intermediates and the reaction mechanism. Despite the fact that it is used in several fields since the '80s, the communication between the different scientific communities (photochemists, photobiologists, etc.) has been to date quite limited. In some cases, this lack of communication happened-and still happens-even inside the same scientific community (for instance between specialists in ultrafast ps/fs IR and those in "fast" ns/µs/ms IR). Even more surprising is the difficulty of non-specialists to understand the potential of time-resolved IR spectroscopy, despite the fact that IR spectroscopy is normally taught to all chemistry and material science students, and to several biology and physics students. This tutorial review aims at helping to solve these issues, first by providing a comprehensive but reader-friendly overview of the different techniques, and second, by focusing on five "case studies" (from photobiology, gas-phase photocatalysis, photochemistry, semiconductors and metal-carbonyl complexes). We are confident that this approach can help the reader-whichever is its background-to understand the capabilities of time-resolved IR spectroscopy to study the mechanism of photoinduced reactions.

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“…The faster phase with a t1/2 ≤ 25 µs is attributed to a proton transfer/release. This fast phase precedes the electron transfer from S2 to the TyrZ • that occurs with a t1/2 ≤ 300 µs [54][55][56][57][58]. It was discussed earlier that the fast phase could correspond to the release of a proton in an intermediate step S2 LS TyrZ  → S2 HS TyrZ  before the S2 HS TyrZ  → S3 S=3 transition occurs [35].…”

Section: Introductionmentioning

confidence: 87%

Probing the proton release by Photosystem II in the S₁ to S₂ high-spin transition

Boussac

Sugiura

Sellés

2022

Preprint

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The stoichiometry and kinetics of the proton release were investigated during each transition of the S-state cycle in Photosystem II (PSII) from Thermosynechococcus elongatus containing either a Mn4CaO5 (PSII/Ca) or a Mn4SrO5 (PSII/Sr) cluster. The measurements were done at pH 6.0 and pH 7.0 knowing that, in PSII/Ca at pH 6.0 and pH 7.0 and in PSII/Sr at pH 6.0, the flash-induced S2-state is in a low-spin configuration (S2LS) whereas in PSII/Sr at pH 7.0, the S2-state is in a high-spin configuration (S2HS) in half of the centers. Two measurements were done; the time-resolved flash dependent i) absorption of either bromocresol purple at pH 6.0 or neutral red at pH 7.0 and ii) electrochromism in the Soret band of PD1 at 440 nm. The fittings of the oscillations with a period of four indicate that one proton is released in the S1 to S2HS transition in PSII/Sr at pH 7.0. It was earlier suggested that the proton released in the S2LS to S3 transition is released in a S2LSTyrZ● to S2HSTyrZ● transition before the electron transfer from the cluster to TyrZ● occurs. The release of a proton in the S1TyrZ● to S2HSTyrZ transition would logically imply that this proton release is missing in the S2HSTyrZ● to S3TyrZ transition. Instead, the proton release in the S1 to S2HS transition in PSII/Sr at pH 7.0 was mainly done at the expense of the proton release in the S3 to S0 and S0 to S1 transitions. However, at pH 7.0, the electrochromism of PD1 seems larger in PSII/Sr when compared to PSII/Ca in the S3 state. This observation points to the complex link between proton movements in and immediately around the Mn4 cluster and the mechanism leading to the release of protons into the bulk.

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Activation energies for two steps in the S2 → S3 transition of photosynthetic water oxidation from time-resolved single-frequency infrared spectroscopy

Abstract: Note: This paper is part of the JCP Special Topic on 65 Years of Electron Transfer.

Cited by 25 publications

References 94 publications

Structural dynamics in the water and proton channels of photosystem II during the S2 to S3 transition

Structural dynamics in the water and proton channels of photosystem II during the S2 to S3 transition

Time-resolved infrared absorption spectroscopy applied to photoinduced reactions: how and why

Probing the proton release by Photosystem II in the S₁ to S₂ high-spin transition

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Activation energies for two steps in the S2 → S3 transition of photosynthetic water oxidation from time-resolved single-frequency infrared spectroscopy

Abstract: Note: This paper is part of the JCP Special Topic on 65 Years of Electron Transfer.

Cited by 25 publications

References 94 publications

Structural dynamics in the water and proton channels of photosystem II during the S2 to S3 transition

Structural dynamics in the water and proton channels of photosystem II during the S2 to S3 transition

Time-resolved infrared absorption spectroscopy applied to photoinduced reactions: how and why

Probing the proton release by Photosystem II in the S1 to S2 high-spin transition

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Probing the proton release by Photosystem II in the S₁ to S₂ high-spin transition