Electrochemically Gated Long‐Distance Charge Transport in Photosystem I

López-Martinez, Montserrat; López-Ortiz, Manuel; Antinori, Maria Elena; Wientjes, Emilie; Nin‐Hill, Alba; Rovira, Carme; Croce, Roberta; Díez‐Pérez, Ismael; Gorostiza, Pau

doi:10.1002/anie.201904374

Cited by 12 publications

(25 citation statements)

References 41 publications

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“…Beyond 2.5 nm the probe current is masked by faradaic currents (~25 pA) due to probe insulation defects. Double exponential behavior has already been reported for DNA molecules 29 and proteins 30,31 and has been attributed to the surface charge screening 28 .…”

Section: Electrochemical Current-distance Spectroscopy Measurementsmentioning

confidence: 57%

“…At sample potentials above 100 mV/SSC, β is around 4-5 nm -1 , similar to previously reported values for Az 28 and PSI complexes. 30 However, at sample potentials equal or below 0 mV/SSC and probe potential 400 mV/SSC we obtained β values below 2 nm -1 , which cannot be accounted for by a tunneling mechanism and are reminiscent of the long distance currents observed for Cc-bc1. 31 The effect of sample and probe potentials on β distributions (see Suppl.…”

Section: Electrochemical Current-distance Spectroscopy Measurementsmentioning

confidence: 68%

“…The lowest rates (corresponding to the farthest-reaching currents) are observed at US = 0 mV/SSC and UP = 400 mV/SSC. It has been reported that β values in redox proteins 28,30,31 and organic compounds 32 depend on the electrode potentials. In PSI-pIQA-cys-Au, β values depend on the probe rather than on the sample potential (provided that Us < -100 mV/SSC).…”

Section: Electrochemical Current-distance Spectroscopy Measurementsmentioning

confidence: 99%

“…In gold electrodes functionalized with azurin proteins 28 , β is 4 nm -1 and similar β values have been obtained for DNA base pairs 29 and redox proteins. 30,31 Moreover, β depends on potential and is lowest (current is most enhanced) where the electrode Fermi level is near the redox level of the protein 28,30,31 or redox-active organic compound 32 . Our previous results with PSI complexes 30 suggest that long distance charge transport is electrochemically gated 30 .…”

Section: Introductionmentioning

confidence: 99%

“…30,31 Moreover, β depends on potential and is lowest (current is most enhanced) where the electrode Fermi level is near the redox level of the protein 28,30,31 or redox-active organic compound 32 . Our previous results with PSI complexes 30 suggest that long distance charge transport is electrochemically gated 30 . In that work we used thiolated self-assembled monolayers (SAM) exposing a negatively charged surface, which have been largely employed for PSI immobilization 33 .…”

Section: Introductionmentioning

confidence: 99%

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Distance and Potential Dependence of Charge Transport Through the P700 Reaction Center of Photosystem I

Ortiz¹,

Zamora²,

Giannotti³

et al. 2021

Preprint

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Photoinduced charge separation and transport through photosystem I (PSI) is an essential part of the photosynthetic electron transport chain. To investigate charge exchange processes mediated by the P700 reaction center of PSI, we have developed a strategy to functionalize gold electrodes with PSI complexes that orients and exposes their luminal side to the electrolyte. Bulk photoelectrochemical measurements demonstrate that PSI remains functional in a wide sample potential range around 0 mV/SSC. Electrochemical scanning tunneling microscopy (ECSTM) imaging of individual complexes shows lateral sizes in agreement with the dimensions of PSI and an apparent height that is gated by the probe potential of ECTSM as reported for smaller globular redox proteins. This experimental setup enables ECSTM current-distance spectroscopic measurements that unequivocally correspond to the P700 side of PSI. In these conditions, we observe that the spatial span of the current is enhanced (the distance-decay rate β is reduced) through the solution at sample potential 0 mV/SSC and probe potential 400 mV/SSC. This process corresponds to hole injection into an electronic state that is available in the absence of illumination. We propose that a pair of tryptophan residues located near P700 and known to integrate the hydrophobic recognition site for plastocyanin may have an additional role as hole exchange mediator involved in charge transport through PSI.<br>

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Section: Electrochemical Current-distance Spectroscopy Measurementsmentioning

confidence: 57%

Section: Electrochemical Current-distance Spectroscopy Measurementsmentioning

confidence: 68%

Section: Electrochemical Current-distance Spectroscopy Measurementsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Distance and Potential Dependence of Charge Transport Through the P700 Reaction Center of Photosystem I

Ortiz¹,

Zamora²,

Giannotti³

et al. 2021

Preprint

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Single‐Molecule Electrical Profiling of Peptides and Proteins

Ju,

Cheng,

et al. 2024

Advanced Science

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In recent decades, there has been a significant increase in the application of single‐molecule electrical analysis platforms in studying proteins and peptides. These advanced analysis methods have the potential for deep investigation of enzymatic working mechanisms and accurate monitoring of dynamic changes in protein configurations, which are often challenging to achieve in ensemble measurements. In this work, the prominent research progress in peptide and protein‐related studies are surveyed using electronic devices with single‐molecule/single‐event sensitivity, including single‐molecule junctions, single‐molecule field‐effect transistors, and nanopores. In particular, the successful commercial application of nanopores in DNA sequencing has made it one of the most promising techniques in protein sequencing at the single‐molecule level. From single peptides to protein complexes, the correlation between their electrical characteristics, structures, and biological functions is gradually being established. This enables to distinguish different molecular configurations of these biomacromolecules through real‐time electrical monitoring of their life activities, significantly improving the understanding of the mechanisms underlying various life processes.

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Distance and Potential Dependence of Charge Transport Through the Reaction Center of Individual Photosynthetic Complexes

López-Ortiz

Zamora

Giannotti

et al. 2021

Small

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Charge separation and transport through the reaction center of photosystem I (PSI) is an essential part of the photosynthetic electron transport chain. A strategy is developed to immobilize and orient PSI complexes on gold electrodes allowing to probe the complex's electron acceptor side, the chlorophyll special pair P700. Electrochemical scanning tunneling microscopy (ECSTM) imaging and current–distance spectroscopy of single protein complex shows lateral size in agreement with its known dimensions, and a PSI apparent height that depends on the probe potential revealing a gating effect in protein conductance. In current–distance spectroscopy, it is observed that the distance‐decay constant of the current between PSI and the ECSTM probe depends on the sample and probe electrode potentials. The longest charge exchange distance (lowest distance‐decay constant β) is observed at sample potential 0 mV/SSC (SSC: reference electrode silver/silver chloride) and probe potential 400 mV/SSC. These potentials correspond to hole injection into an electronic state that is available in the absence of illumination. It is proposed that a pair of tryptophan residues located at the interface between P700 and the solution and known to support the hydrophobic recognition of the PSI redox partner plastocyanin, may have an additional role as hole exchange mediator in charge transport through PSI.

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Electrochemically Gated Long‐Distance Charge Transport in Photosystem I

Cited by 12 publications

References 41 publications

Distance and Potential Dependence of Charge Transport Through the P700 Reaction Center of Photosystem I

Distance and Potential Dependence of Charge Transport Through the P700 Reaction Center of Photosystem I

Single‐Molecule Electrical Profiling of Peptides and Proteins

Distance and Potential Dependence of Charge Transport Through the Reaction Center of Individual Photosynthetic Complexes

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