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Electrochemical detection of quinone reduced by Complex I Complex II and Complex III in full mitochondrial membranes

In the last decades enormous advances have been made in characterizing the atomic and molecular structure of respiratory chain supercomplexes. *

However, it still remains a challenge to stitch this refined spatial atomistic description with functional information provided by biochemical studies of isolated protein material. Development of functional assays that detect respiratory chain complexes in their native membrane environment contribute to address the open questions related to the role played by their association and interactions. *

In the article “Electrochemical detection of quinone reduced by Complex I Complex II and Complex III in full mitochondrial membranes” Daniel G. Cava, Julia Alvarez-Malmagro, Paolo Natale, Sandra López-Calcerrada, Iván López-Montero, Cristina Ugalde, Jose Maria Abad, Marcos Pita, Antonio L. De Lacey and Marisela Vélez present a characterization assay in which a functionalized gold electrode is modified with mitochondrial membrane fragments that allows monitoring electrochemically the activity of different respiratory chain complexes immersed in the mitochondrial membrane. *

Daniel G. Cava et al. measure the intensity of the reducing current of the electron mediator CoQ1 at the electrode surface and its variation upon addition of the corresponding enzymatic substrates. The activities of Complex I, Complex II and Complex III were monitored by the way in which they reduce the current, reflecting the amount of quinone reduced by the complexes in the presence of their substrates. *

The authors detect that CoQ1H2 produced by Complex I remains partially trapped within the membrane and is more easily oxidized by Complex III or the electrode than the quinone reduced by Complex II. *

Atomic Force Microscopy (AFM) was used to image the topography of the membrane modified electrode. NanoWorld Pyrex-Nitride Silicon-Nitride AFM probes (PNP-DB, diving board shaped cantilevers, the short AFM cantilever with a typical force constant of 0.48 N/m and 67 kHz resonance frequency) were used. *

The surfaces analysed were the electrodes. The two surfaces imaged are the same previously polished electrodes used for electrochemical measurements. The microscope sample holder was adapted in-home to support the electrodes. Two surfaces were analysed: the polished gold functionalized with 4-aminothiophenol and the electrode after incubation with mitochondria subparticles prepared similarly to the electrodes used for the electrochemical measurements.*

Fig. 2 from Daniel G. Cava et al 2024 “Electrochemical detection of quinone reduced by Complex I Complex II and Complex III in full mitochondrial membranes”
QCM and AFM characterization of modified gold. Panel A shows the frequency (left, black) and dissipation (right red) changes detected on a gold covered quartz crystal previously modified with a 4-ATP after injection in the chamber of the mitochondrial fragments at the time point indicated by the thick arrow. Panel B show AFM images of the surface topography of a modified gold electrode before (left) and after (right)incubation with the mitochondrial membrane. The inset below shows the height profile of the lines indicated in the images.

*Daniel G. Cava, Julia Alvarez-Malmagro, Paolo Natale, Sandra López-Calcerrada, Iván López-Montero, Cristina Ugalde, Jose Maria Abad, Marcos Pita, Antonio L. De Lacey and Marisela Vélez
Electrochemical detection of quinone reduced by Complex I Complex II and Complex III in full mitochondrial membranes
Electrochimica Acta, Volume 484, 20 April 2024, 144042
DOI: https://doi.org/10.1016/j.electacta.2024.144042

The article “Electrochemical detection of quinone reduced by Complex I Complex II and Complex III in full mitochondrial membranes” by Daniel G. Cava, Julia Alvarez-Malmagro, Paolo Natale, Sandra López-Calcerrada, Iván López-Montero, Cristina Ugalde, Jose Maria Abad, Marcos Pita, Antonio L. De Lacey and Marisela Vélez is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third-party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit https://creativecommons.org/licenses/by/4.0/.

Manipulating hyperbolic transient plasmons in a layered semiconductor

Anisotropic materials with oppositely signed dielectric tensors support hyperbolic polaritons, displaying enhanced electromagnetic localization and directional energy flow. *

However, the most reported hyperbolic phonon polaritons are difficult to apply for active electro-optical modulations and optoelectronic devices. *

In the nature communications letter “Manipulating hyperbolic transient plasmons in a layered semiconductor”, Rao Fu, Yusong Qu, Mengfei Xue, Xinghui Liu, Shengyao Chen, Yongqian Zhao, Runkun Chen, Boxuan Li, Hongming Weng, Qian Liu, Qing Dai and Jianing Chen report a dynamic topological plasmonic dispersion transition in black phosphorus (BP) via photo-induced carrier injection, i.e., transforming the iso-frequency contour from a pristine ellipsoid to a non-equilibrium hyperboloid. *

They introduce a promising approach to optically manipulate robust transient hyperbolic plasmons in the layered semiconductor black phosphorus using a dedicated ultrafast nanoscopy scheme. Optical pumping allows the BP’s IFCs to topologically transit from the pristine ellipsoid to the non-equilibrium hyperboloid, exhibiting exotic non-equilibrium hyperbolic plasmon properties, such as the optically tunable plasmonic dispersion and the coexistence of different transient plasmonic modes. *

Their work also demonstrates the peculiar transient plasmonic properties of the studied layered semiconductor, such as the ultrafast transition, low propagation losses, efficient optical emission from the black phosphorus’s edges, and the characterization of different transient plasmon modes. *

The results that Rao Fu et al. present may be relevant for the development of future optoelectronic applications. *

NanoWorld® ARROW-NCPt AFM probes with a Pt/Ir coating were used for the characterization with ultrafast nanoscopy. The pump and probe pulses were spatially overlapped on the Platinum/Iridium coated Arrow probe through a parabolic mirror of a commercial scattering-type scanning near-field optical microscope. *

Fig. 4 from Rao Fu et al. “Manipulating hyperbolic transient plasmons in a layered semiconductor”:Dynamic analysis of the transient plasmons. a Normalized near-field amplitude s3/s3,Si of a 280-nm-thick BP slab for twelve delay times τ. Scale bar, 1 µm. b Near-field amplitude curves for the corresponding twelve different delay times τ in a. c Dynamics of the relative near-field intensity of the first (∆S1) and the second bright strip (∆S2) in b. Opened circles are the experimental data, and solid lines are bi-exponential fitting for ∆S1 and exponential fitting for ∆S2, respectively. d Dynamics of the near-field amplitude s3 from the black circle in a. The inset displays the s3 at τ = −2 to 6 ps, and the dashed line marks the s3 level of the pristine state. NanoWorld® ARROW-NCPt AFM probes with a Pt/Ir coating were used for the characterization with ultrafast nanoscopy. The pump and probe pulses were spatially overlapped on the Pt/Ir coated Arrow probe through a parabolic mirror of a commercial scattering-type scanning near-field optical microscope. — Fig. 4 from Rao Fu et al. “Manipulating hyperbolic transient plasmons in a layered semiconductor”:
Dynamic analysis of the transient plasmons.
a Normalized near-field amplitude s3/s3,Si of a 280-nm-thick BP slab for twelve delay times τ. Scale bar, 1 µm. b Near-field amplitude curves for the corresponding twelve different delay times τ in a. c Dynamics of the relative near-field intensity of the first (∆S1) and the second bright strip (∆S2) in b. Opened circles are the experimental data, and solid lines are bi-exponential fitting for ∆S1 and exponential fitting for ∆S2, respectively. d Dynamics of the near-field amplitude s3 from the black circle in a. The inset displays the s3 at τ = −2 to 6 ps, and the dashed line marks the s3 level of the pristine state.

*Rao Fu, Yusong Qu, Mengfei Xue, Xinghui Liu, Shengyao Chen, Yongqian Zhao, Runkun Chen, Boxuan Li, Hongming Weng, Qian Liu, Qing Dai and Jianing Chen
Manipulating hyperbolic transient plasmons in a layered semiconductor
Nature Communications volume 15, Article number: 709 (2024)
DOI: https://doi.org/10.1038/s41467-024-44971-3

Please follow this external link to read the full article: https://rdcu.be/dBD85

The article “Manipulating hyperbolic transient plasmons in a layered semiconductor” by Rao Fu, Yusong Qu, Mengfei Xue, Xinghui Liu, Shengyao Chen, Yongqian Zhao, Runkun Chen, Boxuan Li, Hongming Weng, Qian Liu, Qing Dai and Jianing Chen is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third-party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit https://creativecommons.org/licenses/by/4.0/.

Studying the cation dependence of CO2 reduction intermediates at Cu by in situ VSFG spectroscopy

The nature of the electrolyte cation is known to have a significant impact on electrochemical reduction of CO2 at catalyst|electrolyte interfaces. An understanding of the underlying mechanism responsible for catalytic enhancement as the alkali metal cation group is descended is key to guide catalyst development. *

In the article “Studying the cation dependence of CO2 reduction intermediates at Cu by in situ VSFG spectroscopy” Liam C. Banerji, Hansaem Jang, Adrian M. Gardner and Alexander J. Cowan use in situ vibrational sum frequency generation (VSFG) spectroscopy to monitor changes in the binding modes of the CO intermediate at the electrochemical interface of a polycrystalline Cu electrode during CO2 reduction as the electrolyte cation is varied. *

Three alkali metal cations have been chosen for analysis: K+, which is the most commonly used electrolyte cation for eCO2R, Cs+, which has been shown to give the greatest enhancement for C2+ products, and Na+, which shows poorer eCO2R performance than K+ whilst maintaining appreciable levels of C-based products. The ability of VSFG to study catalyst|electrolyte interfaces without the need for modifications, as required in the spectroelectrochemical studies mentioned in the article, which can fundamentally alter the electrodes activity, makes it an important tool to assess the mechanisms occurring on the pc-Cu electrodes routinely employed for eCO2R. *

A CObridge mode is observed only when using Cs+, a cation that is known to facilitate CO2 reduction on Cu, supporting the proposed involvement of CObridge sites in CO coupling mechanisms during CO2 reduction. Ex situ measurements show that the cation dependent CObridge modes correlate with morphological changes of the Cu surface. *

The results presented in the article suggest that a high level of bridge site formation is related to, or facilitated by, the Cu restructuring that happens as a result of the use of the Cs+ cations in the supporting electrolyte. Recent reports have indicated that multiple (bridge) bound CO may be electrochemically inert but this work builds on the emerging evidence that CObridge sites are a key intermediate in the CO–CO coupling step that is required for C2+ formation during eCO2R. *

NanoWorld Pointprobe® CONTR AFM probes for contact mode atomic force microscopy (AFM) were used to characterize the morphology of the CU electrode surface before bulk electrolysis and after bulk electrolysis.*

Fig. 5 from Liam C. Banerji et al. “Studying the cation dependence of CO2 reduction intermediates at Cu by in situ VSFG spectroscopy”: AFM images showing surface morphology of the Cu electrode surface (a) before bulk electrolysis, after bulk electrolysis in CO2 purged 0.5 M (b) NaHCO3, (c) KHCO3 and (d) CsHCO3 and also in (e) CO purged 0.5 M CsHCO3. Image analysis methods are described in the Experimental section.NanoWorld Pointprobe® CONTR AFM probes for contact mode atomic force microscopy (AFM) were used to characterize the morphology of the CU electrode surface before bulk electrolysis and after bulk electrolysis. — Fig. 5 from Liam C. Banerji et al. “Studying the cation dependence of CO2 reduction intermediates at Cu by in situ VSFG spectroscopy”: AFM images showing surface morphology of the Cu electrode surface (a) before bulk electrolysis, after bulk electrolysis in CO2 purged 0.5 M (b) NaHCO3, (c) KHCO3 and (d) CsHCO3 and also in (e) CO purged 0.5 M CsHCO3. Image analysis methods are described in the Experimental section of the original article.

*Liam C. Banerji, Hansaem Jang, Adrian M. Gardner and Alexander J. Cowan
Studying the cation dependence of CO2 reduction intermediates at Cu by in situ VSFG spectroscopy
Chemical Science 2024, 15, 2889-2897
DOI: https://doi.org/10.1039/D3SC05295H

The article “Studying the cation dependence of CO2 reduction intermediates at Cu by in situ VSFG spectroscopy” by Liam C. Banerji, Hansaem Jang, Adrian M. Gardner and Alexander J. Cowan is licensed under a Creative Commons Attribution 3.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third-party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit https://creativecommons.org/licenses/by/3.0/.