Aqueous-soluble bipyridine cobalt(<scp>ii</scp>/<scp>iii</scp>) complexes act as direct redox mediators in photosystem I-based biophotovoltaic devices

Teodor, Alexandra H.; Ooi, Eu-Jee; Medina, Jackeline; Alarcón, Miguel; Vaughn, Michael; Bruce, Barry D.; Bergkamp, Jesse J.

doi:10.1039/d0ra10221k

Cited by 11 publications

(17 citation statements)

References 68 publications

(90 reference statements)

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“…Biophotovoltaic devices were fabricated, and 500:1 BSA:PSI ratio microspheres were chelated overnight and then drop-coated on the semiconductor-coated electrode. A carbon-coated counter electrode and an aqueous synthetic cobalt-based electrolyte [ 42 ] were used to finish fabrication of the device.…”

Section: Resultsmentioning

confidence: 99%

“…PSI specifically has been shown to have promise for the development of bioelectronic electrodes and biohybrid photovoltaic devices. There has been some work interested in the stabilization of PSI for biotechnology applications, including design of designer surfactant peptides and fully aqueous electrolyte systems, but the successful stabilization of proteins for long-term usage in vitro remains a burgeoning research area [ 42 , 53 , 54 ]. Herein, we describe applications of calcium carbonate microspheres, CCMs, as templates for the encapsulation of the protein-pigment complex PSI, forming aqueous, mesoporous non-aggregating proteinaceous microspheres.…”

Section: Discussionmentioning

confidence: 99%

“…The 2 electrodes were then offset and mechanically compressed together, with dual clamps on either side holding the device together. The liquid junction electrolyte using an aqueous bipyridine-based Co(II/III) redox mediator at a concentration of 10 mM was then introduced, prepared as described previously in the same MES buffer used throughout analysis with 0.03% DDM [ 42 ]. Devices were allowed to sit for approximately 30 min to allow for electrolyte integration before device testing.…”

Section: Methodsmentioning

confidence: 99%

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Photosystem I integrated into mesoporous microspheres has enhanced stability and photoactivity in biohybrid solar cells

Teodor

Thal

Vijayakumar

et al. 2021

Materials Today Bio

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Isolated proteins, especially membrane proteins, are susceptible to aggregation and activity loss after purification. For therapeutics and biosensors usage, protein stability and longevity are especially important. It has been demonstrated that photosystem I (PSI) can be successfully integrated into biohybrid electronic devices to take advantage of its strong light-driven reducing potential (−1.2V vs. the Standard Hydrogen Electrode). Most devices utilize PSI isolated in a nanosize detergent micelle, which is difficult to visualize, quantitate, and manipulate. Isolated PSI is also susceptible to aggregation and/or loss of activity, especially after freeze/thaw cycles. CaCO 3 microspheres (CCMs) have been shown to be a robust method of protein encapsulation for industrial and pharmaceutical applications, increasing the stability and activity of the encapsulated protein. However, CCMs have not been utilized with any membrane protein(s) to date. Herein, we examine the encapsulation of detergent-solubilized PSI in CCMs yielding uniform, monodisperse, mesoporous microspheres. This study reports both the first encapsulation of a membrane protein and also the largest protein to date stabilized by CCMs. These microspheres retain their spectral properties and lumenal surface exposure and are active when integrated into hybrid biophotovoltaic devices. CCMs may be a robust yet simple solution for long-term storage of large membrane proteins, showing success for very large, multisubunit complexes like PSI.

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Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Photosystem I integrated into mesoporous microspheres has enhanced stability and photoactivity in biohybrid solar cells

Teodor

Thal

Vijayakumar

et al. 2021

Materials Today Bio

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“…Then, the electrons diffuse through the semiconductor to the photoanode substrate, where they travel through an external circuit and perform work before arriving at the cathode, generating the current. During that time, the redox mediators in the electrolyte regenerate the sensitizer molecule [ 43 , 44 ]. In return, the oxidized redox mediator diffuses to the counter electrode (CE) and gets regenerated [ 41 ].…”

Section: Introductionmentioning

confidence: 99%

“…Most work in the field of DSSCs has focused on the use of cobalt-based redox mediators to try and replace the I − /I 3 − pair [ 58 , 70 , 71 , 72 , 73 , 74 , 75 ] due to the high abundance of cobalt and its stable, reversible redox properties. Previous work from our group has described the synthesis and characterization of novel aqueous-soluble cobalt-based redox mediators and their ability to directly reduce PSI in vitro and the fabrication of fully aqueous BSSCs using the same mediator [ 44 ].…”

Section: Introductionmentioning

confidence: 99%

PEDOT-Carbon Nanotube Counter Electrodes and Bipyridine Cobalt (II/III) Mediators as Universally Compatible Components in Bio-Sensitized Solar Cells Using Photosystem I and Bacteriorhodopsin

Teodor

Monge

Aguilar

et al. 2022

IJMS

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In nature, solar energy is captured by different types of light harvesting protein–pigment complexes. Two of these photoactivatable proteins are bacteriorhodopsin (bR), which utilizes a retinal moiety to function as a proton pump, and photosystem I (PSI), which uses a chlorophyll antenna to catalyze unidirectional electron transfer. Both PSI and bR are well characterized biochemically and have been integrated into solar photovoltaic (PV) devices built from sustainable materials. Both PSI and bR are some of the best performing photosensitizers in the bio-sensitized PV field, yet relatively little attention has been devoted to the development of more sustainable, biocompatible alternative counter electrodes and electrolytes for bio-sensitized solar cells. Careful selection of the electrolyte and counter electrode components is critical to designing bio-sensitized solar cells with more sustainable materials and improved device performance. This work explores the use of poly (3,4-ethylenedioxythiophene) (PEDOT) modified with multi-walled carbon nanotubes (PEDOT/CNT) as counter electrodes and aqueous-soluble bipyridine cobaltII/III complexes as direct redox mediators for both PSI and bR devices. We report a unique counter electrode and redox mediator system that can perform remarkably well for both bio-photosensitizers that have independently evolved over millions of years. The compatibility of disparate proteins with common mediators and counter electrodes may further the improvement of bio-sensitized PV design in a way that is more universally biocompatible for device outputs and longevity.

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Drop-casted Photosystem I/cytochrome c multilayer films for biohybrid solar energy conversion

et al. 2022

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Aqueous-soluble bipyridine cobalt(ii/iii) complexes act as direct redox mediators in photosystem I-based biophotovoltaic devices

Abstract: Sustainable energy production is critical for meeting growing worldwide energy demands.

Cited by 11 publications

References 68 publications

Photosystem I integrated into mesoporous microspheres has enhanced stability and photoactivity in biohybrid solar cells

Photosystem I integrated into mesoporous microspheres has enhanced stability and photoactivity in biohybrid solar cells

PEDOT-Carbon Nanotube Counter Electrodes and Bipyridine Cobalt (II/III) Mediators as Universally Compatible Components in Bio-Sensitized Solar Cells Using Photosystem I and Bacteriorhodopsin

Drop-casted Photosystem I/cytochrome c multilayer films for biohybrid solar energy conversion

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