Molecular mechanism of direct electron transfer in the robust cytochrome-functionalised graphene nanosystem

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dc.authoridUnlu, Cumhur Gokhan/0000-0003-2554-5886
dc.authoridOcakoglu, Kasim/0000-0003-2807-0425
dc.authoridharputlu, ersan/0000-0002-2140-9070
dc.authoridIzzo, Miriam/0000-0003-4586-610X
dc.authoridJacquet, Margot/0000-0002-5842-9761
dc.authoridKargul, Joanna/0000-0003-1410-1905
dc.authoridOsella, Silvio/0000-0001-8541-1914
dc.contributor.authorJacquet, Margot
dc.contributor.authorKiliszek, Malgorzata
dc.contributor.authorOsella, Silvio
dc.contributor.authorIzzo, Miriam
dc.contributor.authorSar, Jaroslaw
dc.contributor.authorHarputlu, Ersan
dc.contributor.authorUnlu, C. Gokhan
dc.date.accessioned2025-03-17T12:25:54Z
dc.date.available2025-03-17T12:25:54Z
dc.date.issued2021
dc.departmentTarsus Üniversitesi
dc.description.abstractConstruction of green nanodevices characterised by excellent long-term performance remains high priority in biotechnology and medicine. Tight electronic coupling of proteins to electrodes is essential for efficient direct electron transfer (DET) across the bio-organic interface. Rational modulation of this coupling depends on in-depth understanding of the intricate properties of interfacial DET. Here, we dissect the molecular mechanism of DET in a hybrid nanodevice in which a model electroactive protein, cytochrome c(553) (cyt c(553)), naturally interacting with photosystem I, was interfaced with single layer graphene (SLG) via the conductive self-assembled monolayer (SAM) formed by pyrene-nitrilotriacetic acid (pyr-NTA) molecules chelated to transition metal redox centers. We demonstrate that efficient DET occurs between graphene and cyt c(553) whose kinetics and directionality depends on the metal incorporated into the bio-organic interface: Co enhances the cathodic current from SLG to haem, whereas Ni exerts the opposite effect. QM/MM simulations yield the mechanistic model of interfacial DET based on either tunnelling or hopping of electrons between graphene, pyr-NTA-M2+ SAM and cyt c(553) depending on the metal in SAM. Considerably different electronic configurations were identified for the interfacial metal redox centers: a closed-shell system for Ni and a radical system for the Co with altered occupancy of HOMO/LUMO levels. The feasibility of fine-tuning the electronic properties of the bio-molecular SAM upon incorporation of various metal centers paves the way for the rational design of the optimal molecular interface between abiotic and biotic components of the viable green hybrid devices, e.g. solar cells, optoelectronic nanosystems and solar-to-fuel assemblies.
dc.description.sponsorshipPolish National Science Centre [UMO-2017/27/B/ST5/00472, UMO-2018/31/D/ST4/01475]
dc.description.sponsorshipMI, MK, MJ, SO and JK gratefully acknowledge the financial support from the Polish National Science Centre (grant no. UMO-2017/27/B/ST5/00472 to JK and UMO-2018/31/D/ST4/01475 to SO). We are grateful to Prof. Rafa Jurczakowski (CBCS & Faculty of Chemistry, University of Warsaw, Poland) for his helpful comments on this manuscript.
dc.identifier.doi10.1039/d1ra02419a
dc.identifier.endpage18869
dc.identifier.issn2046-2069
dc.identifier.issue31
dc.identifier.pmid35478629
dc.identifier.scopus2-s2.0-85106897291
dc.identifier.scopusqualityQ1
dc.identifier.startpage18860
dc.identifier.urihttps://doi.org/10.1039/d1ra02419a
dc.identifier.urihttps://hdl.handle.net/20.500.13099/1908
dc.identifier.volume11
dc.identifier.wosWOS:000655866800021
dc.identifier.wosqualityQ2
dc.indekslendigikaynakWeb of Science
dc.indekslendigikaynakScopus
dc.indekslendigikaynakPubMed
dc.language.isoen
dc.publisherRoyal Soc Chemistry
dc.relation.ispartofRsc Advances
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanı
dc.rightsinfo:eu-repo/semantics/openAccess
dc.snmzKA_WOS_20250316
dc.subjectPhotosystem-I
dc.subjectElectrochemical Properties
dc.subjectPhotocurrent Generation
dc.subjectBiophotovoltaics
dc.subjectPerformance
dc.subjectMonolayers
dc.subjectOxide
dc.subjectGold
dc.titleMolecular mechanism of direct electron transfer in the robust cytochrome-functionalised graphene nanosystem
dc.typeArticle

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