Yazar "Kiliszek, Malgorzata" seçeneğine göre listele

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    Bimodal functionality of highly conductive nanostructured silver film towards improved performance of photosystem I-based graphene photocathode
    (Elsevier Science Sa, 2025) Szalkowski, Marcin; Kiliszek, Malgorzata; Harputlu, Ersan; Izzo, Miriam; Unlu, C. Gokhan; Mackowski, Sebastian; Ocakoglu, Kasim
    We present the novel design of photosystem I (PSI)-based biosolar cell, whereby conductive transparent electrode materials, such as ITO or FTO, are replaced with glass covered with silver island film. This nanostructured metallic layer combines high electric conductance with enhancing the absorption efficiency of the PSI biocatalyst via the plasmonic effect. We demonstrate strong enhancement of the photocurrent generated in the biohybrid electrode composed of oriented layers of PSI reaction centers due to plasmonic interactions of the PSI fluorophores and redox centres with the conductive silver island film.
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    Enhancement of direct electron transfer in graphene bioelectrodes containing novel cytochrome c553 variants with optimized heme orientation
    (Elsevier Science Sa, 2021) Izzo, Miriam; Osella, Silvio; Jacquet, Margot; Kiliszek, Malgorzata; Harputlu, Ersan; Starkowska, Alicja; Lasica, Anna
    The highly efficient bioelectrodes based on single layer graphene (SLG) functionalized with pyrene self-assembled monolayer and novel cytochrome c(553) (cyt c(553)) peptide linker variants were rationally designed to optimize the direct electron transfer (DET) between SLG and the heme group of cyt. Through a combination of photoelectrochemical and quantum mechanical (QM/MM) approaches we show that the specific amino acid sequence of a short peptide genetically inserted between the cyt c(553) - holoprotein and the surface anchoring C-terminal His s -tag plays a crucial role in ensuring the optimal orientation and distance of the heme group with respect to the SLG surface. Consequently, efficient DET occurring between graphene and cyt c(553) leads to a 20-fold enhancement of the cathodic photocurrent output compared to the previously reported devices of a similar type. The QM/MM modeling implies that a perpendicular or parallel orientation of the heme group with respect to the SLG surface is detrimental to DET, whereas the tilted orientation favors the cathodic photocurrent generation. Our work confirms the possibility of fine-tuning the electronic communication within complex bio-organic nanoarchitectures and interfaces due to optimization of the tilt angle of the heme group, its distance from the SLG surface and optimal HOMO/LUMO levels of the interacting redox centers. (C) 2021 The Authors. Published by Elsevier B.V.
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    Molecular mechanism of direct electron transfer in the robust cytochrome-functionalised graphene nanosystem
    (Royal Soc Chemistry, 2021) Jacquet, Margot; Kiliszek, Malgorzata; Osella, Silvio; Izzo, Miriam; Sar, Jaroslaw; Harputlu, Ersan; Unlu, C. Gokhan
    Construction 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.
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    Plasmonic enhancement of photocurrent generation in a photosystem I-based hybrid electrode
    (Royal Soc Chemistry, 2020) Szalkowski, Marcin; Harputlu, Ersan; Kiliszek, Malgorzata; Unlu, C. Gokhan; Mackowski, Sebastian; Ocakoglu, Kasim; Kargul, Joanna
    We experimentally demonstrate that oriented assembly of red algal photosystem I (PSI) reaction centers on a plasmonically active Silver Island Film (SIF) leads to strong enhancement of both the fluorescence intensity and photocurrent generated upon illumination. PSI complexes were specifically attached to a monolayer of graphene deposited on the SIF layer. The results of comprehensive fluorescence microscopy point to the critical role of the SIF layer in enhancing the optical response of PSI, as we observe increased emission intensity. Hence, importantly, the strong increase of photocurrent generation demonstrated for the biohybrid electrodes can be directly associated with the plasmonic enhancement of the optical and electrochemical functionalities of PSI. The results also indicate that the graphene layer is not diminishing the influence of the plasmonic excitations in SIF on the absorption and emission of PSI.
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    Role of Metal Centers in Tuning the Electronic Properties of Graphene-Based Conductive Interfaces
    (Amer Chemical Soc, 2019) Osella, Silvio; Kiliszek, Malgorzata; Harputlu, Ersan; Unlu, Cumhur G.; Ocakoglu, Kasim; Trzaskowski, Bartosz; Kargul, Joanna
    A major bottleneck in the fabrication of efficient bio-organic nanoelectronic devices resides in the strong charge recombination that is present at the different interfaces forming the complex system. An efficient way to overcome this bottleneck is to add a self-assembled monolayer (SAM) of molecules between the biological material and electrode that promotes an efficient direct electron transfer while minimizing wasteful processes of charge recombination. In this work, the presence of a pyrene-nitrilotriacetic acid layer carrying different metal centers as the SAM is physisorbed on graphene is fully described by means of electrochemical analysis, field-emission scanning electron microscopy, photoelectrochemical characterization, and theoretical calculations. Our multidisciplinary study reveals that the metal center holds the key role in the efficient electron transfer at the interface. While Ni2+ is responsible for the electron transfer from the SAM to graphene, Co2+ and Cu2+ force an opposite transfer from graphene to SAM. Moreover, since Cu2+ inhibits the electron transfer due to a strong charge recombination, Co2+ seems to be the transition metal of choice for the efficient electron transfer.