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Filamentous cable bacteria display long-range electron transport, generating electrical currents over centimeter distances through a highly ordered network of fibers embedded in their cell envelope. The conductivity of these periplasmic wires is exceptionally high for a biological material, but their chemical structure and underlying electron transport mechanism remain unresolved. Here, we combine high-resolution microscopy, spectroscopy, and chemical imaging on individual cable bacterium filaments to demonstrate that the periplasmic wires consist of a conductive protein core surrounded by an insulating protein shell layer. The core proteins contain a sulfur-ligated nickel cofactor, and conductivity decreases when nickel is oxidized or selectively removed. The involvement of nickel as the active metal in biological conduction is remarkable, and suggests a hitherto unknown form of electron transport that enables efficient conduction in centimeter-long protein structures.

Cable bacteria are electroactive bacteria that form a long, linear chain of ridged cylindrical cells. These filamentous bacteria conduct centimeter-scale long-range electron transport through parallel, interconnected conductive pathways of which the detailed chemical and electrical properties are still unclear. Here, we combine time-of-flight secondary-ion mass spectrometry (ToF-SIMS) and atomic force microscopy (AFM) to investigate the structure and composition of this naturally occurring electrical network. The enhanced lateral resolution achieved allows differentiation between the cell body and the cell-cell junctions that contain a conspicuous cartwheel structure. Three ToF-SIMS modes were compared in the study of so-called fiber sheaths (i.e., the cell material that remains after the removal of cytoplasm and membranes, and which embeds the electrical network). Among these, fast imaging delayed extraction (FI-DE) was found to balance lateral and mass resolution, thus yielding the following multiple benefits in the study of structure-composition relations in cable bacteria: (i) it enables the separate study of the cell body and cell-cell junctions; (ii) by combining FI-DE with in situ AFM, the depth of Ni-containing protein - key in the electrical transport - is determined with greater precision; and (iii) this combination prevents contamination, which is possible when using an ex situ AFM. Our results imply that the interconnects in extracted fiber sheaths are either damaged during extraction, or that their composition is different from fibers, or both. From a more general analytical perspective, the proposed methodology of ToF-SIMS in the FI-DE mode combined with in situ AFM holds great promise for studying the chemical structure of other biological systems., BT/Environmental Biotechnology

Cable bacteria are an emerging class of electroactive organisms that sustain unprecedented long-range electron transport across centimeter-scale distances. The local pathways of the electrical currents in these filamentous microorganisms remain unresolved. Here, the electrical circuitry in a single cable bacterium is visualized with nanoscopic resolution using conductive atomic force microscopy. Combined with perturbation experiments, it is demonstrated that electrical currents are conveyed through a parallel network of conductive fibers embedded in the cell envelope, which are electrically interconnected between adjacent cells. This structural organization provides a fail-safe electrical network for long-distance electron transport in these filamentous microorganisms. The observed electrical circuit architecture is unique in biology and can inspire future technological applications in bioelectronics., BT/Environmental Biotechnology

Determining the mechanism of charge transport through native DNA remains a challenge as different factors such as measuring conditions, molecule conformations, and choice of technique can significantly affect the final results. In this contribution, we have used a new approach to measure current flowing through isolated double-stranded DNA molecules, using fullerene groups to anchor the DNA to a gold substrate. Measurements were performed at room temperature in an inert environment using a conductive AFM technique. It is shown that the π-stacked B-DNA structure is conserved on depositing the DNA. As a result, currents in the nanoampere range were obtained for voltages ranging between ±1 V. These experimental results are supported by a theoretical model that suggests that a multistep hopping mechanism between delocalized domains is responsible for the long-range current flow through this specific type of DNA., ChemE/Opto-electronic Materials

The open-circuit voltage (V-oc) of polymer:fullerene bulk heterojunction solar cells is determined by the interfacial charge-transfer (CT) states between polymer and fullerene. Fourier-transform photocurrent spectroscopy and electroluminescence spectra of several polymer:fullerene blends are used to extract the relevant interfacial molecular parameters. An analytical expression linking these properties to V-oc is deduced and shown to be valid for photovoltaic devices comprising three commonly used conjugated polymers blended with the fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). V-oc is proportional to the energy of the CT states E-CT. The energetic loss q Delta V between E-CT and qV(oc) vanishes when approaching 0 K. It depends linearly on T and logarithmically on illumination intensity. Furthermore q Delta V can be reduced by decreasing the electronic coupling between polymer and fullerene or by reducing the nonradiative recombination rate. For the investigated devices we find a loss q Delta V of similar to 0.6 eV at room temperature and under solar illumination conditions, of which similar to 0.25 eV is due to radiative recombination via the CT state and similar to 0.35 eV is due to nonradiative recombination., Original Publication:Koen Vandewal, Kristofer Tvingstedt, Abay Gadisa, Olle Inganäs and Jean V Manca, Relating the open-circuit voltage to interface molecular properties of donor:acceptor bulk heterojunction solar cells, 2010, PHYSICAL REVIEW B, (81), 12, 125204.http://dx.doi.org/10.1103/PhysRevB.81.125204Copyright: American Physical Societyhttp://www.aps.org

The power conversion efficiency of polymer: fullerene bulk heterojunction solar cells depends on the generated photocurrent and photovoltage. Here we show, using the thermodynamic theory of detailed balance, that the photovoltage in particular is limited by the presence of polymer: fullerene material interaction, resulting in the formation of a weak donor-acceptor charge transfer complex (CTC). Excited CTCs, or charge transfer (CT) states, are visible in highly sensitive measurements of the absorption and photovoltaic action spectrum, or in photoluminescence and electroluminescence measurements. It is shown that photovoltaic and electroluminescent actions of the polymer: fullerene CTC are related by a reciprocity relation. This relation reproduces the measured open-circuit voltage (V-oc) of the photovoltaic device under solar conditions. Also, the temperature and illumination intensity dependence of V-oc is reproduced by the theory. Assuming perfect conditions for charge generation and recombination, a maximum obtainable V-oc value in function of polymer: fullerene CTC properties is derived.

The increasing amount of research on solution-processable, organic donor-acceptor bulk heterojunction photovoltaic systems, based on blends of conjugated polymers and fullerenes has resulted in devices with an overall power-conversion efficiency of 6%. For the best devices, absorbed photon-to-electron quantum efficiencies approaching 100% have been shown. Besides the produced current, the overall efficiency depends critically on the generated photovoltage. Therefore, understanding and optimization of the open-circuit voltage (V-oc) of organic solar cells is of high importance. Here, we demonstrate that charge-transfer absorption and emission are shown to be related to each other and V-oc in accordance with the assumptions of the detailed balance and quasi-equilibrium theory. We underline the importance of the weak ground-state interaction between the polymer and the fullerene and we confirm that V-oc is determined by the formation of these states. Our work further suggests alternative pathways to improve V-oc of donor-acceptor devices.