Development of bioanodes rich in exoelectrogenic bacteria using iron-rich palaeomarine sediment inoculum.

Microbial Fuel Cells (MFC) convert energy stored in chemicals into electrical energy thanks to exoelectrogenic microorganisms who also play a crucial role in geochemical cycles in their natural environment, including that of iron. In this study, we investigated paleomarine sediments as inoculum for bioanode development in MFCs. These sediments were formed under anoxic conditions ca. 113 million years ago and are rich in clay minerals, organic matter, and iron. The marlstone inoculum was incubated in the anolyte of an MFC using acetate as the added electron donor and ferricyanide as the electron acceptor in the catholyte. After seven weeks of incubation, the current density increased to 0.15 mA.cm-2 and a stable + 700 mV open circuit potential was reached. Community analysis revealed the presence of two exoelectrogenic bacterial genera, Geovibrio and Geobacter. Development of electroactive biofilms was correlated to bulk chemical transformations of the sediment inoculum with an increase in the Fe(II) to Fetotal ratio. Comparisons to sediments sterilized prior to inoculation confirmed that bioanode development derives from the native microbiota of these paleomarine sediments. This study illustrates the feasibility of developing exoelectrogenic biofilms from iron-rich marlstone and has implications for the role of such bacteria in broader paleoenvironmental phenomena.

A Bimetallic Benzene-1,2,4,5-Tetrathiolate (btt) Molybdenocene Complex Cp2 Mo(btt)MoCp2 : Radical and Diradical States.

Benzene-1,2,4,5-tetrathiolate (btt) has been used as a bridging ligand to prepare a redox active (molybdenocene dithiolene)-based bimetallic complex Cp2 Mo(btt)MoCp2 , which exhibits four successive electron transfers up to the tetracation. Spectro-electrochemical investigations together with DFT and TD-DFT calculations evidence that the two electroactive MoS2 C2 metallacycles are electronically coupled in the monocationic as in the dicationic state. Two salts of the dication [Cp2 Mo(btt)MoCp2 ]2+ have been structurally characterized with PF6 - and HSO4 - counterions, showing different chair or boat conformations associated with variable folding angles of the two MoS2 C2 metallacycles along the S-S hinge. The bis-oxidized dicationic complex exhibits a diradical character, with both radicals essentially localized on the metallacycles and with antiferromagnetic coupling evidenced from magnetic susceptibility measurements.

Challenges and applications of nitrate-reducing microbial biocathodes.

Bioelectrochemical systems which employ microbes as electrode catalysts to convert chemical energy into electrical energy (or conversely), have emerged in recent years for water sanitation and energy recovery. Microbial biocathodes, and especially those reducing nitrate are gaining more and more attention. The nitrate-reducing biocathodes can efficiently treat nitrate-polluted wastewater. However, they require specific conditions and they have not yet been applied on a large scale. In this review, the current knowledge on nitrate-reducing biocathodes will be summarized. The fundamentals of microbial biocathodes will be discussed, as well as the progress towards applications for nitrate reduction in the context of water treatment. Nitrate-reducing biocathodes will be compared with other nitrate-removal techniques and the challenges and opportunities of this approach will be identified.

Fe(III) oxide microparticles modulate extracellular electron transfer in anodic biofilms dominated by bacteria of the Pelobacter genus.

Exo-electrogenic microorganisms have been extensively studied for their ability to transfer electrons with solid surfaces using a large variety of metabolic pathways. Most of the studies on these microorganisms consist in the replacement of solid electron acceptors such as Fe(III) oxides found in nature by electrodes with the objective of generating harvestable current in devices such as microbial fuel cells. In this study we show how the presence of solid ferric oxide (Fe2O3) particles in the inoculum during bio-anode development influences extracellular electron transfer to the electrode. Amplification and sequencing of the 16S rRNA (V4-V5 region) show bacteria and archaea communities with a large predominance of the Pelobacter genus, which is known to be phylogenetically close to the Geobacter genus, regardless of the presence or absence of ferric oxide in the inoculum. Data indicate that the bacteria at the bio-anode surface can preferentially utilize solid ferric oxide as terminal electron acceptors instead of the anode, though extracellular electron transfer to the anode can be restored by removing the particles. Mixed inoculum commonly used to develop bioanodes may produce similar bacterial communities with divergent electrochemical responses due to the presence of alternate electron acceptors, with direct implications for microbial fuel cell performance.

Electrografted anthraquinone to monitor pH at the biofilm-anode interface in a wastewater microbial fuel cell.

Electrografted anthraquinone on graphite was used as a probe to monitor the pH change at the biofilm-electrode interface at the anode of a microbial fuel cell inoculated with wastewater. The grafting procedure was optimized so that the pH-dependent electrochemical response of the grafted quinone did not overlay with that of the electroactive biofilm. The variation of the formal potential of the grafted quinone as a function of pH was linear over the pH range 1-10 with a slope of - 64 mV. This allowed to monitor the interfacial pH change over three weeks of biofilm colonization of the electrode. During that time the interfacial pH decreased from neutrality to 5.3 while the anolyte only acidified down to pH 6.2. This finding is relevant as local pH change usually leads to alterations of the bioenergetics process of microbial communities and hence on the performance of bioelectrochemical devices.

Nanoscaffold effects on the performance of air-cathodes for microbial fuel cells: Sustainable Fe/N-carbon electrocatalysts for the oxygen reduction reaction under neutral pH conditions.

Nanostructured electrocatalysts for microbial fuel cell air-cathodes were obtained via use of conductive carbon blacks for the synthesis of high performing 3D conductive networks. We used two commercially available nanocarbons, Black Pearls 2000 and multiwalled carbon nanotubes, as conductive scaffolds for the synthesis of nanocomposite electrodes by combining: a hydrothermally carbonized resin, a sacrificial polymeric template, a nitrogenated organic precursor and iron centers. The resulting materials are micro-mesoporous, possess high specific surface area and display N-sites (N/C of 3-5 at%) and Fe-centers (Fe/C < 1.5at.%) at the carbon surface as evidenced from characterization methods. Voltammetry studies of oxygen reduction reaction activity were carried out at neutral pH, which is relevant to microbial fuel cell applications, and activity trends are discussed in light of catalyst morphology and composition. Tests of the electrocatalyst using microbial fuel cell devices indicate that optimization of the nanocarbon scaffold for the Pt-free carbon-based electrocatalysts results in maximum power densities that are 25% better than those of Pt/C cathodes, at a fraction of the materials costs. Therefore, the proposed Fe/N-carbon catalysts are promising and sustainable high-performance cathodic materials for microbial fuel cells.

Controlling the Carbon-Bio Interface via Glycan Functional Adlayers for Applications in Microbial Fuel Cell Bioanodes.

Surface modification of electrodes with glycans was investigated as a strategy for modulating the development of electrocatalytic biofilms for microbial fuel cell applications. Covalent attachment of phenyl-mannoside and phenyl-lactoside adlayers on graphite rod electrodes was achieved via electrochemically assisted grafting of aryldiazonium cations from solution. To test the effects of the specific bio-functionalities, modified and unmodified graphite rods were used as anodes in two-chamber microbial fuel cell devices. Devices were set up with wastewater as inoculum and acetate as nutrient and their performance, in terms of output potential (open circuit and 1 kΩ load) and peak power output, was monitored over two months. The presence of glycans was found to lead to significant differences in startup times and peak power outputs. Lactosides were found to inhibit the development of biofilms when compared to bare graphite. Mannosides were found, instead, to promote exoelectrogenic biofilm adhesion and anode colonization, a finding that is supported by quartz crystal microbalance experiments in inoculum media. These differences were observed despite both adlayers possessing thickness in the nm range and similar hydrophilic character. This suggests that specific glycan-mediated bioaffinity interactions can be leveraged to direct the development of biotic electrocatalysts in bioelectrochemical systems and microbial fuel cell devices.

Introducing Selenium in Single-Component Molecular Conductors Based on Nickel Bis(dithiolene) Complexes.

Two selenated analogues of the all-sulfur single-component molecular conductor [Ni(Et-thiazdt)2] (Et-thiazdt = N-ethylthiazoline-2-thione-4,5-dithiolate) have been prepared from their precursor radical-anion complexes. Replacement of the thione by a selenone moiety gives the neutral [Ni(Et-thiazSedt)2] complex. It adopts an unprecedented solid-state organization (for neutral nickel complexes), with the formation of perfectly eclipsed dimers and very short intermolecular Se···Se contacts (81% of the van der Waals contact distance). Limited interactions between dimers leads to a large semiconducting gap and low conductivity (σRT = 1.7 × 10-5 S cm-1). On the other hand, going from the neutral [Ni(Et-thiazdt)2] dithiolene complex to the corresponding [Ni(Et-thiazds)2] diselenolene complex gives rise to a more conventional layered structure built out of uniform stacks of the diselenolene complexes, different, however, from the all-sulfur analogue [Ni(Et-thiazdt)2]. Band structure calculations show an essentially 1D electronic structure with large band dispersion and a small HOMO-LUMO gap. Under high pressures (up to 19 GPa), the conductivity increases by 4 orders of magnitude and the activation energy is decreased from 120 meV to only 13 meV, with an abrupt change observed around 10 GPa, suggesting a structural phase transition under pressure.

Denitrifying bio-cathodes developed from constructed wetland sediments exhibit electroactive nitrate reducing biofilms dominated by the genera Azoarcus and Pontibacter.

To limit the nitrate contamination of ground and surface water, stimulation of denitrification by electrochemical approach is an innovative way to be explored. Two nitrate reducing bio-cathodes were developed under constant polarization (-0.5 V vs SCE) using sediments and water from a constructed wetland (Rampillon, Seine-et-Marne, France). The bio-cathodes responded to nitrate addition on chronoamperometry through an increase of the reductive current. The denitrification efficiency of the pilots increased by 47% compared to the negative controls without electrodes after polarization. 16S rRNA gene sequencing of the biofilms and sediments evidenced the significant and discriminating presence of the Azoarcus and Pontibacter genera in the biofilms from biocathodes active for nitrate reduction. Our study shows the possibility to promote the development of efficient Azoarcus-dominated biocathodes from freshwater sediment to enhance nitrate removal from surface waters.

A radical mixed-ligand gold bis(dithiolene) complex.

A mixed-ligand bis(dithiolene) gold complex is isolated from scrambling reaction of two neutral radical symmetric complexes. Its asymmetric character translates into specific structural and electronic properties including larger electrochemical and optical band gaps than those of both precursors.

Activating both Halogen and Chalcogen Bonding Interactions in Cation Radical Salts of Iodinated Tetrathiafulavalene Derivatives.

Halogen bonding (XB) interactions are investigated in cation radical salts of bis(methylthio)-5,5'-diiodotetrathiafulvalene (1). Electrocrystallization of 1 in the presence of Bu4 NCl affords a 1 : 1 salt formulated as (E-1)Cl. Particularly strong I⋅⋅⋅Cl- XB interactions are observed around the Cl- anion with the distances at 78 % the sum of the van der Waals radii, a consequence of the XB charge activation in the cation radical. Moreover, the Cl- environment is complemented by two extra S⋅⋅⋅Cl- chalcogen bonding (ChB) interactions, an original feature among reported halide salts of TTF derivatives. Electrostatic potential calculations on the cation radical further demonstrate the efficient activation of the S atoms of the 1,3-dithiole rings (Vs,max =87.2 kcal/mol), as strong as with the iodine atoms (Vs,max =87.9 kcal/mol). The radical cations form weakly dimerized stacks, as confirmed by the variable-temperature magnetic susceptibility and the weak conductivity (4.8×10-5  S cm-1 ).

Tailored glycosylated anode surfaces: Addressing the exoelectrogen bacterial community via functional layers for microbial fuel cell applications.

Grafting of aryldiazonium cations bearing a p-mannoside functionality over microbial fuel cell (MFC) anode materials was performed to investigate the ability of aryl-glycoside layers to regulate colonisation by biocatalytic biofilms. Covalent attachment was achieved via spontaneous reactions and via electrochemically-assisted grafting using potential step experiments. The effect of different functionalisation protocols on MFC performance is discussed in terms of changes in wettability, roughness and electrochemical response of modified electrodes. Water contact angle measurements (WCA) show that aryl-mannoside grafting yields a significant increase in hydrophilic character. Surface roughness determinations via atomic force microscopy (AFM) suggest a more disordered glycan adlayer when electrografting is used to facilitate chemisorption. MFCs were used as living sensors to successfully test the coated electrodes: the response of the MFCs in terms of start-up time was accelerated when compared to that of MFC equipped with non-modified electrodes, this suggests a faster development of a mature biofilm community resulting from aryldiazonium modifications, as confirmed by cyclic voltammetry of MFC anodes. These results therefore indicate that modification with glycans offers a bioinspired route to accelerating biofilm colonisation without any adverse effects on final MFC outputs.

Lipid Membrane Permeability of Synthetic Redox DMPC Liposomes Investigated by Single Electrochemical Collisions.

The electrochemical detection of synthetic redox DMPC (1,2-dimyristoyl-sn-glycero-3-phosphocholine) liposomes by single collisions at 10 µm diameter carbon and Pt ultramicroelectrodes (UMEs) is reported. To study the parameters influencing the lipid membrane opening/permeability, the electrochemical detection of single redox DMPC liposome collisions at polarized UMEs was investigated under different experimental conditions (addition of surfactant, temperature). The electrochemical responses recorded showed that the permeability of the DMPC lipid membrane (tuned by addition of Triton X-100 surfactant or by the increase of the solution temperature) is a key parameter for the liposome membrane electroporation process and hence for the release and oxidation of its redox content during the collision onto UMEs. The presence of ferrocenemethanol as an additional redox probe in the aqueous solution (at room temperature and without addition of surfactant) is also an interesting strategy to detect current spikes corresponding to single redox DMPC liposome collisions with K3Fe(CN)6/K4Fe(CN)6 as the encapsulated aqueous redox probe.

Cyclization of Terphenyl-Bisfluorenols: A Mechanistic Study of the Regioselectvity.

The mechanism of the bicyclization reaction of a series of terphenyl-bisfluorenols into dispiro[fluorene-9,6'-indeno[1,2-b]fluorene-12',9''-fluorene] and dispiro[fluorene-9,6'-indeno[2,1-a]fluorene-12',9''-fluorene] is reported. Through a combined experimental and theoretical study, the different parameters that drive the regioselectivity of this cyclization reaction have been studied and are presented.

Ambipolar Discotic Liquid Crystals Built Around Platinum Diimine-Dithiolene Cores.

Platinum diimine dithiolene complexes bearing mesogenic groups on one or both ligands have been prepared through an original ligand metathesis reaction to introduce the dithiolene ligand. The neutral diimine ligands, the intermediate platinum dichloride diimine complexes, and the target compounds were characterized by a combination of electronic (electrochemistry, absorption and emission spectroscopy, DFT calculations) and structural (SAXS, DSC) tools. Several novel liquid crystalline platinum diimine-dithiolene were identified over a large temperature range, and the systems were endowed with ambipolar properties, associated with the high reversibility of both oxidation and reduction processes.

Electrochemical Detection of pH-Responsive Grafted Catechol and Immobilized Cytochrome c onto Lipid Deposit-Modified Glassy Carbon Surface.

The electrochemical systems of both grafted catechol as a pH-responsive electrophore and immobilized cytochrome c as a model redox protein are detected by cyclic voltammetry at an optimized lipid deposit-modified glassy carbon electrode. The catechol covalent grafting is successfully performed by the one-pot/three-step electrochemical reduction of 3,4-dihydroxybenzenediazonium salts generated in situ from 4-nitrocatechol. The resulting glassy carbon electrode electrochemically modified by grafted catechol species is evaluated as an efficient electrochemical pH sensor. The optimized molar ratio for the lipid deposit, promoting cytochrome c electrochemical activity in solution onto glassy carbon electrode, is reached for the lipid mixture composed of 75% 1,2-dioleoyl-sn-glycero-3-phosphocholine and 25% cardiolipin. Cytochrome c immobilization into the optimized supported lipid deposit is efficiently achieved by cyclic voltammetry (10 cycles) recorded at the modified glassy carbon electrode in a cytochrome c solution. The pH-dependent redox response of the grafted catechol and that of the immobilized cytochrome c are finally detected at the same lipid-modified glassy carbon electrode without alteration of their structure and electrochemical properties in the pH range 5-9.

Reductive electrografting of in situ produced diazopyridinium cations: Tailoring the interface between carbon electrodes and electroactive bacterial films.

Carbon electrodes were functionalized through the reduction of diazopyridinium cations that are produced from in situ diazotization of 2-, 3- and 4-aminopyridine. Diazopyridinium salts were much more rarely employed for surface functionalization than other aryldiazonium derivatives. A study combining X-ray Photoelectron Spectroscopy (XPS), contact angle, ellipsometry, Atomic Force Microscopy (AFM) measurements and electrochemical analyses demonstrates that films obtained from 4-diazopyridinium cations are hydrophilic, dense, compact but sufficiently thin to preserve fast electronic transfer rate, being then relevant to efficiently tailor the interface between the anode surface and an electroactive biofilm. Microbial Fuels Cells (MFCs) with pyridine-functionalized graphite anodes exhibit faster development and improved performances than MFCs operating with bare graphite anodes.

Electronic Interplay between TTF and Extended-TCNQ Electrophores along a Ruthenium Bis(acetylide) Linker.

A bis(TTF-butadiynyl) ruthenium D-D'-D complex, with intramolecular electronic interplay between the three electron-donating electrophores, was easily converted through a cycloaddition-retroelectrocyclization with TCNQ into a D-A-D'-A-D pentad complex, which exhibits an intense intramolecular charge transfer together with an electronic interplay between the two acceptors along the conjugated organometallic bridge.

Trifluoromethyl-substituted tetrathiafulvalenes.

A series of tetrathiafulvalenes functionalized with one or two trifluoromethyl electron-withdrawing groups (EWG) is obtained by phosphite coupling involving CF3-substituted 1,3-dithiole-2-one derivatives. The relative effects of the EWG such as CF3, CO2Me and CN on the TTF core were investigated from a combination of structural, electrochemical, spectrochemical and theoretical investigations. Electrochemical data confirm the good correlations between the first oxidation potential of the TTF derivatives and the σmeta Hammet parameter, thus in the order CO2Me < CF3 < CN, indicating that, in any case, the mesomeric effect of the substituents is limited. Besides, crystal structure determinations show that the deformation of the unsymmetrically substituted dithiole rings, when bearing one, or two different EWG, and attributed to the mesomeric effect of ester or nitrile groups, is not notably modified or counter-balanced by the introduction of a neighboring trifluoromethyl group. DFT calculations confirm these observations and also show that the low energy HOMO-LUMO absorption band found in nitrile or ester-substituted TTFs is not found in TTF-CF3, where, as in TTF itself, the low energy absorption band is essentially attributable to a HOMO→LUMO + 1 transition. Despite relatively high oxidation potentials, these donor molecules with CF3 EWG can be involved in charge transfer complexes or cation radical salts, as reported here for the CF3-subsituted EDT-TTF donor molecule. A neutral charge transfer complex with TCNQ, (EDT-TTF-CF3)2(TCNQ) was isolated and characterized through alternated stacks of EDT-TTF-CF3 dimers and TCNQ in the solid state. A radical cation salt of EDT-TTF-CF3 is also obtained upon electrocrystallisation in the presence of the FeCl4 (-) anion. In this salt, formulated as (EDT-TTF-CF3)(FeCl4), the (EDT-TTF-CF3)(+•) radical cations are associated two-by-two into centrosymmetric dyads with a strong pairing of the radical species in a singlet state.