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Controlling and understanding electron correlations in quantum matter is one of the most challenging tasks in materials engineering. In the past years a plethora of new puzzling correlated states have been found by carefully stacking and twisting two-dimensional van der Waals materials of different kind. Unique to these stacked structures is the emergence of correlated phases not foreseeable from the single layers alone. In Ta-dichalcogenide heterostructures made of a good metallic "1H"- and a Mott insulating "1T"-layer, recent reports have evidenced a cross-breed itinerant and localized nature of the electronic excitations, similar to what is typically found in heavy fermion systems. Here, we put forward a new interpretation based on first-principles calculations which indicates a sizeable charge transfer of electrons (0.4-0.6 e) from 1T to 1H layers at an elevated interlayer distance. We accurately quantify the strength of the interlayer hybridization which allows us to unambiguously determine that the system is much closer to a doped Mott insulator than to a heavy fermion scenario. Ta-based heterolayers provide therefore a new ground for quantum-materials engineering in the regime of heavily doped Mott insulators hybridized with metallic states at a van der Waals distance. Recent experiments reported the Kondo effect in 1H/1T dichalcogenide hetero-bilayers. Crippa et al. re-examine this interpretation using ab initio calculations and dynamical mean-field theory demonstrating strong charge transfer sensitive to the interlayer separation, indicative of a doped Mott insulator regime. [ABSTRACT FROM AUTHOR]

The Wisconsin high-temperature superconductor axisymmetric mirror experiment (WHAM) will be a high-field platform for prototyping technologies, validating interchange stabilization techniques and benchmarking numerical code performance, enabling the next step up to reactor parameters. A detailed overview of the experimental apparatus and its various subsystems is presented. WHAM will use electron cyclotron heating to ionize and build a dense target plasma for neutral beam injection of fast ions, stabilized by edge-biased sheared flow. At 25 keV injection energies, charge exchange dominates over impact ionization and limits the effectiveness of neutral beam injection fuelling. This paper outlines an iterative technique for self-consistently predicting the neutral beam driven anisotropic ion distribution and its role in the finite beta equilibrium. Beginning with recent work by Egedal et al. (Nucl. Fusion , vol. 62, no. 12, 2022, p. 126053) on the WHAM geometry, we detail how the FIDASIM code is used to model the charge exchange sources and sinks in the distribution function, and both are combined with an anisotropic magnetohydrodynamic equilibrium solver method to self-consistently reach an equilibrium. We compare this with recent results using the CQL3D code adapted for the mirror geometry, which includes the high-harmonic fast wave heating of fast ions. [ABSTRACT FROM AUTHOR]

The second flavor of hydrogen atoms (SFHA) refers to the kind of hydrogen atoms that have only the states of the zero orbital angular momentum (the S-states), both in the discrete and continuous spectra. They were first discovered theoretically in one of my earlier papers, where a proof of their existence was also provided by analyzing atomic experiments concerning the high-energy tail of the linear momentum distribution in the ground state of hydrogen atoms. From a theoretical point of view, the discovery was based on the standard Dirac equation for hydrogen atoms without changing the existing physical laws. Recently, the existence of the SFHA was seemingly also confirmed by two types of astrophysical observations: the allowance for the SFHA explained the puzzling results concerning both the anomalous absorption of the redshifted 21 cm spectral line from the early Universe, and the observations by the Dark Energy Survey (DES) team where it was found that the distribution of dark matter in the Universe is noticeably smoother than predictions employing Einstein’s relativity. In the present review, we exhibit results from two recent papers where attention was brought to a visible difference in the cross-sections of the resonant charge exchange for collisions of the SFHA with incoming protons, compared to collisions of the usual hydrogen atoms with incoming protons. It was shown that, after taking into account the SFHA, there is a better agreement with the corresponding experimental cross-section. Coupled with the previous evidence of the existence of the SFHA, deduced from the analysis of the other kind of atomic experiments, and evidenced by two different kinds of astrophysical observations, this strengthens the standing of the SFHA as the most probable candidate for all or a part of dark matter.

Abstract The 3-GeV Rapid Cycling Synchrotron at the Japan Proton Accelerator Research Complex supplies a high-intensity proton beam for neutron experiments and to the Main Ring synchrotron. Various parameters are monitored to achieve a stable operation, and it was found that the oscillations of the charge-exchange efficiency and cooling water temperature were synchronized. We evaluated the orbit fluctuations at the injection point using a beam current of the injection dump, which is proportional to the number of particles that miss the foil and fail in the charge exchange, and profile of the injection beam. The total width of the fluctuations was approximately 0.072 mm. This value is negligible from the user operation viewpoint as our existing beam position monitors cannot detect such a small signal deviation. This displacement corresponds to a 1.63 × 10− 5 variation in the dipole magnetic field. Conversely, the magnetic field variation in the L3BT dipole magnet, which was estimated by the temperature change directly, is 4.08 × 10− 5. This result suggested that the change in the cooling water temperature is one of the major causes of the efficiency fluctuation.

We have studied single-electron turnstile operation in common-gated one-dimensional arrays of four tunnel junctions (three dots) having inhomogeneous junction capacitances. Analytical calculations show that the source-drain voltage range with a current plateau due to single-electron turnstile operation is increased when the outer two tunnel capacitances are adjusted to be smaller than the inner ones. In fact, we have demonstrated in phosphorous-doped silicon-on-insulator field-effect transistors (FETs) that back-gate voltage works to assist the turnstile operation, which is primarily ascribed to electrical control of junction capacitance dispersion, i.e., reduction in outer junction capacitances. As a result, postfabrication control of capacitance dispersion in multijunction FETs can be achieved, resulting in successful turnstile operation. [ABSTRACT FROM AUTHOR]

We theoretically investigate the coherent transfer of one electron between the ground states of a double coupled quantum dot structure. The coherent transfer of the electron is externally controlled by applied electromagnetic fields with on- or close-resonance driving frequencies and various shapes and duration. We derive the analytical expressions for the parameters of the external fields by approximating the quantum dot system as a three-level Λ-type system. The analytical solutions are compared with numerical results and good agreement is found. The control methods developed here are applicable in symmetric and asymmetric quantum dot nanostructures. [ABSTRACT FROM AUTHOR]

Rigorous expressions for the calculation of nonadiabatic electron transfer rates are presented in closed forms for donor-acceptor systems incorporated fluctuating bridges and their non-Condon electronic couplings. In high temperature limit, they show a similar property to the Marcus formula. However, the Marcus parabolic with respect to the driving force is shifted for the exponential coupling while it becomes an overlap of several Gaussian functions for the linear coupling. Furthermore, the effective couplings are exponentially and linearly dependent on temperature and the squared frequencies of bridge modes for the exponential and linear couplings, respectively. [ABSTRACT FROM AUTHOR]

A comprehensive analysis is presented for the acid-base double-exchange reaction as well as the associated acid-displacement and base-displacement “half-reactions” with the goal of elucidating the meaning of the hard/soft acid/base (HSAB) principle and the conditions for its validity. When electron-transfer effects are important and other effects are negligible, the HSAB principle is driven by the surpassing stability of the soft acid/soft base product. When electrostatic effects dominate the reactivity, the HSAB principle is driven by the surpassing stability of the hard acid/hard base product. Because electron-transfer effects favor soft/soft interactions, while electrostatic effects favor hard/hard interactions, acid-base exchange reactions may be used to determine whether a reagent’s reactivity is dominated by electron-transfer or by electrostatic effects. Because electron-transfer and electrostatic considerations separately favor the HSAB principle whenever the electronic chemical potentials of the acids and bases involved in the reaction are similar, our analysis provides strong support for the HSAB principle. The electronic chemical potential measures the intrinsic strength of acids and bases. [ABSTRACT FROM AUTHOR]

The paper develops a theory of electron transfer with torsionally induced non-Condon (NC) effects. The starting point of the theory is a generalized spin-boson Hamiltonian, where an additional torsional oscillator bilinearly coupled to other bath modes causes a sinusoidal NC modulation. We derive closed form time dependent nonadiabatic rate expressions for both sudden and relaxed initial conditions, which are applicable for general spectral densities and energetic condition. Under the assumption that the torsional motion is not correlated with the polaronic shift of the bath, simple stationary limit rate expression is obtained. Model calculations of this rate expression illustrate the effects of torsional quantization and gating on the driving force and temperature dependences of the electron transfer rate. The classical limit of the rate expression consists of three Marcus-type terms, and is shown to agree very well with the exact numerical result.© 2005 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We report on exchange bias of Mn100-xPtx/Co90Fe10 bottom-pinned bilayers prepared by ion beam deposition. The Pt content in the film was varied 6 at. % with x between 46 and 52 at. % by changing the angle of substrate relative to the target in a range of 40°. Exchange coupling for a Mn100-xPtx(20 nm)/Co90Fe10(5 nm) bilayer was found to be maximum (Jex=0.34 erg/cm2) at a composition with x=50 at. %. Structure and magnetic properties of the bilayers deposited on Ta, Ta/Ru, and Ta/Ni81Fe19 seed layers were studied by vibrating sample magnetometry, x-ray diffraction, Rutherford backscattering spectroscopy, and atomic force microscopy. Exchange bias and coercive field can be tuned as functions of the seed layer. The effect of different annealing conditions on exchange bias is discussed to improve thermal stability of the bilayers. Maximum exchange coupling is obtained at an annealing temperature TA>=280 °C, while the blocking temperature TB keeps increasing with annealing up to TA=420 °C. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Photoemission spectroscopy of an interface between Mg and a silole derivative, 2,5-bis[6[sup ′]-(2[sup ′],2[sup ″]-bipyridyl)]-1,1-dimethyl-3,4-diphenyl silacyclopentadiene (PyPySPyPy) reveals the formation of two gap states both at metal-on-organic (Mg/PyPySPyPy) and organic-on-metal (PyPySPyPy/Mg) interfaces. The appearance of gap states is interpreted as the result of electron transfer from Mg to PyPySPyPy, leading to the formation of a charge transfer complex. A strong correlation found between the metal and organic core level shifts, and the changes in the Fermi level position at the Mg/PyPySPyPy interface further supports the model of charge transfer between the metal and the organic. Despite the similar chemical character of the two interfaces, the binding energy (BE) of the gap states at the PyPySPyPy/Mg interface is 0.2–0.3 eV higher than the gap state BE measured at the reversed interface. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Photoinduced electron transfer (ET) between coumarin dyes and aromatic amines has been investigated in Triton-X-100 micellar solutions and the results have been compared with those observed earlier in homogeneous medium. Significant static quenching of the coumarin fluorescence due to the presence of high concentration of amines around the coumarin fluorophore in the micelles has been observed in steady-state fluorescence studies. Time-resolved studies with nanosecond resolutions mostly show the dynamic part of the quenching for the excited coumarin dyes by the amine quenchers. A correlation of the quenching rate constants, estimated from the time-resolved measurements, with the free energy changes (ΔG[sup 0]) of the ET reactions shows the typical bell shaped curve as predicted by Marcus outer-sphere ET theory. The inversion in the ET rates for the present systems occurs at an exergonicity (-ΔG[sup 0]) of ∼0.7–0.8 eV, which is unusually low considering the polarity of the Palisade layer of the micelles where the reactants reside. Present results have been rationalized on the basis of the two dimensional ET model assuming that the solvent relaxation in micellar media is much slower than the rate of the ET process. Detailed analysis of the experimental data shows that the diffusional model of the bimolecular quenching kinetics is not applicable for the ET reactions in the micellar solutions. In the present systems, the reactions can be better visualized as equivalent to intramolecular electron transfer processes, with statistical distribution of the donors and acceptors in the micelles. A low electron coupling (V[sub el]) parameter is estimated from the correlation of the experimentally observed and the theoretically calculated ET rates, which indicates that the average donor–acceptor separation in the micellar ET reactions is substantially larger than for the donor–acceptor contact distance. Comparison of the V[sub el] values in the micellar solution and in the donor–acceptor close contact suggests that there is an intervention of a surfactant chain between the interacting donor and acceptor in the micellar ET reaction. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Energy fluctuations of a solute molecule embedded in a polar solvent are investigated to depict the energy landscape for solvation dynamics. The system is modeled by a charged molecule surrounded by two layers of solvent dipolar molecules with simple rotational dynamics. Individual solvent molecules are treated as simple dipoles that can point toward or away from the central charge (Ising spins). Single-spin-flip Monte Carlo kinetics simulations are carried out in a two-dimensional lattice for different central charges, radii of outer shell, and temperatures. By analyzing the density of states as a function of energy and temperatures, we have determined the existence of multiple freezing transitions. Each of them can be associated with the freezing of a different layer of the solvent. [ABSTRACT FROM AUTHOR]

Titanium dioxide nanoparticles co-modified with CuOx (0≤x≤2) and carbonaceous materials were prepared with a simple hydrolysis and photo-reduction method for photocatalytic hydrogen generation. SEM/TEM and XPS analysis indicated that the carbonaceous materials were mostly coated on the TiO2 surface and clearly revealed that the Cu species exhibited multivalence states, existing as CuOx (0≤x≤2). The optimal catalyst showed a 56-fold enhanced hydrogen evolution rate compared with that of the pure C/TiO2 catalyst. Further, an intensive multiple electron transfer effect originating from CuOx and the carbonaceous materials is proposed to be responsible for the elevated photoactivity. CuOx species serve as electron donors facilitating charge carrier transfer and proton reduction sites. The carbonaceous materials function as the “bridge” that transfers the electrons of TiO2 to the CuOx species, which provides a new route for electron transfer and reinforces the effect of CuOx as a co-catalyst. In this study, the CuOx and C co-modified TiO2 catalyst was prepared with multiple electron transport pathways and enhanced hydrogen production evolution, which provides a deep understanding for the design of co-catalyst-based photocatalysts. [ABSTRACT FROM AUTHOR]

Collisions with cold particles can dissipate a hot particle’s energy and therefore can be exploited as a cooling mechanism. Kinetics teach us that cooling a particle down by several orders of magnitude typically takes many elastic collisions as each one only carries away a fraction of the collision energy. Recently, for a system comprising hot ions and cold atoms, a very fast cooling process has been suggested (Ravi et al 2012 Nat. Commun. 3 1126 ) where cooling over several orders of magnitude can occur in a single step. Namely, in a homo-nuclear atom–ion collision, an electron can resonantly hop from an ultracold atom onto the hot ion, converting the cold atom into a cold ion. Here, we demonstrate such swap cooling in a direct way as we experimentally observe how a single energetic ion loses energy in a cold atom cloud. In order to contrast swap cooling with sympathetic cooling, we perform the same measurements with a hetero-nuclear atom–ion system, for which swap cooling cannot take place, and indeed observe very different cooling dynamics. Ab initio numerical model calculations agree well with our measured data and corroborate our interpretations.

Adenosine deaminase (ADA) catalyzes the deamination of adenosine, which is important in purine metabolism. ADA is ubiquitous to almost all human tissues, and ADA abnormalities have been reported in various diseases, including rheumatoid arthritis. ADA can be divided into two conformations based on the inhibitor that it binds to: open and closed forms. Here, we chose three ligands, namely, FR117016 (FR0), FR221647 (FR2) (open form), and HDPR (PRH, closed form), to investigate the inhibition mechanism of ADA and its effect on ADA through molecular dynamics simulations. In open forms, Egap and electrostatic potential (ESP) indicated that electron transfer might occur more easily in FR0 than in FR2. Binding free energy and hydrogen bond occupation revealed that the ADA-FR0 complex had a more stable structure than ADA-FR2. The probability of residues Pro159 to Lys171 of ADA-FR0 and ADA-FR2 to form a helix moderately increased compared with that in nonligated ADA. In comparison with FR0 and FR2 PRH could maintain ADA in a closed form to inhibit the function of ADA. The α7 helix (residues Thr57 to Ala73) of ADA in the closed form was mostly unfastened because of the effect of PRH. The number of H bonds and the relative superiority of the binding free energy indicated that the binding strength of PRH to ADA was significantly lower than that of an open inhibitor, thereby supporting the comparison of the inhibitory activities of the three ligands. Alanine scanning results showed that His17, Gly184, Asp295, and Asp296 exerted the greatest effects on protein energy, suggesting that they played crucial roles in binding to inhibitors. This study served as a theoretical basis for the development of new ADA inhibitors. [ABSTRACT FROM AUTHOR]

We investigate functional role of the P76GTKMIFA83 fragment of the primary structure of cytochrome c. Based on the data obtained by the analysis of informational structure (ANIS), we propose a model of functioning of cytochrome c. According to this model, conformational rearrangements of the P76GTKMIFA83 loop fragment have a significant effect on conformational mobility of the heme. It is suggested that the conformational mobility of cytochrome c heme is responsible for its optimal orientation with respect to electron donor and acceptor within ubiquinol–cytochrome c oxidoreductase (complex III) and cytochrome c oxidase (complex IV), respectively, thus, ensuring electron transfer from complex III to complex IV. To validate the model, we design several mutant variants of horse cytochrome c with multiple substitutions of amino acid residues in the P76GTKMIFA83 sequence that reduce its ability to undergo conformational rearrangements. With this, we study the succinate–cytochrome c reductase and cytochrome c oxidase activities of rat liver mitoplasts in the presence of mutant variants of cytochrome c. The electron transport activity of the mutant variants decreases to different extent. Resonance Raman spectroscopy (RRS) and surface-enhanced Raman spectroscopy (SERS) data demonstrate, that all mutant cytochromes possess heme with the higher degree of ruffling deformation, than that of the wild-type (WT) cytochrome c. The increase in the ruffled deformation of the heme of oxidized cytochromes correlated with the decrease in the electron transport rate of ubiquinol–cytochrome c reductase (complex III). Besides, all mutant cytochromes have lower mobility of the pyrrol rings and methine bridges, than WT cytochrome c. We show that a decrease in electron transport activity in the mutant variants correlates with conformational changes and reduced mobility of heme porphyrin. This points to a significant role of the P76GTKMIFA83 fragment in the electron transport function of cytochrome c. [ABSTRACT FROM AUTHOR]

High-potential iron-sulfur protein (HiPIP) is a soluble electron carrier protein of photosynthetic bacteria with an Fe4S4 cluster. Although structural changes accompanying the electron transfer are important for understanding of the functional mechanism, the changes have not been clarified in sufficient detail. We previously reported the high-resolution crystal structures of HiPIP from a thermophilic purple bacterium Thermochromatium tepidum in the reduced state. In order to perform a detailed comparison between the structures in different redox states, the oxidized structure should also be revealed at high resolution. Therefore, in the present study we performed a crystallographic analysis of oxidized HiPIP and a structural comparison with the reduced form at a high resolution of 0.8 Å. The comparison highlighted small but significant contraction in the iron-sulfur cluster. The changes in Fe-S bond lengths were similar to that predicted by theoretical calculation, although some discrepancies were also found. Almost distances between the sulfur atoms of the iron-sulfur cluster and the protein environment are elongated upon the oxidation. Positional changes of hydrogen atoms in the protein environment, such as on the amide-hydrogen of Cys75 in the proximity of the iron-sulfur cluster, were also observed in the accurate analyses. None of the water molecules exhibited significant changes in position or anisotropy of atomic displacement parameter between the two states, while the orientations of some water molecules were different. [ABSTRACT FROM AUTHOR]

Electrogenic bacteria are organisms that can transfer electrons to extracellular electron acceptors and have the potential to be used in devices such as bioelectrochemical systems (BES). In this study, Dietzia sp. RNV-4 bacterium has been isolated and identified based on its biochemical, physiological and morphological characteristics, as well as by its 16S rRNA sequence analysis. Furthermore, the current density production and electron transfer mechanisms were investigated using bioelectrochemical methods. The chronoamperometric data showed that the biofilm of Dietzia sp. RNV-4 grew as the current increased with time, reaching a maximum of 176.6 ± 66.1 mA/m2 at the end of the experiment (7 d); this highly suggests that the current was generated by the biofilm. The main electron transfer mechanism, indicated by the cyclic voltammograms, was due to secreted redox mediators. By high performance liquid chromatography, canthaxanthin was identified as the main compound involved in charge transfer between the bacteria and the solid electrodes. Dietzia sp. RNV-4 was used as biological material in a microbial fuel cell (MFC) and the current density production was 299.4 ± 40.2 mA/m2. This is the first time that Dietzia sp. RNV-4 has been electrochemically characterized and identified as a new electrogenic strain. [ABSTRACT FROM AUTHOR]

Three-dimensional (3D) nanometal scaffolds have gained considerable attention recently because of their promising application in high-performance supercapacitors compared with plain metal foils. Here, a highly oriented nickel (Ni) nanowire array (NNA) film was prepared via a simple magnetic-field-driven aqueous solution deposition process and then used as the electrode scaffold for the vapor-phase polymerization of 3,4-ethylenedioxythiophene (EDOT). Benefiting from the unique 3D open porous structure of the NNA that provided a highly conductive and oriented backbone for facile electron transfer and fast ion diffusion, the as-obtained poly(3,4-ethylenedioxythiophene) (PEDOT) exhibited an ultra-long cycle life (95.7% retention of specific capacitance after 20 000 charge/discharge cycles at 5 A/g) and superior capacitive performance. Furthermore, two electrodes were fabricated into an aqueous symmetric supercapacitor, which delivered a high energy density (30.38 Wh/kg at 529.49 W/kg) and superior long-term cycle ability (13.8% loss of capacity after 20 000 cycles). Based on these results, the vapor-phase polymerization of EDOT on metal nanowire array current collectors has great potential for use in supercapacitors with enhanced performance. [ABSTRACT FROM AUTHOR]

Copper is a crucial ion in cells, but needs to be closely controlled due to its toxic potential and ability to catalyse the formation of radicals. In chloroplasts, an important step for the proper functioning of the photosynthetic electron transfer chain is the delivery of copper to plastocyanin in the thylakoid lumen. The main route for copper transport to the thylakoid lumen is driven by two PIB-type ATPases, Heavy Metal ATPase 6 (HMA6) and HMA8, located in the inner membrane of the chloroplast envelope and in the thylakoid membrane, respectively. Here, the crystal structures of the nucleotide binding domain of HMA6 and HMA8 from Arabidopsis thaliana are reported at 1.5Å and 1.75Å resolution, respectively, providing the first structural information on plants Cu+-ATPases. The structures reveal a compact domain, with two short helices on both sides of a twisted beta-sheet. A double mutant, aiding in the crystallization, provides a new crystal contact, but also avoids an internal clash highlighting the benefits of construct modifications. Finally, the histidine in the HP motif of the isolated domains, unable to bind ATP, shows a side chain conformation distinct from nucleotide bound structures. [ABSTRACT FROM AUTHOR]

Certain species of sulfate-reducing bacteria (SRB) use cathodes as electron donors for metabolism, and this electron transfer process may influence the proper protection potential choice for structures. The interaction between SRB and polarized electrodes had been the focus of numerous investigations. In this paper, the impact of cathodic protection (CP) on Desulfovibrio caledoniens metabolic activity and its influence on highs trength steel EQ70 were studied by bacterial analyses and electrochemical measurements. The results showed that EQ70 under -0.85 VSCE CP had a higher corrosion rate than that without CP, while EQ70 with -1.05 VSCE had a lower corrosion rate. The enhanced SRB metabolic activity at -0.85 VSCE was most probably caused by the direct electron transfer from the electrode polarized at -0.85 VSCE. This direct electron transfer pathway was unavailable in -1.05 VSCE. In addition, the application of cathodic protection led to the transformation of sulfide rusts into carbonates rusts. These observations have been employed to provide updated recommendations for the optimum CP potential for steel structures in the presence of SRB. [ABSTRACT FROM AUTHOR]

While most biological materials are insulating in nature, efficient extracellular electron transfer is a critical property of biofilms associated with microbial electrochemical systems and several microorganisms are capable of establishing conductive aggregates and biofilms. Though construction of these conductive microbial networks is an intriguing and important phenomenon in both natural and engineered systems, few studies have been published related to conductive biofilms/aggregates and their conduction mechanisms, especially in mixed-species environments. In the present study, current-producing mixed species biofilms exhibited high conductivity across non-conductive gaps. Biofilm growth observed on the inactive electrode contributed to overall power outputs, suggesting that an electrical connection was established throughout the biofilm assembly. Electrochemical gating analysis of the biofilms over a range of potentials (-600–200 mV, vs. Ag/AgCl) resulted in a peak-manner response with maximum conductance of 3437 ± 271 μS at a gate potential of -360 mV. Following removal of the electron donor (acetate), a 96.6% decrease in peak conductivity was observed. Differential responses observed in the absence of an electron donor and over varying potentials suggest a redox driven conductivity mechanism in mixed-species biofilms. These results demonstrated significant differences in biofilm development and conductivity compared to previous studies using pure cultures. [ABSTRACT FROM AUTHOR]

Cytochrome bd-I is one of the three proton motive force-generating quinol oxidases in the O2-dependent respiratory chain of Escherichia coli. It contains one low-spin haem (b558) and the two high-spin haems (b595 and d) as the redox-active cofactors. In order to examine the flash-induced intraprotein reverse electron transfer (the so-called ''electron backflow''), CO was photolyzed from the ferrous haem d in one-electron reduced (b5583+b5953+d2+-CO) cytochrome bd-I, and the fully reduced (b5582+b5952+d2+-CO) oxidase as a control. In contrast to the fully reduced cytochrome bd-I, the transient spectrum of one-electron reduced oxidase at a delay time of 1.5 μs is clearly different from that at a delay time of 200 ns. The difference between the two spectra can be modeled as the electron transfer from haem d to haem b595 in 3–4% of the cytochrome bd-I population. Thus, the interhaem electron backflow reaction induced by photodissociation of CO from haem d in one-electron reduced cytochrome bd-I comprises two kinetically different phases: the previously unnoticed fast electron transfer from haem d to haem b595 within 0.2–1.5 μs and the slower well-defined electron equilibration with τ ~16 μs. The major new finding of this work is the lack of electron transfer at 200 ns. [ABSTRACT FROM AUTHOR]