Although proteins are considered as nonconductors that transfer electrons only up to 1 to 2 nanometers via tunneling, Geobacter sulfurreducens transports respiratory electrons over micrometers, to insoluble acceptors or syntrophic partner cells, via nanowires composed of polymerized cytochrome OmcS. However, the mechanism enabling this long-range conduction is unclear. Here, we demonstrate that individual nanowires exhibit theoretically predicted hopping conductance, at rate (>10 10 s −1 ) comparable to synthetic molecular wires, with negligible carrier loss over micrometers. Unexpectedly, nanowires show a 300-fold increase in their intrinsic conductance upon cooling, which vanishes upon deuteration. Computations show that cooling causes a massive rearrangement of hydrogen bonding networks in nanowires. Cooling makes hemes more planar, as revealed by Raman spectroscopy and simulations, and lowers their reduction potential. We find that the protein surrounding the hemes acts as a temperature-sensitive switch that controls charge transport by sensing environmental perturbations. Rational engineering of heme environments could enable systematic tuning of extracellular respiration.

Multifunctional living materials are attractive due to their powerful ability to self-repair and replicate. However, most natural materials lack electronic functionality. Here we show that an electric field, applied to electricity-producing Geobacter sulfurreducens biofilms, stimulates production of previously unknown cytochrome OmcZ nanowires with 1,000-fold higher conductivity (30 S/cm), and 3-fold higher stiffness (1.5 GPa), than the cytochrome OmcS nanowires that are important in natural environments. Using chemical imaging-based multimodal nanospectroscopy, we correlate protein structure with function, and observe pH-induced conformational switching to β-sheets in individual nanowires, which increases their stiffness and conductivity by 100-fold due to enhanced π-stacking of heme groups; this was further confirmed by computational modelling and bulk spectroscopic studies. These nanowires can transduce mechanical and chemical stimuli into electrical signals to perform sensing, synthesis and energy production. These findings of biologically-produced, highly-conductive protein nanowires may help to guide the development of seamless, bidirectional interfaces between biological and electronic systems.

We consider estimation of the covariance matrix of a multivariate random vector under the constraint that certain covariances are zero. We first present an algorithm, which we call Iterative Conditional Fitting, for computing the maximum likelihood estimator of the constrained covariance matrix, under the assumption of multivariate normality. In contrast to previous approaches, this algorithm has guaranteed convergence properties. Dropping the assumption of multivariate normality, we show how to estimate the covariance matrix in an empirical likelihood approach. These approaches are then compared via simulation and on an example of gene expression.

We demonstrate that the 10-phenyl-10 H-phenothiazine radical cation (PTZ) has a manifold of excited doublet states accessible using visible and near-infrared light that can serve as super-photooxidants with excited-state potentials is excess of +2.1 V vs SCE to power energy demanding oxidation reactions. Photoexcitation of PTZ in CHCN with a 517 nm laser pulse populates a D electronically excited doublet state that decays first to the unrelaxed lowest electronic excited state, D' (τ < 0.3 ps), followed by relaxation to D (τ = 10.9 ± 0.4 ps), which finally decays to D (τ = 32.3 ± 0.8 ps). D' can also be populated directly using a lower energy 900 nm laser pulse, which results in a longer D'→D relaxation time (τ = 19 ± 2 ps). To probe the oxidative power of PTZ photoexcited doublet states, PTZ was covalently linked to each of three hole acceptors, perylene (Per), 9,10-diphenylanthracene (DPA), and 10-phenyl-9-anthracenecarbonitrile (ACN), which have oxidation potentials of 1.04, 1.27, and 1.6 V vs SCE, respectively. In all three cases, photoexcitation wavelength dependent ultrafast hole transfer occurs from D, D', or D of PTZ to Per, DPA, and ACN. The ability to take advantage of the additional oxidative power provided by the upper excited doublet states of PTZ will enable applications using this chromophore as a super-oxidant for energy-demanding reactions.