There has been great interest in the development of stable, inexpensive, efficient catalysts capable of reducing aqueous protons to hydrogen (H2), an alternative to fossil fuels. While synthetic H2 evolution catalysts have been in development for decades, recently there has been great progress in engineering biomolecular catalysts and assemblies of synthetic catalysts and biomolecules. In this Forum Article, progress in engineering proteins to catalyze H2 evolution from water is discussed. The artificial enzymes described include assemblies of synthetic catalysts and photosynthetic proteins, proteins with cofactors replaced with synthetic catalysts, and derivatives of electron-transfer proteins. In addition, a new catalyst consisting of a thermophilic cobalt-substituted cytochrome c is reported. As an electrocatalyst, the cobalt cytochrome shows nearly quantitative Faradaic efficiency and excellent longevity with a turnover number of >270000.

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Using a capacitive photocurrent measurement technique, we demonstrate the ability of both semiconducting and metallic single wall nanotubes to function as photodetectors over a wide spectral range. We observe clear peaks in the photo induced displacement current of a nanotube-plated capacitor that correspond directly to the semiconducting and metallic transitions in the nanotube absorbance spectrum. The signal increases substantially as the carrier drift velocity is raised with applied bias. A large increase in the photocurrent observed below temperatures of 100 K suggests that the nanotube hot carrier relaxation rate decreases substantially at low temperatures.

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A thermal transport mechanism leading to the enhanced thermal conductivity of Graphene nanofluids has been proposed. The Graphene sheet size is postulated to be the key to the underlying mechanism. Based on a critical sheet size derived from Stokes-Einstein equation for the poly-dispersed nanofluid, sheet percolation and Brownian motion assisted sheet collisions are used to explain the heat conduction. A collision dependant dynamic conductivity considering Debye approximated volumetric specific heat due to phonon transport in Graphene has been incorporated. The model has been found to be in good agreement with experimental data.

This paper presents an analytical expression for the diffusing capacity (Theta(t)) of the red blood cell (RBC) for any reactive gas in terms of size and shape of the RBC, thickness of the unstirred plasma layer surrounding the RBC, diffusivities and solubilities of the gas in RBC and boundary layer, hematocrit, and the slope of the dissociation curve. The expression for Theta(t) has been derived by spatial averaging of the fundamental convection-diffusion-reaction equation for O(2) in the RBC and has been generalized to all cell shapes and for other reactive gases such as CO, NO, and CO(2). The effects of size and shape of the RBC, thickness of the unstirred plasma layer, hemoglobin concentration, and hematocrit on Theta(t) have been analyzed, and the analytically obtained expression for Theta(t) has been validated by comparison with different sets of existing experimental data for O(2) and CO(2). Our results indicate that the discoidal shape of the human RBC with average dimensions of 1.6-mum thickness and 8-mum diameter is close to optimal design for O(2) uptake and that the true reaction velocity in the RBC is suppressed significantly by the mass transfer resistance in the surrounding unstirred layer. In vitro measurements using rapid-mixing technique, which measures Theta(t) in the presence of artificially created large boundary layers, substantially underpredicts the in vivo diffusing capacity of the RBC in the diffusion-controlled regime. Depending on the conditions in the RBC, uptake of less reactive gases (such as CO) undergoes transition from reaction-limited to diffusion-limited regime. For a constant set of morphological parameters, the theoretical expression for Theta(t) predicts that Theta(t,NO) > Theta(t,)(CO(2)) > Theta(t,)(O(2)) > Theta(t,CO).

CoGGH, a Gly-Gly-His tripeptide coordinated to a cobalt ion, is shown to catalyze the reduction of aqueous protons to hydrogen (H 2 ) in a light-driven reaction in water near neutral pH. Using [Ru(bpy) 3 ] 2+ as a photosensitizer and ascorbate as an electron donor, a turnover number up to 2200 with respect to CoGGH has been observed with the system remaining active for more than 48 h. The reaction conditions that favor H 2 production are consistent with a reductive quenching mechanism. Results also suggest that CoGGH is robust under these reaction conditions and loss of activity over time results from [Ru(bpy) 3 ] 2+ degradation.