Functionalizing nanocrystalline metal oxide electrodes with robust synthetic redox proteins

De novo designed synthetic redox proteins (maquettes) are structurally simpler, working counterparts of natural redox proteins. The robustness and adaptability of the maquette protein scaffold are ideal for functionalizing electrodes. A positive amino acid patch has been designed into a maquette surface for strong electrostatic anchoring to the negatively charged surfaces of nanocrystalline, mesoporous TiO(2) and SnO(2) films. Such mesoporous metal oxide electrodes offer a major advantage over conventional planar gold electrodes by facilitating formation of high optical density, spectroelectrochemically active thin films with protein loading orders of magnitude greater (up to 8 nmol cm(-2)) than that achieved with gold electrodes. The films are stable for weeks, essentially all immobilized-protein display rapid, reversible electrochemistry. Furthermore, carbon monoxide ligand binding to the reduced heme group of the protein is maintained, can be sensed optically and reversed electrochemically. Pulsed UV excitation of the metal oxide results in microsecond or faster photoreduction of an immobilized cytochrome and millisecond reoxidation. Upon substitution of the heme-group Fe by Zn, the light-activated maquette injects electrons from the singlet excited state of the Zn protoporphyrin IX into the metal oxide conduction band. The kinetics of cytochrome/metal oxide interfacial electron transfer obtained from the electrochemical and photochemical data obtained are discussed in terms of the free energies of the observed reactions and the electronic coupling between the protein heme group and the metal oxide surface.     

BINANA: a novel algorithm for ligand-binding characterization

Computational chemists and structural biologists are often interested in characterizing ligand-receptor complexes for hydrogen-bond, hydrophobic, salt-bridge, van der Waals, and other interactions in order to assess ligand binding. When done by hand, this characterization can become tedious, especially when many complexes need be analyzed. In order to facilitate the characterization of ligand binding, we here present a novel Python-implemented computer algorithm called BINANA (BINding ANAlyzer), which is freely available for download at http://www.nbcr.net/binana/. To demonstrate the utility of the new algorithm, we use BINANA to confirm that the number of hydrophobic contacts between a ligand and its protein receptor is positively correlated with ligand potency. Additionally, we show how BINANA can be used to search through a large ligand-receptor database to identify those complexes that are remarkable for selected binding features, and to identify lead candidates from a virtual screen with specific, desirable binding characteristics. We are hopeful that BINANA will be useful to computational chemists and structural biologists who wish to automatically characterize many ligand-receptor complexes for key binding characteristics.     

The Microstructure of Direct Squeeze Cast and Gravity Die Cast 7050 (Al–6.2Zn–2.3Cu–2.3Mg) Wrought Al Alloy

A 7050 (Al–6.2 wt% Zn–2.3 wt% Cu–2.3 wt% Mg) Al alloy, conventionally used for wrought products, has been successfully cast to near-net shape using direct squeeze casting. Squeeze casting with an applied pressure of 50 MPa removes the defects observed in gravity die cast billets, in particular, (1) shrinkage pipe, (2) poor die replication and waisting, and (3) microporosity. Squeeze casting results in considerable refinement of the microstructure due to an increase in cooling rate from 0.5°C s^–1 for gravity casting to 11°C s^–1 for squeeze casting in a tool steel die lined with porous insulation, and from 2.5 to 10°C s^–1, respectively, in an uninsulated die. A normal segregation pattern of increasing eutectic toward the center of the billet is found for squeeze casting, compared to an inverse segregation pattern of increasing eutectic toward the edge of the billet for gravity casting. This change in segregation pattern is due to a higher radial temperature gradient and reduced time in the semisolid state for squeeze casting.     

End Group Tuning in Acceptor–Donor–Acceptor Nonfullerene Small Molecules for High Fill Factor Organic Solar Cells

High fill factors have only recently become commonplace in nonfullerene‐based organic solar cells, with the balance of charge carrier mobilities often cited as the contributing factor. Here an end‐group modification to a commonly used nonfullerene acceptor (O‐IDTBR) is reported, in which the rhodanine end groups are replaced with dicyano moieties, resulting in the acceptor O‐IDTBCN. This new acceptor affords significant improvement in the fill factor (73%) and photocurrent (19.8 mA cm^?2) in organic solar cells with the low bandgap polymer PTB7‐Th. A narrowing of the bandgap, as a result of greater push–pull hybridization, allows complementary absorption to the donor and thus improved photon harvesting. Additionally, the measurement of charge carrier mobilities and lifetimes in both systems reveal that the PTB7‐Th:O‐IDTBCN blend possesses more balanced charge carrier mobilities, and longer lifetimes. Morphology studies reveal a slightly greater degree of molecular mixing of the O‐IDTBCN when blended with PTB7‐Th, despite the greater and more balanced charge carrier mobilities in this blend.     

Parameters Influencing Charge Separation in Solid‐State Dye‐Sensitized Solar Cells Using Novel Hole Conductors

Solid‐state dye‐sensitized solar cells employing a solid organic hole‐transport material (HTM) are currently under intensive investigation, since they offer a number of practical advantages over liquid‐electrolyte junction devices. Of particular importance to the design of such devices is the control of interfacial charge transfer. In this paper, the factors that determine the yield of hole transfer at the dye/HTM interface and its correlation with solid‐state‐cell performance are identified. To this end, a series of novel triarylamine type oligomers, varying in molecular weight and mobility, are studied. Transient absorption spectroscopy is used to determine hole‐transfer yields and pore‐penetration characteristics. No correlation between hole mobility and cell performance is observed. However, it is found that the photocurrent is directly proportional to the hole‐transfer yield. This hole‐transfer yield depends on the extent of pore penetration in the dye‐sensitized film as well as on the thermodynamic driving force ΔG_dye–HTM for interfacial charge transfer. Future design of alternative solid‐state HTMs should focus on the optimization of pore‐filling properties and the control of interfacial energetics rather than on increasing material hole mobilities.     

Fluorinated polymer films from r.f. plasmas containing benzene and sulfur hexafluorine

Mixtures of C₆H₆ and SF₆ were polymerized in an r.f. discharge. Actinometry (quantitative optical emission spectroscopy) was used to determine trends in the plasma concentrations of the species F, H and CH as a function of the proportion of SF₆ in the feed. Infrared spectroscopy and electron spectroscopy for chemical analysis were employed to characterize the deposited material. Increasing proportions of SF₆ in the feed produced increased fragmentation of the benzene molecules and greater fluorination of the deposited material. The deposition rate, as determined by optical interferometry, was found to be enhanced about 4 times by the presence of 10–20% SF₆ in the feed. At 50% SF₆ in the feed, deposition rates were greater than in pure C₆H₆ plasmas despite the (probably large) etching effect of atomic fluorine from the discharge. Relationships between the plasma composition, electron density and temperature, film composition and growth rate are discussed.     

Photophysical Study of DPPTT‐T/PC70BM Blends and Solar Devices as a Function of Fullerene Loading: An Insight into EQE Limitations of DPP‐Based Polymers

Diketopyrrolopyrrole (DPP)‐based polymers have been consistently used for the fabrication of solar cell devices and transistors due to the existence of intermolecular short contacts, resulting in high electron and hole mobilities. However, they also often show limited external quantum efficiencies (EQEs). In this contribution, the authors analyze the limitations on EQE by a combined study of exciton dissociation efficiency, charge separation, and recombination kinetics in thin films and solar devices of a DPP‐based donor polymer, DPPTT‐T (thieno[3,2‐b]thiophene‐diketopyrrolopyrrole copolymer) blended with varying weight fractions of the fullerene acceptor PC₇₀BM. From the correlations between photoluminescence quenching, transient absorption studies, and EQE measurements, it is concluded that the main limitation of photon‐to‐charge conversion in DPPTT‐T/PC₇₀BM devices is poor exciton dissociation. This exciton quenching limit is related not only to the low affinity/miscibility of the materials, as confirmed by wide angle X‐ray diffraction diffraction and transmission electron microscopy data, but also to the relatively short DPPTT‐T singlet exciton lifetime, possibly associated with high nonradiative losses. A further strategy to improve EQE in this class of polymers without sacrificing the good extraction properties in optimized blends is therefore to limit those nonradiative decay processes.     

Toxicity-directed approach of polyester manufacturing industry wastewater provides useful information for conducting treatability studies

A broader characterization of industrial wastewaters, especially in respect to hazardous compounds and their potential toxicity, is often necessary in order to determine the best practical treatment (or pretreatment) technology available to reduce the discharge of harmful pollutants to the environment or publicly owned treatment works. Using a toxicity-directed approach, this paper sets the base for a rational treatability study of polyester resin manufacturing. Relevant physical and chemical characteristics were determined. Respirometry was used for toxicity reduction evaluation after physical and chemical effluent fractionation. Of all the procedures investigated, only air stripping was significantly effective in reducing wastewater toxicity. Air stripping in pH 7 reduced toxicity in 18.2%, while in pH 11 a toxicity reduction of 62.5% was observed. Results indicated that toxicants responsible for the most significant fraction of the effluent's instantaneous toxic effect to unadapted activated sludge were organic compounds poorly or not volatilized in acid conditions. These results led to useful directions for conducting treatability studies which will be grounded on actual effluent properties rather than empirical or based on the rare specific data on this kind of industrial wastewater.