Changes in metal specificity due to iron ligand substitutions in reaction centers fromRhodobacter sphaeroides

Bacterial reaction centers have a single nonheme iron that is located between two bound quinones, Q_A and Q_B, which are the primary and secondary electron acceptors during photosynthesis, respectively. InRhodobacter sphaeroides, the iron is coordinated by four nitrogen atoms, contributed by histidines at L190, L230, M219, and M266, and two oxygen atoms, contributed by Glu at M234. The roles of these ligands in determining the metal-binding specificity and electron transfer properties of the quinones were investigated by mutagenesis. Each of the four His ligands was changed to Glu, Gln, and Cys, whereas Glu was changed to His, Gln, Cys, and Asp. All mutants supported photosynthetic growth except for those with substitutions of Glu or Cys at L190 or M219. The metal specificity of isolated mutant RCs was determined by measurements using atomic absorption and 35 GHz electron paramagnetic resonance spectroscopy. The M234 mutants had a lesser iron specificity than the wild type with a mole fraction of 0.7 to 0.8 iron but retained a total metal content of 1.0. All His mutants had an even lower iron content with mole fractions of 0.04 to 0.16. The His to Cys at M266 mutant had a significantly greater amount of bound zinc that was further enhanced when the strain was grown in zinc-supplemented media. The charge recombination rates from Q _B ^?. , which ranged from 0.5 to 1 s^?1 in the mutants, were comparable to the 1 s^?1 value for the wild type. Charge recombination from Q _A ^?. showed complex kinetics, with rates of 15 to 30 s^?1 for the L190, L230, and M234 mutants and 200 s^?1 for the M266 mutants compared with 8 s^?1 for the wild type. The faster rates in the mutants most likely reflected a smaller free energy difference between Q _A ^?. and Φ _A ^? , a nearby bacteriopheophytin, with the smaller energy difference facilitating indirect recombination. All of the mutants transferred electrons to the secondary quinone, with rates (1200 to 4700 s^?1) comparable to that of the native (3700 s^?1). The data demonstrate that neither the ligands nor the bound metal play a critical role in the electron transfer processes at the acceptor side.     

Liquid membrane transport: a survey

The literature pertaining to facilitated transport and liquid membrane separations is reviewed and summarized, especially work reported since 1977. Liquid membranes of all geometries are discussed, including immobilized liquid membranes and liquid surfactant or emulsion liquid membranes. Emphasis is placed on facilitated, or carrier-mediated transport in both configurations although other mechanisms such as coupled-transport and transport due to solubility differences are discussed. Mathematical modeling and analytical solutions for facilitated transport models are summarized. The possibility of industrial application of liquid membrane technology is mentioned and the most important experimental techniques for liquid membrane research are discussed. Also, directions for future research are recommended.     

The effect of air exposure on palladium–copper composite membranes

It was found that when electrolessly deposited thin Pd and Pd–Cu membranes were exposed to air at temperatures above 350 °C, their H₂ flux increased substantially immediately after the air exposure, then decreased to a new steady-state value. While this was a quasi-reversible change for the H₂ flux, the flux of insoluble species, such as N₂, irreversibly increased with every air exposure but by a much smaller extent. The extent of these changes was found to be dependent on the exposure time and the temperature of the tests. Thus, we decided to investigate the effect of gas exposures on the properties of these materials.

Palladium and palladium–copper films, prepared by electroless deposition on ceramic supports, and commercial foils were exposed to air, hydrogen and helium at 500 and 900 °C for times varying from 1 h to 1 week with the objective of determining the effect of the different exposure conditions on the surface morphology, the flux of different penetrants and the crystalline structure of the materials. Atomic force microscopy (AFM) and X-ray diffraction (XRD) were used to study the changes occurring in the films under those conditions.

It was observed that the exposure of both the electroless films and the foils to hydrogen and air markedly modified their surface morphology. The hydrogen exposure tended to smooth the surface features whereas the oxygen exposure created new surface features such holes and large peaks. Additionally it was found that the air exposure produced some oxidation of the film to create PdO.

These results suggested that a common hypothesis stating that air oxidation just cleans the surface of the membrane might not be sufficient to explain all of those changes. A contributing effect of air exposure may be the increase in surface area due to the formation of palladium oxide. However, the extent of the surface area increase was insufficient to explain the increase in steady-state H₂ flux.     

High Entropy Alloys as Filler Metals for Joining

In the search for applications for alloys developed under the philosophy of the High Entropy Alloy (HEA)-type materials, the focus may be placed on applications where current alloys also use multiple components, albeit at lower levels than those found in HEAs. One such area, where alloys with complex compositions are already found, is in filler metals used for joining. In soldering (<450 °C) and brazing (>450 °C), filler metal alloys are taken above their liquidus temperature and used to form a metallic bond between two components, which remain both unmelted and largely unchanged throughout the process. These joining methods are widely used in applications from electronics to aerospace and energy, and filler metals are highly diverse, to allow compatibility with a broad range of base materials (including the capability to join ceramics to metals) and a large range of processing temperatures. Here, we review recent developments in filler metals relevant to High Entropy materials, and argue that such alloys merit further exploration to help overcome a number of current challenges that need to be solved for filler metal-based joining methods.     

Application of Mathematical Programming to a Large-scale Agricultural Production and Distribution System

This paper addresses an actual production planning problem for a large seed corn production company. Various scenarios are included in different mathematical programming models in order to help the management make production decisions. A linear programming package and a mixed-integer programming package are combined by a designed heuristic program to solve the problem. The solutions obtained and an accompanying sensitivity analysis provide the management with insight into the system's operation and potentials of cost savings.     

Dynamic load and inflation pressure effects on contact pressures of a forestry forwarder tire

A Trelleborg Twin 421 Mark II 600/55-26.5 steel-reinforced bias-ply forwarder drive tire at inflation pressures of 100 and 240 kPa and dynamic loads of 23.9 and 40 kN was used at 5% travel reduction on a firm clay soil. Effects of dynamic load and inflation pressure on soil–tire contact pressures were determined using six pressure transducers mounted on the tire tread. Three were mounted on the face of a lug and three at corresponding locations on the undertread. Contact angles increased with decreases in inflation pressure and increases in dynamic load. Contact pressures on a lug at the edge of the tire increased as dynamic load increased. Mean and peak pressures on the undertread generally were less than those on a lug. The peak pressures on a lug occurred forward of the axle in nearly all combinations of dynamic load, inflation pressure, and pressure sensor location, and peak pressures on the undertread occurred to the rear of the axle in most of the combinations. Ratios of the peak contact pressure to the inflation pressure ranged from 0 at the edge of the undertread for three combinations of dynamic load and inflation pressure to 8.39 for the pressure sensor on a lug, near the tire centerline, when the tire was underinflated. At constant dynamic load, net traction and tractive efficiency decreased as inflation pressure increased.     

A computational and experimental study of the structures and Raman and 77Se NMR spectra of SeX3+ and SeX2 (X = Cl, Br, I): FT-Raman spectrum of (SeI3)[AsF6

The ability of MP2, B3PW91 and PBE0 methods to produce reliable predictions in structural and spectroscopic properties of small selenium-halogen molecules and cations has been demonstrated by using 6-311G(d) and cc-pVTZ basis sets. Optimized structures and vibrational frequencies agree closely with the experimental information, where available. Raman intensities are also well reproduced at all levels of theory. Calculated GIAO isotropic shielding tensors yield a reasonable linear correlation with the experimental chemical shift data at each level of theory. The largest deviations between calculated and experimental chemical shifts are found for selenium-iodine species. The agreement between observed and calculated chemical shifts for selenium-iodine species can be improved by inclusion of relativistic effects using the ZORA method. The best results are achieved by adding spin-orbit correction terms from ZORA calculations to nonrelativistic GIAO isotropic shielding tensors. The calculated isotropic shielding tensors can be utilized in the spectroscopic assignment of the 77Se chemical shifts of novel selenium-halogen molecules and cations. The experimental FT-Raman spectra of (SeI3)[AsF6] in the solid state and in SO2(l) solution are also reported.     

A Consistent Determination of the Dimerization Constants of the Self‐Association of 2,2‐Dimethyl‐3‐ethyl‐3‐pentanol in Carbon Tetrachloride from its Infrared Spectral Data

Two equations of linear type (Eqs. 10 and 17 in the text) have been derived to analyze the IR data to determine the dimerization constant consistently. Equation 10 is to be used to fit the integrated absorbances of the monomer band to obtain the molar monomer absorptivity, ?_m, and dimerization constant, K; Eq. 17 is to be used to fit the integrated absorbances of the dimer bands to obtain the molar dimer absorptivity, ?_d, and dimerization constant, K. Thus the same dimerization constant can be independently determined either from the monomer band or from the dimer band. The discrepancy between the two determined values provides an assessment of the consistency of determination. The monomer‐dimer self‐association of 2,2‐dimethyl‐3‐ethyl‐3‐pentanol in the solvent of carbon tetrachloride was chosen to demonstrate the utility of these two equations.