Imidazole facilitates electron transfer from organic reductants

In cyclic voltammetry studies at pH 8, imidazole facilitates oxidation of organic compounds that normally lose hydrogen atoms. High concentrations of imidazole shift the oxidizing wave of ascorbic acid, 2,3-dimethoxy-5-methyl-1,4-hydroquinone, and the vitamin E analogue Trolox toward lower potentials. By contrast, imidazole has no effect on the cyclic voltammogram of methyl viologen, which undergoes electron rather than hydrogen-atom transfer. The effect of imidazole is observed at pH 8.0 but only to a lesser extent at pH 5.5 indicating that imidazole must be unprotonated to facilitate oxidation. Digital simulation shows that these results are consistent with a mechanism in which imidazole acts as a proton acceptor permitting concerted proton/electron transfer by the organic reductant.     

Surface Smoothing of Copper Single Crystals Using POM (Potential Oscillating Method)

The deposition of metals is a process to get metallic coatings on metals. The potential oscillating method (POM) allows dissolution and deposition processes in parallel. Using this method the crystal's habit becomes more perfect, and the equilibrium form can be obtained. It is mostly dominated by the {111}- and the {100}-face, as usual for cubic face centered crystals. The crystallographic faces develop more clearly and become smoother. This paper deals with the determination of the ideal conditions for the electrochemical experiment using copper single crystals, and the analysis of the surface topography using light microscopy, and scanning force microscopy.     

The Tetracyanopyridinide Dimer Dianion, σ‐[TCNPy]22−

The reaction of 2,3,5,6‐tetracyanopyridine (TCNPy) and Cr(C₆H₆)₂ forms diamagnetic σ‐[TCNPy]₂^2? possessing a 1.572(3) Å intrafragment sp³–sp³ bond. This is in contrast to the structurally related 1,2,4,5‐tetracyanobenzene and 1,2,4,5‐tetracyanopyrazine that form π‐dimer dianions possessing long, multicenter bonds.     

An ideal column algorithm for integer programs with special ordered sets of variables

One of the most frequently occurring integer programming structures is the one which has special ordered sets of variables included in multiple choice constraints. For problems with this structure a set of ideal columns are defined from the linear programming relaxation of the integer program and a reduced integer program is formed by keeping only those columns within a specified distance from the ideal column. Conditions are established which guarantee when the optimal solution to the reduced problem is als optimal for the original problem. When these conditions are not satisfied, bounds on the optimal solution value are provided. Ideal columns are also used to establish weights for the special ordered set variables. This procedure has been implemented through a control program written by the authors for MPSX/370-MIP/370. Computational results are given.     

Focusing light with a reflection photon sieve

An advanced type of diffractive optical element is presented that combines the concept of the photon sieve with an off-axis, off-normal incidence reflection geometry. Compared to transmission optical elements, the signal-to-background ratio is significantly increased by separating the first from other diffraction orders without drastically reducing the size of the smallest diffractive element. The reflection photon sieve produces sharp foci at maximum contrast and offers the advantages of effective heat dissipation and a large working space above the focal plane. Experimental results for a device working at a photon energy of 100 eV are presented and compared to theory.     

Mass-dependent bond vibrational dynamics influence catalysis by HIV-1 protease

Protein motions that occur on the microsecond to millisecond time scale have been linked to enzymatic rates observed for catalytic turnovers, but not to transition-state barrier crossing. It has been hypothesized that enzyme motions on the femtosecond time scale of bond vibrations play a role in transition state formation. Here, we perturb femtosecond motion by substituting all nonexchangeable carbon, nitrogen, and hydrogen atoms with (13)C, (15)N, and (2)H and observe the catalytic effects in HIV-1 protease. According to the Born-Oppenheimer approximation, isotopic substitution alters vibrational frequency with unchanged electrostatic properties. With the use of a fluorescent peptide to report on multiple steps in the reaction, we observe significantly reduced rates in the heavy enzyme relative to the light enzyme. A possible interpretation of our results is that there exists a dynamic link between mass-dependent bond vibrations of the enzyme and events in the reaction coordinate.     

A Note on Feasible Flows in Lower-Bounded Multicommodity Networks

This note considers the feasibility for two types of multicommodity flow problems: maximal flow problems with both upper and lower arc capacities, and capacitated minimal cost trans-shipment problems. Although closed form conditions analogous to those known for single commodity problems cannot be derived, it is shown that feasibility is equivalent to finding a maximal multicommodity flow of a specified value on a related network with zero lower bounds, a direct extension of well-known results for single commodity networks.     

Ultrafast melting of a charge-density wave in the Mott insulator 1T-TaS2

Femtosecond time-resolved core-level photoemission spectroscopy with a free-electron laser is used to measure the atomic-site specific charge-order dynamics of the charge-density?wave in the Mott insulator 1T-TaS2. After strong photoexcitation, a prompt loss of charge order and subsequent fast equilibration dynamics of the electron-lattice system are observed. On the time scale of electron-phonon thermalization, about 1?ps, the system is driven across a phase transition from a long-range charge ordered state to a quasiequilibrium state with domainlike short-range charge and lattice order. The experiment opens the way to study the nonequilibrium dynamics of condensed matter systems with full elemental, chemical, and atomic-site selectivity.