Valence-state mixing and separation in SmBaFe2O5+w

A mixed-valence state, formally denoted as Fe2.5+, is observed in the 300 K Mössbauer spectra of the most reduced samples of SmBaFe2O5+w. Upon cooling below the Verwey-type transition temperature (TV≈200K), the component assigned to Fe2.5+ separates into a high-spin Fe3+ state and an Fe2+ state with an unusually low internal field. The separation of the mixed-valence state at TV is also confirmed by magnetic susceptibility measurements and differential scanning calorimetry. A model is proposed which accounts for the variation of the amount of the mixed-valence state with the oxygen content parameter w.Peer reviewe

Electroactive Polyhydroquinone Coatings for Marine Fouling Prevention—A Rejected Dynamic pH Hypothesis and a Deceiving Artifact in Electrochemical Antifouling Testing

Nanometer-thin coatings of polyhydroquinone (PHQ), which release and absorb protons upon oxidation and reduction, respectively, were tested for electrochemically induced anti-biofouling activity under the hypothesis that a dynamic pH environment would discourage fouling. Antifouling tests in artificial seawater using the marine, biofilm-forming bacterium Vibrio alginolyticus proved the coatings to be ineffective in fouling prevention but revealed a deceiving artifact from the reactive species generated at the counter electrode (CE), even for electrochemical bias potentials as low as |400| mV versus Ag|AgCl. These findings provide valuable information on the preparation of nanothin PHQ coatings and their electrochemical behavior in artificial seawater. The results further demonstrate that it is critical to isolate the CE in electrochemical anti-biofouling testing

Valence-state mixing and separation in SmBaFe2O5+w

A mixed-valence state, formally denoted as Fe2.5+, is observed in the 300 K Mössbauer spectra of the most reduced samples of SmBaFe2O5+w. Upon cooling below the Verwey-type transition temperature (TV≈200K), the component assigned to Fe2.5+ separates into a high-spin Fe3+ state and an Fe2+ state with an unusually low internal field. The separation of the mixed-valence state at TV is also confirmed by magnetic susceptibility measurements and differential scanning calorimetry. A model is proposed which accounts for the variation of the amount of the mixed-valence state with the oxygen content parameter w.Peer reviewe

Decay times in turnover statistics of single enzymes

The first passage times for enzymatic turnovers in non-equilibrium steady state display a statistical symmetry property related to non-equilibrium fluctuation theorems, that makes it possible to extract the chemical driving force from single molecule trajectories in non-equilibrium steady state. Below, we show that this system violates the general expectation that the number of decay constants needed to fit a first passage time distribution reflects the number of states in the escape problem. In fact, the structure of the kinetic mechanism makes half of the decay times vanish identically from the turnover time distribution. The terms that cancel out correspond to the eigenvalues of a certain sub-matrix of the master equation matrix for the first exit time problem. We discuss how these results make modeling and data analysis easier for such systems, and how the turnovers can be measured.Comment: 4 pages, 1 figure v2: Published version, minor corrections in response to referee comment

151Eu Mössbauer spectroscopy and x-ray-diffraction studies on the Pb2Ba2EuCu3O8+[delta] system

Simultaneous replacement of Sr by Ba and Y by Eu in the Pb-2213 system was found to yield single-phase Pb2Ba2EuCu3O8+δ samples, suitable for Eu151 Mössbauer measurements. The samples were synthesized by a solid-state reaction of metal oxides and carbonates under an inert atmosphere. An oxygen-rich sample corresponding to δ=1.79 was obtained by annealing the as-synthesized material (δ=0.16) in oxygen. The oxygen annealing increased the size of the lattice constants and led to an orthorhombic-to-tetragonal phase transition of the structure. The samples were also oriented in an 11.7-T magnetic field. The x-ray-diffraction spectra showed that the c axes tended to orient perpendicular to the applied field. The measured Mössbauer spectra exhibited an electric quadrupole interaction typical of the Eu site in high-Tc cuprates. The average orientation angles obtained from fittings of the Mössbauer spectra were in accordance with the results from the x-ray-diffraction measurements.Peer reviewe

Europium-based high-temperature superconductors studied by x-ray diffraction and 151Eu Mössbauer spectroscopy

Isotropic powders and magnetically aligned crystallites of EuBa2Cu3O7−δ (1:2:3) and europium-doped Bi2Sr2CaCu2O8 (2:2:1:2) were studied by means of x-ray diffraction and Eu151 Mössbauer spectroscopy. The degree of crystallite orientation of the samples and the values of the lattice constants were determined by x-ray diffraction. The Mössbauer spectra were analyzed considering the full hyperfine Hamiltonian of the nuclear states of the 21.5-keV γ transition. The Mössbauer hyperfine parameters obtained from the superconducting and semiconducting phases are presented. A small change is seen in the Eu151 isomer shift when the oxygen deficiency δ of the 1:2:3 compound is varied. The shift can be explained by a decrease in the s-electron density due to lattice expansion. The changes in the oxidation state of the copper atoms with varying δ were determined from the Mössbauer data: The Cu(2) atoms retain their oxidation state, whereas the Cu(1) atoms adjust their valence according to the value of δ. In the 2:2:1:2 samples, the Eu concentration clearly affected the value of the electric-field gradient at the Eu nucleus. Using a standard procedure, magnetically aligned 2:2:1:2 samples were prepared. The preferred direction of the crystal c axis changed from parallel to perpendicular alignment with the external magnetic field, when the Eu concentration exceeded 20% of the Ca atoms.Peer reviewe