On the Validity of Entropy Production Principles for Linear Electrical Circuits

We explain the (non-)validity of close-to-equilibrium entropy production principles in the context of linear electrical circuits. Both the minimum and the maximum entropy production principles are understood within dynamical fluctuation theory. The starting point are Langevin equations obtained by combining Kirchoff’s laws with a Johnson-Nyquist noise at each dissipative element in the circuit. The main observation is that the fluctuation functional for time averages, that can be read off from the path-space action, is in first order around equilibrium given by an entropy production rate. That allows to understand beyond the schemes of irreversible thermodynamics (1) the validity of the least dissipation, the minimum entropy production, and the maximum entropy production principles close to equilibrium; (2) the role of the observables’ parity under time-reversal and, in particular, the origin of Landauer’s counterexample (1975) from the fact that the fluctuating observable there is odd under time-reversal; (3) the critical remark of Jaynes (1980) concerning the apparent inappropriateness of entropy production principles in temperature-inhomogeneous circuits.     

Internal magnetic fields in submicron particles of barium hexaferrite detected by 57Fe NMR

⁵⁷Fe nuclear magnetic resonance (NMR) spectra of hexaferrite BaFe₁₂O₁₉ powder samples prepared by glass crystallization method were measured at 4.2 K and analyzed in comparison to spectra of single crystals. Samples with various mean particle dimensions were tested. NMR spectral lines corresponding to individual iron sublattices showed pronounced frequency shifts of their positions and a significant line broadening compared to single crystals. The significant contribution to the line shifts and line shape had a uniform macroscopic origin giving identical absolute value of shifts and the same line shapes for all measured lines of a particular sample. Estimations of demagnetization fields based on mean particle dimensions reasonably corresponded to the observed frequency shifts for particle mean diameter 67 nm, or had a higher value for a sample with mean diameter of 340 nm, for which a presence of domain walls was detected by NMR. In the spectrum of a sample with the smallest particles (～16 nm), an additional contribution having broader lines and faster spin-spin relaxations was found. It could be assigned to weaker exchange interactions or deviations of magnetic moment directions from the hexagonal axis in a surface layer.     

Monitoring of the Proton Electrochemical Gradient in Reconstituted Vesicles: Quantitative Measurements of Both Transmembrane Potential and Intravesicular pH by Ratiometric Fluorescent Probes

Proteoliposomes carrying reconstituted yeast plasma membrane H⁺-ATPase in their lipid membrane or plasma membrane vesicles are model systems convenient for studying basic electrochemical processes involved in formation of the proton electrochemical gradient (Δμ_H ⁺) across the microbial or plant cell membrane. Δψ- and pH-sensitive fluorescent probes were used to monitor the gradients formed between inner and outer volume of the reconstituted vesicles. The Δψ-sensitive fluorescent ratiometric probe oxonol VI is suitable for quantitative measurements of inside-positive Δψ generated by the reconstituted H⁺-ATPase. Its Δψ response can be calibrated by the K⁺/valinomycin method and ratiometric mode of fluorescence measurements reduces undesirable artefacts. In situ pH-sensitive fluorescent probe pyranine was used for quantitative measurements of pH inside the proteoliposomes. Calibration of pH-sensitive fluorescence response of pyranine entrapped inside proteoliposomes was performed with several ionophores combined in order to deplete the gradients passively formed across the membrane. Presented model system offers a suitable tool for simultaneous monitoring of both components of the proton electrochemical gradient, Δψ and ΔpH. This approach should help in further understanding how their formation is interconnected on biomembranes and even how transport of other ions is combined to it.     

Structure and NMR properties of 6‐substituted‐5,6‐dihydrobenzo[c]phenanthridine alkaloids

We report a preparation of new 6‐substituted‐5,6‐dihydrobenzo[c]phenanthridines by the reaction of azoles with quaternary benzo[c]phenanthridine alkaloids sanguinarine and chelerythrine. The prepared compounds have been characterized by NMR spectroscopy, mass spectrometry, and single‐crystal X‐ray diffraction. Conformational behaviors of carbazole derivatives in solution have been investigated by low‐temperature NMR experiments. Barriers to rotation around newly formed C6–N bonds were determined to be 12–13 kcal/mol. Quantum chemical calculations have been used to reproduce the experimental observations. Large structural effects on several ¹H NMR resonances were observed experimentally, analyzed by Density Functional Theory (DFT) calculations at B3LYP/6‐311+G(d,p)/PCM level, and interpreted by ring‐current effects of the benzo[c]phenanthridine and carbazole units. Copyright © 2013 John Wiley & Sons, Ltd.     

Nonlinear theory of the compressible gas flows over a nonuniform boundary in the gravitational field in the shallow-water approximation

A set of equations is derived for the motion of a compressible ideal gas over a nonuniform boundary in the gravitational field in the shallow-water approximation. Classical simple waves are shown not to be the solutions to this set of equations. Generalized simple waves are found to exist only in the case of a linear underlying-surface profile. All continuous and discontinuous solutions are obtained in an explicit form for the case of the boundary in the form of an inclined plane, and an analytical solution is found for the problem of the decay of an arbitrary discontinuity. This solution consists of four wave configurations. Necessary and sufficient conditions are determined for the existence of each configuration.     

Self-phase-locked degenerate femtosecond optical parametric oscillator

We demonstrated a stable degenerate synchronously pumped femtosecond optical parametric oscillator (SPOPO) as a divide-by-2 subharmonic generator. The SPOPO exhibited passive all-optical self-phase-locking between the pump and signal/idler and thus required no external electronic feedback to produce the phase-locked subharmonic. We employed a type I phase-matched, 1-mm-long, periodically poled MgO:LiNbO3 crystal as the nonlinear gain element and an 80 MHz mode-locked Ti:sapphire laser with 180 fs pulses tuned at 775 nm as the pump. The SPOPO generated transform-limited 70 fs phase-locked output pulses centered at 1550 nm. The self-phase-locking operation was confirmed by separate beat-note measurement techniques with respect to the pump laser and with respect to an external cw laser.     

Linearly polarized, 3.35 W narrow-linewidth, 1150 nm fiber master oscillator power amplifier for frequency doubling to the yellow

A high-power linearly polarized Yb-doped silica fiber master oscillator power amplifier at 1150 nm is reported. It produced 3.35 W cw and 2.33 W of average power in 1 micros pulses at a 100 kHz repetition rate, both with 8 pm linewidth. This is the first report, to the best of our knowledge, of a high-power Yb-doped fiber amplifier at a wavelength longer than 1135 nm. The pulsed output was frequency doubled in a bulk periodically poled near-stoichiometric LiTaO(3) chip to generate 976 mW of average power at 575 nm with an overall system optical-to-optical efficiency of 9.8% with respect to launched pump power.