A physical organic mechanistic approach to understanding the complex reaction network of hemostasis (blood clotting)

This review focuses on how the mechanistic approach of physical organic chemistry can be used to elucidate the mechanisms behind complex biochemical networks. The dynamics of biochemical reaction networks is difficult to describe by considering their individual reactions, just as the dynamics of organic reactions is difficult to describe by considering individual electrons and atomic nuclei. Physical organic chemists have developed a useful set of tools to predict the outcome of organic reactions by separating the interacting molecules into modules (functional groups), and defining general rules for how these modules interact (mechanisms). This review shows how these tools of physical organic chemistry may be used to describe reaction networks. In addition, it describes the application of these tools to develop a mechanistic understanding of the dynamics of the complex network of hemostasis, which regulates blood clotting. Copyright © 2007 John Wiley & Sons, Ltd.     

Observation of nonlinear self-trapping in triangular photonic lattices

We experimentally study light self-trapping in triangular photonic lattices induced optically in nonlinear photorefractive crystals. We observe the formation of two-dimensional discrete and gap spatial solitons originating from the first and second bands of the linear transmission spectrum.     

Coherence and wavefront characterization of Si‐111 monochromators using double‐grating interferometry

A study of the coherence and wavefront properties of a pseudo‐channel‐cut monochromator in comparison with a double‐crystal monochromator is presented. Using a double‐grating interferometer designed for the hard X‐ray regime, the complex coherence factor was measured and the wavefront distortions at the sample position were analyzed. A transverse coherence length was found in the vertical direction that was a factor of two larger for the channel‐cut monochromator owing to its higher mechanical stability. The wavefront distortions after different optical elements in the beam, such as monochromators and mirrors, were also quantified. This work is particularly relevant for coherent diffraction imaging experiments with synchrotron sources.     

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.     

Laser Doppler imaging through tissues phantoms by using self-mixing interferometry with a laser diode

Laser Doppler imaging has been widely used for the evaluation of cutaneous blood flow. We report on how the self-mixing interferometry configuration with a laser diode is explored for what is believed to be the first time to generate flow maps. The experiment was carried out by sensing the laser intensity power spectrum at each pixel as the laser was scanned over a model that mimics the properties of skin and circulating blood.     

The importance for speech intelligibility of random fluctuations in "steady" background noise

Spectrally shaped steady noise is commonly used as a masker of speech. The effects of inherent random fluctuations in amplitude of such a noise are typically ignored. Here, the importance of these random fluctuations was assessed by comparing two cases. For one, speech was mixed with steady speech-shaped noise and N-channel tone vocoded, a process referred to as signal-domain mixing (SDM); this preserved the random fluctuations of the noise. For the second, the envelope of speech alone was extracted for each vocoder channel and a constant was added corresponding to the root-mean-square value of the noise envelope for that channel. This is referred to as envelope-domain mixing (EDM); it removed the random fluctuations of the noise. Sinusoidally modulated noise and a single talker were also used as backgrounds, with both SDM and EDM. Speech intelligibility was measured for N?=?12, 19, and 30, with the target-to-background ratio fixed at -7 dB. For SDM, performance was best for the speech background and worst for the steady noise. For EDM, this pattern was reversed. Intelligibility with steady noise was consistently very poor for SDM, but near-ceiling for EDM, demonstrating that the random fluctuations in steady noise have a large effect.     

The dynamic range of useful temporal fine structure cues for speech in the presence of a competing talker

Within an auditory channel, the speech waveform contains both temporal envelope (E(O)) and temporal fine structure (TFS) information. Vocoder processing extracts a modified version of the temporal envelope (E') within each channel and uses it to modulate a channel carrier. The resulting signal, E'(Carr), has reduced information content compared to the original "E(O)?+ TFS" signal. The dynamic range over which listeners make additional use of E(O)?+ TFS over E'(Carr) cues was investigated in a competing-speech task. The target-and-background mixture was processed using a 30-channel vocoder. In each channel, E(O)?+ TFS replaced E'(Carr) at either the peaks or the valleys of the signal. The replacement decision was based on comparing the short-term channel level to a parametrically varied "switching threshold," expressed relative to the long-term channel level. Intelligibility was measured as a function of switching threshold, carrier type, target-to-background ratio, and replacement method. Scores showed a dependence on all four parameters. Derived intensity-importance functions (IIFs) showed that E(O)?+ TFS information from 8-13 dB below to 10 dB above the channel long-term level was important. When E(O)?+ TFS information was added at the peaks, IIFs peaked around -2 dB, but when E(O)?+ TFS information was added at the valleys, the peaks lay around +1 dB.     

Thermal stability of the cubic phase in Ba0.5Sr0.5Co0.8Fe0.2O3 - δ (BSCF)1

Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 - δ (BSCF) is a material with excellent oxygen ionic and electronic transport properties reported by many research groups. In its cubic phase, this mixed ionic-electronic conducting (MIEC) perovskite is a promising candidate for oxygen permeation membranes. For this application, its long-term stability under operating conditions (especially temperature and oxygen partial pressure) is of crucial importance.The present work is focused on the thermal stability of the BSCF cubic phase in the targeted temperature range for applications (700…900 °C) in light of previous studies in literature reporting a reversible transition to a hexagonal phase somewhere below 900 °C.To this end, single phase cubic BSCF powders were annealed at different temperatures over varying periods of time. Phase composition was subsequently analysed by X-ray diffractometry (XRD) in order to determine both the temperature limit and the time-scale for the formation of the hexagonal phase. Additionally, the long-term behaviour of the electrical conductivity was examined on bulk samples at 700 °C, 800 °C and 900 °C over several hundreds of hours, showing a prolonged decrease at 800 °C. The decrease in electrical conductivity at this temperature was also examined on bulk samples with different grain sizes, showing a more pronounced decrease the smaller the average grain size.Coexistence of both phases (cubic and hexagonal) could also be shown for 700 °C, however with a different phase equilibrium than at 800 °C.     

High-order harmonic generation enhanced by XUV light

The combination of high-order harmonic generation (HHG) with resonant XUV excitation of a core electron into the transient valence vacancy that is created in the course of the HHG process is investigated theoretically. In this setup, the first electron performs a HHG three-step process, whereas the second electron Rabi flops between the core and the valence vacancy. The modified HHG spectrum due to recombination with the valence and the core is determined and analyzed for krypton on the 3d→4p resonance in the ion. We assume an 800?nm laser with an intensity of about 10(14)?W/cm2 and XUV radiation from the Free Electron Laser in Hamburg (FLASH) with an intensity in the range 10(13)-10(16)W cm2. Our prediction opens perspectives for nonlinear XUV physics, attosecond x rays, and HHG-based spectroscopy involving core orbitals.     

Nonlinear ultrasonic standing waves: two-dimensional simulations in bubbly liquids

We present the results of numerical predictions for analyzing the behavior of nonlinear ultrasonic standing waves in two-dimensional cavities filled with bubbly liquids. The model we solve accounts for nonlinearity, dissipation, and dispersion of the two-dimensional media due to the bubbles. The numerical simulations are based on a finite-difference scheme. They consider the bubbles evenly distributed in the liquid. Results are shown for high-amplitude signals. They make it possible to observe how the linear modes turn into multi-frequency nonlinear fields.