Dynamic surface tension of aqueous solutions of ionic surfactants: role of electrostatics

The adsorption kinetics of the cationic surfactant dodecyltrimethylammonium bromide at the air-water interface has been studied by the maximum bubble pressure method at concentrations below the critical micellar concentration. At short times, the adsorption is diffusion-limited. At longer times, the surface tension shows an intermediate plateau and can no longer be accounted for by a diffusion-limited process. Instead, adsorption appears kinetically controlled and slowed down by an adsorption barrier. A Poisson-Boltzmann theory for the electrostatic repulsion from the surface does not fully account for the observed potential barrier. The possibility of a surface phase transition is expected from the fitted isotherms but has not been observed by Brewster angle microscopy.     

Functional holography analysis: simplifying the complexity of dynamical networks

We present a novel functional holography (FH) analysis devised to study the dynamics of task-performing dynamical networks. The latter term refers to networks composed of dynamical systems or elements, like gene networks or neural networks. The new approach is based on the realization that task-performing networks follow some underlying principles that are reflected in their activity. Therefore, the analysis is designed to decipher the existence of simple causal motives that are expected to be embedded in the observed complex activity of the networks under study. First we evaluate the matrix of similarities (correlations) between the activities of the network's components. We then perform collective normalization of the similarities (or affinity transformation) to construct a matrix of functional correlations. Using dimension reduction algorithms on the affinity matrix, the matrix is projected onto a principal three-dimensional space of the leading eigenvectors computed by the algorithm. To retrieve back information that is lost in the dimension reduction, we connect the nodes by colored lines that represent the level of the similarities to construct a holographic network in the principal space. Next we calculate the activity propagation in the network (temporal ordering) using different methods like temporal center of mass and cross correlations. The causal information is superimposed on the holographic network by coloring the nodes locations according to the temporal ordering of their activities. First, we illustrate the analysis for simple, artificially constructed examples. Then we demonstrate that by applying the FH analysis to modeled and real neural networks as well as recorded brain activity, hidden causal manifolds with simple yet characteristic geometrical and topological features are deciphered in the complex activity. The term "functional holography" is used to indicate that the goal of the analysis is to extract the maximum amount of functional information about the dynamical network as a whole unit.     

Imaginaries in Hilbert spaces

We characterise imaginaries (up to interdefinability) in Hilbert spaces using a Galois theory for compact unitary groups.The authors would like to thank Frank Wagner and the CIRM for their hospitality during the Simpleton 2002 meeting during which the discussions that led to this paper took place.The first author would like to thank Ilan Hirshberg for a few important hintsAt the time of the writing of this paper, the first author was a graduate student with the Équipe de logique mathématique of Université Paris VIIMathematics Subject Classification (2000): 03C45, 03C95     

Diagram X-ray emission spectra of a hollow atom: the Kh alpha1,2 and Kh beta1,3 hypersatellites of Fe

High-resolution Fe K(h) beta(1,3) and K(h) alpha(1,2) hypersatellite spectra were measured, using monochromatized synchrotron radiation photoexcitation. The lines' energies, splitting, excitation thresholds, and the K(h) alpha(1)/K(h) alpha(2) intensity ratio were derived with high accuracy. Having both spectra, not hitherto available for any atom with high resolution, allows separating out the energy shifts of the outer levels caused by a K shell spectator vacancy. Comparison with ab initio relativistic multiconfigurational Dirac-Fock calculations reveals that while the influence of relativity and QED effects is mostly accounted for, discrepancies remain in the lines' intensity ratio, which sensitively measures the intermediacy of the coupling. Similar discrepancies, of unknown origin, are found in the energy shifts of the outer levels due to the final-state K shell spectator vacancy.     

Über die directe Einführung von Hydroxylgruppen in Oxychinoline

Ohne ZusammenfassungHerrn Prof. Weidel, mit dessen Unterstützung ich vorliegende Arbeit ausgeführt habe, spreche ich an dieser Stelle meinen verbindlichsten Dank aus.     

Membrane assembly driven by a biomimetic coupling reaction

One of the major goals of synthetic biology is the development of non-natural cellular systems. In this work, we describe a catalytic biomimetic coupling reaction capable of driving the de novo self-assembly of phospholipid membranes. Our system features a coppercatalyzed azide-alkyne cycloaddition that results in the formation of a triazole-containing phospholipid analogue. Concomitant assembly of membranes occurs spontaneously, not requiring preexisting membranes to house catalysts or precursors. The substitution of efficient synthetic reactions for key biochemical processes may offer a general route toward synthetic biological systems.     

Ultrafast excited-state intermolecular proton transfer of cyanine fluorochrome dyes

Steady-state and time-resolved emission spectroscopy techniques were employed to study the excited-state proton transfer (ESPT) to water and D(2)O from QCy7, a recently synthesized near-infrared (NIR)-emissive dye with a fluorescence band maximum at 700 nm. We found that the ESPT rate constant, k(PT), of QCy7 excited from its protonated form, ROH, is ~1.5 × 10(12) s(-1). This is the highest ever reported value in the literature thus far, and it is comparable to the reciprocal of the longest solvation dynamics time component in water, τ(S) = 0.8 ps. We found a kinetic isotope effect (KIE) on the ESPT rate of ~1.7. This value is lower than that of weaker photoacids, which usually have KIE value of ~3, but comparable to the KIE on proton diffusion in water of ~1.45, for which the average time of proton transfer between adjacent water molecules is similar to that of QCy7.     

Smoothening transition of a two-dimensional pressurized polymer ring

We revisit the problem of a two-dimensional polymer ring subject to an inflating pressure differential. The ring is modeled as a freely jointed closed chain of N monomers. Using a Flory argument, mean-field calculation and Monte Carlo simulations, we show that at a critical pressure, p_c ∼ N^-1, the ring undergoes a second-order phase transition from a crumpled, random-walk state, where its mean area scales as 〈A〉 ∼ N, to a smooth state with 〈A〉 ∼ N². The transition belongs to the mean-field universality class. At the critical point a new state of polymer statistics is found, in which 〈A〉 ∼ N^3/2. For p ≫ p_c we use a transfer-matrix calculation to derive exact expressions for the properties of the smooth state.     

Hydrodynamic pair attractions between driven colloidal particles

Colloidal spheres driven through water along a circular path by an optical ring trap display unexpected dynamical correlations. We use Stokesian dynamics simulations and a simple analytical model to demonstrate that the path's curvature breaks the symmetry of the two-body hydrodynamic interaction, resulting in particle pairing. The influence of this effective nonequilibrium attraction diminishes as either the temperature or the stiffness of the radial confinement increases. We find a well-defined set of dynamically paired states whose stability relies on hydrodynamic coupling in curving trajectories.