The Armstrong experiment revisited

When a high-voltage direct-current is applied to two beakers filled with water or polar liquid dielectrica, a horizontal bridge forms between the two beakers. This experiment was first carried out by Lord Armstrong in 1893 and then forgotten until recently. Such bridges are stable by the action of electrohydrodynamic (EHD) forces caused by electric field gradients counteracting gravity. Due to these gradients a permanent pumping of liquid from one beaker into the other is observed. At macroscopic scale several of the properties of a horizontal water bridge can be explained by modern electrohydrodynamics, analyzing the motion of fluids in electric fields. Whereas on the molecular scale water can be described by quantum mechanics, there is a conceptual gap at mesoscopic scale which is bridged by a number of theories including quantum mechanical entanglement and coherent structures in water – theories that we discuss here. Much of the phenomenon is already understood, but even more can still be learned from it, since such “floating” liquid bridges resemble a small high voltage laboratory of their own: The physics of liquids in electric fields of some kV/cm can be studied, even long time experiments like neutron or light scattering are feasible since the bridge is in a steady-state equilibrium and can be kept stable for hours. It is also an electro-chemical reactor where compounds are transported through by the EHD flow, enabling the study of electrochemical reactions under potentials which are otherwise not easily accessible. Last but not least the bridge provides the experimental biologist with the opportunity to expose living organisms such as bacteria to electric fields without killing them, but with a significant influence on their behavior, and possibly, even on their genome.     

Computer modelling studies of 18-crown-6 with urea and thiourea

Abstract

Computer modelling studies have been carried out on the interaction of 18-crown-6 with a variety of guest molecules, including urea, thiourea and substituted ureas. The five known crystal structures of these host/guest systems were used as models. We were interested to establish whether the arrangement of guest molecules around a host molecule in the crystal was indicative of the lowest energy configuration for a host/guest fragment or was a consequence of packing effects. Two models were therefore considered for each structure and the structures minimised via molecular mechanics. In the first mode, the structure consisted of one unit cell and periodic boundary conditions were used in the calculation. Coulombic effects were calculated using the Ewald summation. In the second model, the structure consisted of an 18-crown-6 molecule surrounded by two hydrogen-bonded guest molecules. Both models were minimised using the CERIUS package using the DreidingII forcefield.

The crystal structure minimisations reproduced the structures very well with an average change in cell volume of 3.6% and a mean r.m.s. positional deviation of 0.20 Å. The fits for the fragment models were significantly larger for all structures (mean 0.30 Å) but even so it can be concluded that the arrangement in the crystal gave a good indication of the lowest energy configuration of the host/guest in vacuo.     

On the Nature of Interactions between Ionic Liquids and Small Amino‐Acid‐Based Biomolecules

During the last decade, ionic liquids (ILs) have revealed promising properties and applications in many research fields, including biotechnology and biological sciences. The focus of this contribution is to give a critical review of the phenomena observed and current knowledge of the interactions occurring on a molecular basis. As opposed to the huge advances made in understanding the properties of proteins in ILs, complementary investigations dealing with interactions between ILs and peptides or oligopeptides are underrepresented and are mostly only of phenomenological nature. However, the field has received more attention in the last few years. This Review features a meta‐analysis of the available data and findings and should, therefore, provide a basis for a scientifically profound understanding of the nature and mechanisms of interactions between ILs and structured or nonstructured peptides. Fundamental aspects of the interactions between different peptides/oligopeptides and ILs are complemented by sections on the experimental (spectroscopy, structural biology) and theoretical (computational chemistry) possibilities to explain the phenomena reported so far in the literature. In effect, this should lead to the development of novel applications and support the understanding of IL–solute interactions in general.     

Straightforward synthesis of cholic acid stabilized loop mimetics

We here report on a new straightforward strategy for the synthesis of cyclic cholic acid–peptide conjugates. A solid-phase synthesis method is presented in which a selected anti-lysozyme CDR3 fragment, Asp-Ser-Thr-Ile-Tyr-Ala-Ser-Tyr-Tyr-Glu-Ser, is immobilized onto a steroidal cholic acid derived scaffold in order to yield a loop-like structure. Therefore, part of the desired sequence, that is, Ser-Tyr-Tyr-Glu-Ser, is introduced, at the C12 position of the scaffold. Subsequently, the remainder of the envisaged sequence is introduced at C3 via a Cu-catalyzed cyclo-addition reaction. Finally, amide bond formation delivers the desired cyclic peptidosteroid. This new synthetic strategy offers an easy and short access to cyclic peptidosteroids via convergent peptide ligation and macrocyclization.     

The Norwegian Façade Insulation Study: the efficacy of façade insulation in reducing noise annoyance due to road traffic

The ergodic propriety of a room has strong effects on its reverberation. If the room is ergodic, the reverberation can be broken up in two steps: a deterministic process followed by a stochastic one. The late reverberation can be then modeled by a reverberation algorithm instead of more computationally consuming methods. In this study, the free path temporal distribution obtained by ray-tracing is used as an indicator of the room's mixing: the energetic average of the path lengths is computed at each time step. Ergodic rooms are thus characterized by rapidly convergent distributions. The free path value becomes independent of time. On the other hand, path selection mechanism and orbits are observed in non-ergodic rooms. The transition time from the deterministic process to the stochastic one is also studied through the evaluation of the room's time constant. It is shown that its value depends only on the mean free path and the boundaries scattering value. An empirical expression is obtained which agrees well with simulations carried out in a concert hall. This transition time from a deterministic model to a stochastic one can be used to speed up the acoustical predictions and auralizations in ergodic rooms.     

Electron diffraction self-imaging of molecular fragmentation in two-step double ionization of water

We doubly ionize H(2)O by single photon absorption at 43 eV leading to H(+) + OH(+). A direct double ionization and a sequential process in which single ionization is followed by rapid dissociation into a proton and an autoionizing OH(*) are identified. The angular distribution of this delayed autoionization electron shows a preferred emission in the direction of the emitted proton. From this diffraction feature we obtain internuclear distances of 700 to 1100 a.u. at which the autoionization of the OH(*) occurs. The experimental findings are in line with calculations of the excited potential energy surfaces and their lifetimes.     

Multiple recapture of electrons in multiple ionization of the argon dimer by a strong laser field

We observe multiply frustrated tunneling ionization-induced dissociation of the argon dimers by intense linearly polarized ultrashort laser pulses. By measuring the kinetic energy release and angular distribution of the Coulomb explosion of up to eightfold ionized argon dimers, we can trace the recapture of up to two electrons to Rydberg states of the highly charged compound at the end of the laser pulse. Upon dissociation of the dimer, the Rydberg electron prefers to localize at the atomic ion with the higher charge state. We probe the electron recapture dynamics by a time-delayed weak pulse.