Photomechanical actuation and manipulation of the electronic properties of linear pi-conjugated systems

A photodynamic molecular architecture has been synthesized by covalent fixation of a photoisomerizable azobenzene group at two fixed points of a conformationally flexible pi-conjugated quaterthiophene chain. The crystallographic structure shows that the two systems lie in parallel planes with a short interplane distance. Theoretical modelization and experimental analysis by 1H NMR and cyclic voltammetry unequivocally show that trans to cis photoisomerization of the azobenzene group induces dimensional and conformational changes in the underlying pi-conjugated system. These geometrical changes produce, in turn, an increase of the HOMO level and a narrowing of the HOMO-LUMO gap, thus providing a first example of photomechanical control of the electronic properties of the pi-conjugated system.     

Transport of long neutral polymers in the semidilute regime through a protein nanopore

We investigate the entrance of single poly(ethylene glycol) chains into an α-hemolysin channel. We detect the frequency and duration of the current blockades induced by large neutral polymers, where chain radius is larger than pore diameter. In the semidilute regime, these chains pass only if the monomer concentration is larger than a well-defined threshold. Experiments are performed in a very large domain of concentration and molecular mass, up to 35% and 200 kDa, respectively, which was previously unexplored. The variation of the dwell time as a function of molecular mass shows that the chains are extracted from the semidilute solution in contact with the pore by a reptation mechanism.     

Distances in evidence theory: Comprehensive survey and generalizations

The purpose of the present work is to survey the dissimilarity measures defined so far in the mathematical framework of evidence theory, and to propose a classification of these measures based on their formal properties. This research is motivated by the fact that while dissimilarity measures have been widely studied and surveyed in the fields of probability theory and fuzzy set theory, no comprehensive survey is yet available for evidence theory. The main results presented herein include a synthesis of the properties of the measures defined so far in the scientific literature; the generalizations proposed naturally lead to additions to the body of the previously known measures, leading to the definition of numerous new measures. Building on this analysis, we have highlighted the fact that Dempster’s conflict cannot be considered as a genuine dissimilarity measure between two belief functions and have proposed an alternative based on a cosine function. Other original results include the justification of the use of two-dimensional indexes as (cosine; distance) couples and a general formulation for this class of new indexes. We base our exposition on a geometrical interpretation of evidence theory and show that most of the dissimilarity measures so far published are based on inner products, in some cases degenerated. Experimental results based on Monte Carlo simulations illustrate interesting relationships between existing measures.     

Host–Guest Complexation of [60]Fullerenes and Porphyrins Enabled by “Click Chemistry”

Herein the synthesis, characterization, and organization of a first‐generation dendritic fulleropyrrolidine bearing two pending porphyrins are reported. Both the dendron and the fullerene derivatives were synthesized by Cu^I‐catalyzed alkyne–azide cycloaddition (CuAAC). The electron‐donor–acceptor conjugate possesses a shape that allows the formation of supramolecular complexes by encapsulation of C₆₀ within the jaws of the two porphyrins of another molecule. The interactions between the two photoactive units (i.e., C₆₀ and Zn–porphyrin) were confirmed by cyclic voltammetry as well as by steady‐state and time‐resolved spectroscopy. For example, a shift of about 85 mV was found for the first reduction of C₆₀ in the electron‐donor–acceptor conjugate compared with the parent molecules, which indicates that C₆₀ is included in the jaws of the porphyrin. The fulleropyrrolidine compound exhibits a rich polymorphism, which was corroborated by AFM and SEM. In particular, it was found to form supramolecular fibrils when deposited on substrates. The morphology of the fibrils suggests that they are formed by several rows of fullerene–porphyrin complexes.     

Smart Foams: Switching Reversibly between Ultrastable and Unstable Foams

Smart foams: Ultrastable foams with an optimal foamability are obtained using hydroxy fatty acids tubes. The stabilization results from the adsorption of monomers at the air-water interface and from the presence of tubes in the plateau borders. Upon heating, tubes transform to micelles, leading to foam destabilization and thus to the first foams to exhibit temperature-tuneable stability.     

Bubble cell for magnetic bead trapping in capillary electrophoresis

A bubble cell capillary classically used to extend the optical path length for UV–vis detection is employed here to trap magnetic beads. With this system, a large amount of beads can be captured without inducing a strong pressure drop, as it is the case with magnetic beads trapped in a standard capillary, thereby having less effect on the experimental conditions. Using numerical simulations and microscopic visualizations, the capture of beads inside a bubble cell was investigated with two magnet configurations. Pressure-driven and electro-osmotic flow velocities were measured for different amounts of protein-A-coated beads or C18-functionalized beads (RPC-18). Solid-phase extraction of a model antibody on protein-A beads and preconcentration of fluorescein on RPC-18 beads were performed as proof of concept experiments.     

An investigation of the stored energy and thermal stability in a Cu–Ni–Si alloy processed by high-pressure torsion

ABSTRACT

The stored energy and activation energy for recrystallization were investigated for a Cu-Ni-Si alloy after high-pressure torsion processing for N?=?½, 1, 5 and 10 turns at room temperature. The contributions of geometrically necessary dislocations (GNDs), statistically stored dislocations (SSDs) and vacancies to the stored energy were calculated through the Vickers microhardness measurements, kernel average misorientation (KAM) measurements and an analysis by differential scanning calorimetry (DSC). The results show that the total stored energy decreases rapidly after equivalent strain of ε_eq?～?9 and then saturates through ε_eq?～?86 at ～70 J/mol. Concurrently, the local stored energy in GNDs and SSDs was found to depend strongly on the radial distance from the centre of the disc and increase with increasing equivalent strain at ε_eq?～?16 and saturate with further straining. Accordingly, the results indicate that the GNDs and vacancies are responsible for the high stored energy in the initial stage of deformation at equivalent strain range of ε_eq?=?8.6–16 and thereafter their contribution decreases slightly due to the occurrence of dynamic recrystallization and the formation of fine grains. At the same time, the contribution of the SSDs is similar to that of the GNDs only in high strain deformation as at ε_eq?=?49.3 to accommodate the deformation process. An activation energy for recrystallization was estimated in the range of ～?89.7–98.7 kJ/mol, thereby suggesting poor thermal stability.     

Mathematical study of rotating fluids with resonant surface stress

We are interested here in describing the linear response of a highly rotating fluid to some surface stress tensor, which admits fast time oscillations and may be resonant with the Coriolis force. In addition to the usual Ekman layer, we exhibit another - much larger - boundary layer, and we prove that for large times, the effect of the surface stress may no longer be localized in the vicinity of the surface. From a mathematical point of view, the main novelty here is to introduce some systematic approach for the study of boundary effects.