Simultaneously measuring the dichroism and the dielectric response of an azobenzene-doped organic glass former.

We have designed an experimental setup allowing to simultaneously measure both the dielectric response of a supercooled liquid and the dynamics of azobenzene chromophores dispersed in it. Both the azobenzene chromophores and the organic glass former have been synthesized with similar reaction paths: they are chemically similar, apart from the azobenzene group responsible for the strong optical absorption in the [350; 450 nm] range for the chromophores, while the embedding supercooled liquid is optically transparent. This material is deposited on transparent electrodes with an inter-electrode gap as small as 4 µm-obtained thanks to optical lithographic techniques. We show that our setup is sensitive enough to measure the coupling between the dielectric macroscopic response and the isomerization dynamics of 1% of chromophores excited by a 0.5-5 mW/cm2 light beam. We demonstrate that this coupling neither comes from the heating of the sample due to the light absorption nor from changes of the sample shape with light. Finally, we discuss the few physical effects, which may give rise to this coupling, and show that our experiment could test some recent predictions done in the framework of random first order transition theory of the glassy state.

A silicone-based slippery polymer coating with humidity-dependent nanoscale topography.

HYPOTHESIS: Slippery Omniphobic Covalently Attached Liquids (SOCAL) have been proposed for making omnirepellent thin films of self-assembled dimethylsiloxane polymer brushes grafted from silica surfaces. Smooth and flat at very small scale, these fluid surfaces could exhibit a more complex multiscale structure though showing very weak contact angle hysteresis (less than 5°). EXPERIMENT: In this work, coatings were deposited on glass surfaces from an acidic dimethoxydimethylsilane solution under carefully controlled relative humidity. Ellipsometry mapping was used to analyze the surface structuration with nanometric thickness sensitivity. The sliding properties were determined using a drop shape analyzer with a tilting device, and chemical analyses of the coatings were performed using on-surface techniques (XPS, ATR-FTIR spectroscopy). FINDINGS: Coated materials possessed an unexpected surface structure with multiscale semispherical-like features, which surprisingly, did not increase the contact angle hysteresis. A careful study of some parameters of the coating process and the related evolution of the surface properties allowed us to propose a new model of the chemical organization of the polymer to support this remarkable liquid-like behavior. These structures are made of end-grafted strongly adsorbed Guiselin brushes with humidity-dependent thickness: the higher the humidity, the thinner and the more slippery the coating.

The study of the pseudo-polyrotaxane architecture as a route for mild surface functionalization by click chemistry of poly(ε-caprolactone)-based electrospun fibers.

Polycaprolactone (PCL) electrospun fibers are widely developed for biomedical applications. However, their hydrophobicity and passivity towards cell growth is an important limitation. An original method to functionalize PCL nanofibers, making them reactive for bioconjugation of proteins or other molecules of interest in water under mild conditions, is reported here. This method involves the preparation of pseudo-polyrotaxanes (pPRs) of cyclodextrin (CD) and PCL. Core:shell PCL:pPR fibers were then prepared by coaxial electrospinning in order to bring available reactive hydroxyl groups from the CD to the fiber surface. Different pPR architectures (star, miktoarm and block-copolymer-like) were synthesized to study the effect of the pPR structure on fiber morphology and surface reactivity by grafting fluorescein isothiocyanate (FITC). Finally, bicyclononyne groups were grafted onto the star-pPR based fibers allowing the conjugation of a fluorescent dye by click chemistry in water without any copper catalyst proving the potential of the method for the biofunctionalization of PCL-based fibers.

[3H]RP 62203, a ligand of choice to label in vivo brain 5-HT2 receptors.

There are only a few ligands available for labelling brain receptors simply because in vivo binding requires more severe experimental conditions than in vitro binding. We now describe the in vivo binding properties of [3H]RP 62203, a new potent and selective 5-HT2 antagonist. After intravenous injection into rats, [3H]RP 62203 accumulated predominantly in brain regions containing 5-HT2 receptors, with a frontal cortex/cerebellum ratio of 6 to 7. A good correlation was obtained between the regional distribution of [3H]RP 62203 in the brain and the density of 5-HT2 receptors measured in vitro. In vivo binding of [3H] RP 62203 was saturable in the frontal cortex but not in the cerebellum. The Bmax in the frontal cortex was equal to 42.5 fmol/mg, thus in the same range as was found in vitro. The 5-HT2 selectivity was ascertained by displacement (prevention) experiments; 5-HT2 antagonists or the agonist 2,5-dimethoxy- 4-iodophenylisopropylamine could prevent specific labelling of [3H]RP 62203 only in brain regions containing 5-HT2 receptors. Interestingly, the radioactivity remaining in various brain regions after displacement with pipamperone corresponded exactly to that measured in the cerebellum, with or without pipamperone. In conclusion, [3H]RP 62203 possesses striking properties of in vivo binding which make it a suitable candidate for examining 5-HT2 receptors in human brain by positron emission tomography scanning.