Separation efficiency is ideally controlled by molecular diffusion in capillary electrophoresis (CE). However, other adverse phenomena, such as solute adsorption on capillary surface, tend to increase the peak dispersion. An interesting alternative to limit the solute adsorption is to avoid as much as possible the contact of the solute with the capillary surface by elaborating superhydrophobic (SH) coatings on fused silica capillary surfaces. This work describes an optimized protocol to get non-wettable SH coating using hydrophobically modified silica nanoparticle suspensions (Glaco TM), based on simple capillary flushes and thermal stabilization. In this protocol, the control of the air flushing after the introduction of the Glaco TM suspension in the capillary was found crucial to get optimized coating coverage and reproducibility. The SH coating was characterized by ellipsometry, atomic force microscopy, scanning electron microscopy, contact angle (about 159°) and the observation of the meniscus of water in the coated capillary. The hydrodynamic behavior of the SH coated capillary was investigated by plotting the Poiseuille law. Finally, electrophoretic separations of a peptide mixture in acidic conditions demonstrated the interest of this approach with an increase by a factor 2 of the separation efficiency compared to fused silica capillary.

Hard and soft proteins at fluid interfaces

We have investigated the wetting and surface diffusion of mesoporous colloidal silica particles at the water surface and the adsorption of cationic cetyltrimethylammonium (CTA+) surfactant on these particles. Porous silica colloids diffuse at the surface of water and in the volume, interacting with cationic surfactants that can adsorb inside the pores of the particles. We observed that surfactant adsorption on mesoporous silica depends dramatically not only on the particle pore size but also on specific counterion effects. We measured striking differences both on a macroscopic property of the interface, i.e., surface tension, and also at a single particle level by evaluating the translational diffusion of partially wetted particles at the fluid interface. We varied the pore size from 2 to 7 nm and explored the effects of ions possessing different hydration number and kosmotropic/chaotropic character. At concentrations lower than the critical micellar concentration, we evidence that cationic surfactants adsorb on silica as surface micelles and surfactant adsorption inside the pores occurs only if the pore diameter is larger than the size of surface micelles. With a view to understand the surprising different adsorption behavior of CTA+OH– and CTA+Br– on porous silica particles, we investigated the effect of counterions on the surfactant adsorption on porous silica colloids by tuning the pH and the counterion properties.

Les techniques de microrhéologie basées sur le suivi optique de particules microniques sont très intéressantes lorsqu’il s’agit de mesurer les propriétés viscoélastiques de fluides complexes de petit volume. Elles peuvent également paraître très intéressantes pour sonder localement des milieux hétérogènes. Dans le cas de milieux anisotropes comme les cristaux liquides nématiques, ces techniques doivent cependant être utilisées avec précaution. Nous l’illustrerons à travers le cas d’un cristal liquide lyotrope, le cromoglycate de sodium (DSCG) pour lequel nous avons examiné la pertinence des données rhéologiques extraites à partir de la dynamique de microparticules.Le mouvement Brownien, inhabituel, de microsphères dans la phase nématique de ce système avait en effet attiré récemment l’attention [1,2] suggérant un couplage complexe entre les fluctuations du directeur et les fluctuations de positions des billes. Bien qu’il ait été récemment proposé que des mesures par suivi de particules puissent être utilisées pour obtenir les différentes viscosités de la phase nématique [3], ce phénomène peut en effet conduire à des mesures rhéologiques incohérentes. Afin d’explorer ces différents problèmes, nous avons étudié le mouvement Brownien de particules dans des échantillons alignés en cellules minces (épaisseur 50µm) tout en variant à la fois la concentration de DSCG et la taille des particules (0.5, 1, 3, and 6µm de diamètre).Des propriétés viscoélastiques effectives ont été extraites de nos mesures de microrhéologie passive ainsi que de mesures actives basées sur l’utilisation de pinces optiques et le mouvement forcé des particules[4]. Nos résultats expliquent pourquoi différents comportements viscoélastiques ont été obtenus précédemment sur ce même système et l’origine des modules élastiques mesurés.

In previous work [Opt. Lett. 44, 2827 (2019)], we presented a method based on digital holography and orthogonal matching pursuit, which is able to determine the 3D positions of small objects moving within a larger motionless object. Indeed, if the scattering density is sparse in direct 3D space, compressive sensing algorithms can be used. The method was validated by imaging red blood cell trajectories in the trunk vascular system of a zebrafish (Danio rerio) larva. We give here further details on the reconstruction technique and present a more robust version of the algorithm based on multiple illuminations.

Soft adhesion to a horizontal flat substrate of micron-sized colloids coated by acontrolled molar fraction f of PLL-g-PNIPAM is tuned and triggered by controllingthe temperature of the sample. This mechanism is possible becausePNIPAM is a thermo-responsive polymer, which undergoes a phase transitionat a LCST (lower critical solution temperature) Tc = 32 +- 1°C. In order tocapture the very final events before the immobilization of colloids the T-rampprotocol is designed: the particles suspension is injected in cell at room temperature,the temperature is increased at a constant rate up to 38°C> Tc, andkept constant until the end of the acquisition. Attraction between beads andthe flat substrate is thereby triggered when crossing the critical temperatureTc. Ascending and descending ramp experiments are performed in order to accessboth adsorption and desorption kinetics. 3-D motion of beads is real-timetracked using slightly defocused microscopy in parallel illumination. We usetrack records to have access to pre-adsorption dffusion coeffcients and to characterizeadsorption and desorption dynamics. Present results corroborate thatadsorption is controlled by PNIPAM doping, and indeed dominated by rollingand memory (aging) effect on the contact domain. On the contrary, the desorption kinetics is independent of doping. Moreover, the sharpness (in T) ofthe PNIPAM transition is quantified in a set of experiments at different rampspeeds. We show that the transition smearing can reach up to +-1°C for higherPNIPAM coverage, while it is not detectable for the lowest ones. The combinationof all these observations paves the way to practical applications. Asan example, we will discuss a soft adhesion-based method to sort and separatecolloids in microfluidic channels.

Heliconal nematic twist bend (NTB) phases are usually not well oriented in planar commercial cells, even in thin (~1 µm) ones where a micron-sized periodic texture is usually observed [1,2,3] (see Fig.1-a). The origin of the stripe patterns is attributed to the rapid shrinking of the pseudo-layers below the N-NTB phase transition temperature, which yields an undulation instability. The observed periodicity is found to be twice the cell gap [1].We have explored the effect of the strength of the anchorings of the substrates on the resulting patterns. We used polymer aligning layers of tunable azimuthal and zenithal strengths to design liquid crystal cells with surface anchorings ranging from ultraweak to strong. We then have studied the patterns formed by the NTB phase of 1,7-bis-4-(4-cyanobiphenyl) heptane (CB7CB). We will show how the period of the stripes can be varied in a large range in cells of the same thickness but with different anchoring preparations. With adequate anchoring conditions (see Fig.1-b-c), an excellent and spontaneous planar alignment of the NTB phase of CB7CB can be obtained much below the phase transition temperature.
References:
[1] Panov V.P. et al, Phys. Rev. Lett., 2010, 105; 167801.
[2] Challa P. K. et al, Phys. Rev. E: Stat., Nonlinear, Soft Matter Phys., 2014, 89, 060501.
[3] Vaupotič N. et al., Chem. Phys. Chem., 2018, 19,2566.