Interfacial Characterization of Ruthenium-Based Amphiphilic Photosensitizers.

Nonreactive surfactant molecules have long been used and characterized for a wide range of applications in industries, life science, and everyday life. Recently, new types of functional amphiphilic molecules have emerged that bear another function, for example, a light-absorbing action, or catalytic properties. However, the surfactant properties of these molecules remain to date essentially unknown. In this context, we investigated here the interfacial activity of photocatalytic surfactants based on a ruthenium(II) tris-bipyridine core, functionalized with two alkyl tails. We realized a systematic characterization of the surfactant properties of these molecules at a water-air interface and studied the effect of the alkyl chain length and of the counterions (hexafluorophosphate or chloride) on these properties. Our data demonstrate that ruthenium surfactants with chloride counteranions form a denser layer at the interface, but their surfactant properties can dramatically deteriorate when the chain length of the alkyl tail increases, leading to simple hydrophobic molecules with poor surfactant properties for the longest chains (C17). These findings pave the way for a better use and understanding of photocatalytic soft interfaces.

Sculpting Liquids with Ultrathin Shells.

Thin elastic films can spontaneously attach to liquid interfaces, offering a platform for tailoring their physical, chemical, and optical properties. Current understanding of the elastocapillarity of thin films is based primarily on studies of planar sheets. We show that curved shells can be used to manipulate interfaces in qualitatively different ways. We elucidate a regime where an ultrathin shell with vanishing bending rigidity imposes its own rest shape on a liquid surface, using experiment and theory. Conceptually, the pressure across the interface "inflates" the shell into its original shape. The setup is amenable to optical applications as the shell is transparent, free of wrinkles, and may be manufactured over a range of curvatures.

Gas Marbles: Much Stronger than Liquid Marbles.

Enwrapping liquid droplets with hydrophobic particles allows the manufacture of so-called "liquid marbles" [Aussillous and Quéré Nature (London) 411, 924 (2001); NATUAS0028-083610.1038/35082026Mahadevan Nature (London)411, 895 (2001)NATUAS0028-083610.1038/35082164]. The recent intensive research devoted to liquid marbles is justified by their very unusual physical and chemical properties and by their potential for various applications, from microreactors to water storage, including water pollution sensors [Bormashenko Curr. Opin. Colloid Interface Sci. 16, 266 (2011)COCSFL1359-029410.1016/j.cocis.2010.12.002]. Here we demonstrate that this concept can be successfully applied for encapsulating and protecting small gas pockets within an air environment. Similarly to their liquid counterparts, those new soft-matter objects, that we call "gas marbles," can sustain external forces. We show that gas marbles are surprisingly tenfold stronger than liquid marbles and, more importantly, they can sustain both positive and negative pressure differences. This magnified strength is shown to originate from the strong cohesive nature of the shell. Those interesting properties could be exploited for imprisoning valuable or polluted gases or for designing new aerated materials.

Viscosity of particulate soap films: approaching the jamming of 2D capillary suspensions.

We compute the effective viscosity of particulate soap films thanks to local velocity fields obtained by Particle Image Velocimetry (PIV) during film retraction experiments. We identify the jamming of these 2D capillary suspensions at a critical particle surface fraction (≃0.84) where effective viscosity diverges. Pair correlation function and number of neighbors in contact or close to contact reveal the cohesive nature of this 2D capillary granular media. The experimental 2D dynamic viscosities can be predicted by a model considering viscous dissipation at the liquid interfaces induced by the motion of individual particles.

Low gas permeability of particulate films slows down the aging of gas marbles.

Introducing solid particles into liquid films drastically changes their properties: "gas marbles" can resist overpressure and underpressure ten times larger than their pure liquid counterparts - also known as soap bubbles - before deforming. Such gas marbles can therefore prove to be useful as gas containers able to support stresses. Yet, as their liquid counterparts, they can undergo gas transfer, which can reduce the scope of their applications. However, their permeability has never been characterized. In this paper, we measure the gas permeability of gas marbles through dedicated experiments. Our results show that particulate films are less permeable to gas than their pure liquid counterparts. We attribute this limited overall gas flux to the particles that reduce the surface area through which gas diffuses.