Realizing Symmetry-Breaking Architectures in Soap Films.

We show here that soap films-typically expected to host symmetric molecular arrangements-can be constructed with differing opposite surfaces, breaking their symmetry, and making them reminiscent of functional biological motifs found in nature. Using fluorescent molecular probes as dopants on different sides of the film, resonance energy transfer could be employed to confirm the lack of symmetry, which was found to persist on timescales of several minutes. Further, a theoretical analysis of the main transport phenomena involved yielded good agreement with the experimental observations.

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.

Emergence of Electric Fields at the Water-C12E6 Surfactant Interface.

We study the properties of the interface of water and the surfactant hexaethylene glycol monododecyl ether (C12E6) with a combination of heterodyne-detected vibrational sum frequency generation (HD-VSFG), Kelvin-probe measurements, and molecular dynamics (MD) simulations. We observe that the addition of the hydrogen-bonding surfactant C12E6, close to the critical micelle concentration (CMC), induces a drastic enhancement in the hydrogen bond strength of the water molecules close to the interface, as well as a flip in their net orientation. The mutual orientation of the water and C12E6 molecules leads to the emergence of a broad (∼3 nm) interface with a large electric field of ∼1 V/nm, as evidenced by the Kelvin-probe measurements and MD simulations. Our findings may open the door for the design of novel electric-field-tuned catalytic and light-harvesting systems anchored at the water-surfactant-air interface.

A novel concept of photosynthetic soft membranes: a numerical study.

We focus on a novel concept of photosynthetic soft membranes, possibly able to allow the conversion of solar energy and carbon dioxide (CO[Formula: see text]) into green fuels. The considered membranes rely on self-assembled functional molecules in the form of soap films. We elaborate a multi-scale and multi-physics model to describe the relevant phenomena, investigating the expected performance of a single soft photosynthetic membrane. First, we present a macroscale continuum model, which accounts for the transport of gaseous and ionic species within the soap film, the chemical equilibria and the two involved photocatalytic half reactions of the CO[Formula: see text] reduction and water oxidation at the two gas-surfactant-water interfaces of the soap film. Second, we introduce a mesoscale discrete Monte Carlo model, to deepen the investigation of the structure of the functional monolayers. Finally, the morphological information obtained at the mesoscale is integrated into the continuum model in a multi-scale framework. The developed tools are then used to perform sensitivity studies in a wide range of possible experimental conditions, to provide scenarios on fuel production by such a novel approach.