Polar Self-Organization of Ferroelectric Nematic-Liquid-Crystal Molecules on Atomically Flat Au(111) Surface.

Understanding nanoscale mechanisms responsible for the recently discovered ferroelectric nematics can be helped by direct visualization of self-assembly of strongly polar molecules. Here, we report on scanning tunneling microscopy studies of monomolecular layers of a ferroelectric nematic liquid crystal on a reconstructed Au(111) surface. The monolayers are obtained by deposition from a solution at ambient conditions. The adsorbed ferroelectric nematic molecules self-assemble into regular rows with tilted orientation, resembling a layered structure of a smectic C. Remarkably, each molecular dipole in this architecture is oriented along the same direction giving rise to polar ferroelectric ordering.

Changing Liquid Crystal Helical Pitch with a Reversible Rotaxane Switch.

The transmission of chiral information between the molecular, meso and microscopic scales is a facet of biology that remains challenging to understand mechanistically and to mimic with artificial systems. Here we demonstrate that the dynamic change in the expression of the chirality of a rotaxane can be transduced into a change in pitch of a soft matter system. Shuttling the position of the macrocycle from far-away-from to close-to a point-chiral center on the rotaxane axle changes the expression of the chiral information that is transmitted across length scales; from nanometer scale constitutional chirality that affects the conformation of the macrocycle, to the centimeter scale chirality of the liquid crystal phase, significantly changing the pitch length of the chiral nematic structure.

Light-activated helical inversion in cholesteric liquid crystal microdroplets.

Cholesteric liquid crystal (CLC) droplets exhibit nontrivial topological features, which are controlled by the ratio between the cholesteric pitch and the droplet radius. The radial spherical structure (RSS) is of particular interest, as it reveals an onion-like concentric organization of the cholesteric helices, leading to the expression of spherical Bragg microcavities. Using an overcrowded alkene-based unidirectional molecular motor as a dopant, we show that the topological defect structure in the droplet can be activated by illumination. By using appropriate molecular motor concentrations, light can either break the symmetry of topological defects (as observed for the bent-twisted bipolar structure), or it can induce inversion of handedness in an onion-like organization (in the case of RSS). This latter feature may pave the way toward alternative activation modes of lasers based on cholesteric droplets. By also studying CLC droplets once they have reached full photoconversion at photostationary state (PSS), we highlight that the strong influence of confinement on the droplets structure occurs to the same extent after the helix inversion event. Our results are interpreted in terms of numerical simulations of the droplets' structure, which shed light on the major role played by curvature close to the droplets' center, this latter one becoming dominant when the droplet radius is small.

Molecular photoswitches mediating the strain-driven disassembly of supramolecular tubules.

Chemists have created molecular machines and switches with specific mechanical responses that were typically demonstrated in solution, where mechanically relevant motion is dissipated in the Brownian storm. The next challenge consists of designing specific mechanisms through which the action of individual molecules is transmitted to a supramolecular architecture, with a sense of directionality. Cellular microtubules are capable of meeting such a challenge. While their capacity to generate pushing forces by ratcheting growth is well known, conversely these versatile machines can also pull microscopic objects apart through a burst of their rigid tubular structure. One essential feature of this disassembling mechanism is the accumulation of strain in the tubules, which develops when tubulin dimers change shape, triggered by a hydrolysis event. We envision a strategy toward supramolecular machines generating directional pulling forces by harnessing the mechanically purposeful motion of molecular switches in supramolecular tubules. Here, we report on wholly synthetic, water-soluble, and chiral tubules that incorporate photoswitchable building blocks in their supramolecular architecture. Under illumination, these tubules display a nonlinear operation mode, by which light is transformed into units of strain by the shape changes of individual switches, until a threshold is reached and the tubules unleash the strain energy. The operation of this wholly synthetic and stripped-down system compares to the conformational wave by which cellular microtubules disassemble. Additionally, atomistic simulations provide molecular insight into how strain accumulates to induce destabilization. Our findings pave the way toward supramolecular machines that would photogenerate pulling forces, at the nanoscale and beyond.

Shape-Persistent Actuators from Hydrazone Photoswitches.

Interfacing molecular photoswitches with liquid crystal polymers enables the amplification of their nanoscale motion into macroscopic shape transformations. Typically, the mechanism responsible for actuation involves light-induced molecular disorder. Here, we demonstrate that bistable hydrazones can drive (chiral) shape transformations in liquid crystal polymer networks, with photogenerated polymer shapes displaying a long-term stability that mirrors that of the switches. The mechanism involves a photoinduced buildup of tension in the polymer, with a negligible influence on the liquid crystalline order. Hydrazone-doped liquid crystal systems thus diversify the toolbox available to the field of light-adaptive molecular actuators and hold promise in terms of soft robotics.

Dynamic Spirals of Nanoparticles in Light-Responsive Polygonal Fields.

Nanoparticles tend to aggregate once integrated into soft matter and consequently, self-assembling nanoparticles into large-scale, regular, well-defined, and ultimately chiral patterns remains an ongoing challenge toward the design and realization of organized superstructures of nanoparticles. The patterns of nanoparticles that are reported in liquid crystals so far are all static, and this lack of responsiveness extends to assemblies of nanoparticles formed in topological singularities and other localized structures of anisotropic matter. Here, it is shown that gold nanoparticles form spiral superstructures in polygonal fields of cholesteric liquid crystals. Moreover, when the cholesteric liquid crystals incorporate molecular photoswitches in their composition, the pitch of the nanoparticulate spirals follows the light-induced reorganization of the cholesteric liquid crystals. These experimental findings indicate that chiral liquid crystals can be used as chiral and dynamic templates for soft photonic nanomaterials. Controlling the geometry of these spirals of nanoparticles will ultimately allow modulating the plasmonic signature of hybrid and chiral systems.

Photoprogramming Allostery in Human Serum Albumin.

Developing strategies to interfere with allosteric interactions in proteins not only promises to deepen our understanding of vital cellular processes but also allows their regulation using external triggers. Light is particularly attractive as a trigger being spatiotemporally selective and compatible with the physiological environment. Here, we engineered a hybrid protein in which irradiation with light opens a new allosteric communication route that is not inherent to the natural system. We select human serum albumin, a promiscuous protein responsible for transporting a variety of ligands in plasma, and show that by covalently incorporating a synthetic photoswitch to subdomain IA we achieve optical control of the ligand binding in subdomain IB. Molecular dynamics simulations confirm the allosteric nature of the interactions between IA and IB in the engineered protein. Specifically, upon illumination, photoconversion of the switch is found to correlate with a less-coordinated motion of the two subdomains and an increased flexibility of the binding pocket in subdomain IB, whose fluctuations are cooperatively enhanced by the presence of ligands, ultimately facilitating their release. Our combined experimental and computational work demonstrates how harnessing artificial molecular switches enables photoprogramming the allosteric regulation of binding activities in such a prominent protein.

Long-Lived Supramolecular Helices Promoted by Fluorinated Photoswitches.

Chiral azobenzenes can be used as photoswitchable dopants to control supramolecular helices in liquid crystals. However, the lack of thermal stability of the cis-isomer precludes envisioning the generation of long-lived supramolecular helices with light. Here, this study demonstrates thermally stable and axially chiral azobenzene switches that can be used as chiral dopants to create supramolecular helices from (achiral) nematic liquid crystals. Their trans-to-cis photoisomerization leads to a variation of helical twisting power that reaches up to 60%, and the helical superstructure that is engineered with light displays a relaxation time that reaches tens of hours. These results demonstrate that combining ortho-fluorination with axial chirality in molecular photoswitches constitutes an efficient strategy to promote long-lived helical states. Further, this approach shows potential to design supramolecular machines that are controlled by light entirely.

Humidity-responsive actuators from integrating liquid crystal networks in an orienting scaffold.

Developing shape-shifting materials requires combining the flexibility needed by shape-shifting properties, with the toughness that is demanded to maintain their mechanical performance. Typically, in liquid crystal networks, the amplitude of the shape transformation can be hindered by large cross-linking densities. Here, we argue that a promising strategy to address this limitation consists in integrating liquid crystal networks into an anisotropic and porous material that acts as an orienting scaffold. This strategy shows similarities with the principles of stimuli-responsive deformation in plants, where inflexible elements with specific orientations are integrated into a stimuli-responsive matrix. By aligning liquid crystals in a porous polypropylene orienting scaffold, we demonstrate liquid crystal networks that respond to humidity with a shape change, yet they display high elastic modulus and toughness. Various chiral shapes can be generated in single and double layers of these films, and the complexity of their actuation modes is enhanced, including twisting, curling or winding. We anticipate that these hybrid composites and the strategy they embody can find application to other stimuli-responsive anisotropic soft materials.

Electrically driven directional motion of a four-wheeled molecule on a metal surface.

Propelling single molecules in a controlled manner along an unmodified surface remains extremely challenging because it requires molecules that can use light, chemical or electrical energy to modulate their interaction with the surface in a way that generates motion. Nature's motor proteins have mastered the art of converting conformational changes into directed motion, and have inspired the design of artificial systems such as DNA walkers and light- and redox-driven molecular motors. But although controlled movement of single molecules along a surface has been reported, the molecules in these examples act as passive elements that either diffuse along a preferential direction with equal probability for forward and backward movement or are dragged by an STM tip. Here we present a molecule with four functional units--our previously reported rotary motors--that undergo continuous and defined conformational changes upon sequential electronic and vibrational excitation. Scanning tunnelling microscopy confirms that activation of the conformational changes of the rotors through inelastic electron tunnelling propels the molecule unidirectionally across a Cu(111) surface. The system can be adapted to follow either linear or random surface trajectories or to remain stationary, by tuning the chirality of the individual motor units. Our design provides a starting point for the exploration of more sophisticated molecular mechanical systems with directionally controlled motion.

High-Power Actuation from Molecular Photoswitches in Enantiomerically Paired Soft Springs.

Motion in plants often relies on dynamic helical systems as seen in coiling tendrils, spasmoneme springs, and the opening of chiral seedpods. Developing nanotechnology that would allow molecular-level phenomena to drive such movements in artificial systems remains a scientific challenge. Herein, we describe a soft device that uses nanoscale information to mimic seedpod opening. The system exploits a fundamental mechanism of stimuli-responsive deformation in plants, namely that inflexible elements with specific orientations are integrated into a stimuli-responsive matrix. The device is operated by isomerization of a light-responsive molecular switch that drives the twisting of strips of liquid-crystal elastomers. The strips twist in opposite directions and work against each other until the pod pops open from stress. This mechanism allows the photoisomerization of molecular switches to stimulate rapid shape changes at the macroscale and thus to maximize actuation power.

Labelling Bacterial Nanocages with Photo-switchable Fluorophores.

The robustness and biocompatibility of bacterial nanocages holds promise for bio-nanotechnologies. The propensity of these nano-carriers to penetrate cells has been demonstrated, which calls for the development of tracking strategies, both in vitro and in vivo. Here, we label bacterial nanocages with photo-switchable fluorophores, to facilitate their imaging by super-resolution microscopy. We demonstrate the functionalization of the encapsulin from Brevibacterium linens with a spiropyran, which is not fluorescent, by covalent attachment to the amine residues at the outer encapsulin shell. Upon alternating irradiation with ultraviolet and visible light, the spiropyran switches forth and back to its fluorescent merocyanine photo-isomer and thus the fluorescence can be switched on and off, reversibly. We also show that the bacterial compartments preserve their structural integrity upon covalent modification and over at least five irradiation cycles.

Fluorinated Azobenzenes for Shape-Persistent Liquid Crystal Polymer Networks.

Liquid crystal polymer networks respond with an anisotropic deformation to a range of external stimuli. When doped with molecular photoswitches, these materials undergo complex shape modifications under illumination. As the deformations are reversed when irradiation stops, applications where the activated shape is required to have thermal stability have been precluded. Previous attempts to incorporate molecular switches into thermally stable photoisomers were unsuccessful at photogenerating macroscopic shapes that are retained over time. Herein, we show that to preserve photoactivated molecular deformation on the macroscopic scale, it is important not only to engineer the thermal stability of the photoswitch but also to adjust the cross-linking density in the polymer network and to optimize the molecular orientations in the material. Our strategy resulted in materials containing fluorinated azobenzenes that retain their photochemical shape for more than eight days, which constitutes the first demonstration of long-lived photomechanical deformation in liquid-crystal polymer networks.

Emergence of chirality in hexagonally packed monolayers of hexapentyloxytriphenylene on Au(111): a joint experimental and theoretical study.

We investigate the expression of chirality in a monolayer formed spontaneously by 2,3,6,7,10,11-pentyloxytriphenylene (H5T) on Au(111). We resolve its interface morphology by combining scanning tunneling microscopy (STM) with theoretical calculations of intermolecular and interfacial interaction potentials. We observe two commensurate structures. While both of them belong to a hexagonal space group, analogical to the triangular symmetry of the molecule and the hexagonal symmetry of the substrate surface, they surprisingly reveal a 2D chiral character. The corresponding breaking of symmetry arises for two reasons. First it is due to the establishment of a large molecular density on the substrate, which leads to a rotation of the molecules with respect to the molecular network crystallographic axes to avoid steric repulsion between neighboring alkoxy chains. Second it is due to the molecule-substrate interactions, leading to commensurable large crystallographic cells associated with the large size of the molecule. As a consequence, molecular networks disoriented with respect to the high symmetry directions of the substrate are induced. The high simplicity of the intermolecular and molecule-substrate van der Waals interactions leading to these observations suggests a generic character for this kind of symmetry breaking. We demonstrate that, for similar molecular densities, only two kinds of molecular networks are stabilized by the molecule-substrate interactions. The most stable network favors the interfacial interactions between terminal alkoxy tails and Au(111). The metastable one favors a specific orientation of the triphenylene core with its symmetry axes collinear to the Au⟨110⟩. This specific orientation of the triphenylene cores with respect to Au(111) appears associated with an energy advantage larger by at least 0.26 eV with respect to the disoriented core.

Soft magnets from the self-organization of magnetic nanoparticles in twisted liquid crystals.

Organizing magnetic nanoparticles into long-range and dynamic assemblies would not only provide new insights into physical phenomena but also open opportunities for a wide spectrum of applications. In particular, a major challenge consists of the development of nanoparticle-based materials for which the remnant magnetization and coercive field can be controlled at room temperature. Our approach consists of promoting the self-organization of magnetic nanoparticles in liquid crystals (LCs). Using liquid crystals as organizing templates allows us to envision the design of tunable self-assemblies of magnetic nanoparticles, because liquid crystals are known to reorganize under a variety of external stimuli. Herein, we show that twisted liquid crystals can be used as efficient anisotropic templates for superparamagnetic nanoparticles and demonstrate the formation of hybrid soft magnets at room temperature.

Molecular machines: nanomotor rotates microscale objects.

Nanomachines of the future will require molecular-scale motors that can perform work and collectively induce controlled motion of much larger objects. We have designed a synthetic, light-driven molecular motor that is embedded in a liquid-crystal film and can rotate objects placed on the film that exceed the size of the motor molecule by a factor of 10,000. The changes in shape of the motor during the rotary steps cause a remarkable rotational reorganization of the liquid-crystal film and its surface relief, which ultimately causes the rotation of submillimetre-sized particles on the film.

Motile behaviour of droplets in lipid systems.

Motility is the capacity for living organisms to move autonomously and with purpose, and is essential to life. The transition from abiotic chemistry into motile cellular compartments has yet to be understood, but motile behaviour likely followed chemical evolution because primeval cell survival depended on scouting for resources effectively. Minimalistic motile systems provide an experimental framework to delineate the emergence mechanisms of such an evolutionary asset. In this Review, we discuss frontier developments in controlling the movement of droplets in lipid systems, in particular, chemotactic behaviours driven by fluctuations in interfacial tension, because of its simple mechanism and prebiotic relevance. Although most efforts have focused on designing oil droplet motility in lipid-rich aqueous solutions, we highlight that water droplets can also move in lipid-enriched oils. First, we describe how droplets evolve chemotactic motility in lipid systems. Next, we review how these oil droplets can adapt their movement to illumination conditions. Finally, we discuss examples where chemical reactivity brings complexity to motility. This work contributes to systems chemistry, where chemical reactions combined with physicochemical phenomena can yield new functions, such that a limited set of molecules can promote complex movement at larger functional scales by following the rules of molecular chemistry.

Run-and-halt motility of droplets in response to light.

Microscopic motility is a property that emerges from systems of interacting molecules. Unraveling the mechanisms underlying such motion requires coupling the chemistry of molecules with physical processes that operate at larger length scales. Here, we show that photoactive micelles composed of molecular switches gate the autonomous motion of oil droplets in water. These micelles switch from large trans-micelles to smaller cis-micelles in response to light, and only the trans-micelles are effective fuel for the motion. Ultimately, it is this light that controls the movement of the droplets via the photochemistry of the molecules composing the micelles used as fuel. Notably, the droplets evolve positive photokinetic movement, and in patchy light environments, they preferentially move toward peripheral areas as a result of the difference in illumination conditions at the periphery. Our findings demonstrate that engineering the interplay between molecular photo-chemistry and microscopic motility allows designing motile systems rationally.

Light-Fueled Nanoscale Surface Waving in Chiral Liquid Crystal Networks.

Nano- and micro-actuating systems are promising for application in microfluidics, haptics, tunable optics, and soft robotics. Surfaces capable to change their topography at the nano- and microscale on demand would allow control over wettability, friction, and surface-driven particle motility. Here, we show that light-responsive cholesteric liquid crystal (LC) networks undergo a waving motion of their surface topography upon irradiation with light. These dynamic surfaces are fabricated with a maskless one-step procedure, relying on the liquid crystal alignment in periodic structures upon application of a weak electric field. The geometrical features of the surfaces are controlled by tuning the pitch of the liquid crystal. Pitch control by confinement allows engineering one-dimensional (1D) and two-dimensional (2D) structures that wave upon light exposure. This work demonstrates the potential that self-organizing systems might have for engineering dynamic materials, and harnessing the functionality of molecules to form dynamic surfaces, with nanoscale precision over their waving motion.