A key goal of nanotechnology is the development of artificial machines capable of converting molecular movement into macroscopic work. Although conversion of light into shape changes has been reported and compared to artificial muscles, real applications require work against an external load. Here, we describe the design, synthesis and operation of spring-like materials capable of converting light energy into mechanical work at the macroscopic scale. These versatile materials consist of molecular switches embedded in liquid-crystalline polymer springs. In these springs, molecular movement is converted and amplified into controlled and reversible twisting motions. The springs display complex motion, which includes winding, unwinding and helix inversion, as dictated by their initial shape. Importantly, they can produce work by moving a macroscopic object and mimicking mechanical movements, such as those used by plant tendrils to help the plant access sunlight. These functional materials have potential applications in micromechanical systems, soft robotics and artificial muscles.
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.
Molecular machines operated by light have been recently shown to be able to produce oriented motion at the molecular scale as well as do macroscopic work when embedded in supramolecular structures. However, any supramolecular movement irremediably ceases as soon as the concentration of the interconverting molecular motors or switches reaches a photo-stationary state. To circumvent this limitation, researchers have typically relied on establishing oscillating illumination conditions-either by modulating the source intensity or by using bespoke illumination arrangements. In contrast, here we report a supramolecular system in which the emergence of oscillating patterns is encoded at the molecular level. Our system comprises chiral liquid crystal structures that revolve continuously when illuminated, under the action of embedded light-driven molecular motors. The rotation at the supramolecular level is sustained by the diffusion of the motors away from a localized illumination area. Above a critical irradiation power, we observe a spontaneous symmetry breaking that dictates the directionality of the supramolecular rotation. The interplay between the twist of the supramolecular structure and the diffusion of the chiral molecular motors creates continuous, regular and unidirectional rotation of the liquid crystal structure under non-equilibrium conditions.
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.
Polymer springs that twist under irradiation with light, in a manner that mimics how plant tendrils twist and turn under the effect of differential expansion in different sections of the plant, show potential for soft robotics and the development of artificial muscles. The soft springs prepared using this protocol are typically 1 mm wide, 50 μm thick and up to 10 cm long. They are made from liquid crystal polymer networks in which an azobenzene derivative is introduced covalently as a molecular photo-switch. The polymer network is prepared by irradiation of a twist cell filled with a mixture of shape-persistent liquid crystals, liquid crystals having reactive end groups, molecular photo-switches, some chiral dopant and a small amount of photoinitiator. After postcuring, the soft polymer film is removed and cut into springs, the geometry of which is determined by the angle of cut. The material composing the springs is characterized by optical microscopy, scanning electron microscopy and tensile strength measurements. The springs operate at ambient temperature, by mimicking the orthogonal contraction mechanism that is at the origin of plant coiling. They shape-shift under irradiation with UV light and can be pre-programmed to either wind or unwind, as encoded in their geometry. Once illumination is stopped, the springs return to their initial shape. Irradiation with visible light accelerates the shape reversion.
Doping cholesteric liquid crystals with photo-responsive molecules enables controlling the colour and polarisation of the light they reflect. However, accelerating the rate of relaxation of these photo-controllable liquid crystals remains challenging. Here we show that the relaxation rate of the cholesteric helix is fully determined by helix inversion of the molecular dopants.
Biofouling on surfaces immersed in aquatic environment induces catastrophic corrosion of metallic materials in petrochemical infrastructures, maritime facilities, and power plants. To combat the synergistic effect of biofouling and corrosion on the deterioration of metallic materials, smart coatings possessing a dual function of antibiofouling and anticorrosion properties are needed. Herein, redox‐responsive copolymer conjugates are synthesized and employed as coatings with the dual function of biofouling and corrosion mitigation. The dual function of copolymers is attributed to fluorinated units and the corrosion inhibitor 2‐mercaptobenzothiazole (MBT) conjugated via disulfide linkages. Indeed, the disulfide linkages can be cleaved in a reducing environment, yielding controlled release of the corrosion inhibitor MBT during corrosion process. The antibiofouling action against protein adsorption and algal attachment is enabled by cooperation of the repellent characteristic of fluorinated moieties and the biocidal effect of conjugated MBT.
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.
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