Bioinspired underwater locomotion of light-driven liquid crystal gels.

Soft-bodied aquatic invertebrates, such as sea slugs and snails, are capable of diverse locomotion modes under water. Recapitulation of such multimodal aquatic locomotion in small-scale soft robots is challenging, due to difficulties in precise spatiotemporal control of deformations and inefficient underwater actuation of existing stimuli-responsive materials. Solving this challenge and devising efficient untethered manipulation of soft stimuli-responsive materials in the aquatic environment would significantly broaden their application potential in biomedical devices. We mimic locomotion modes common to sea invertebrates using monolithic liquid crystal gels (LCGs) with inherent light responsiveness and molecular anisotropy. We elicit diverse underwater locomotion modes, such as crawling, walking, jumping, and swimming, by local deformations induced by selective spatiotemporal light illumination. Our results underpin the pivotal role of the physicomechanical properties of LCGs in the realization of diverse modes of light-driven robotic underwater locomotion. We envisage that our results will introduce a toolbox for designing efficient untethered soft robots for fluidic environments.

Programmable and Self-Healable Liquid Crystal Elastomer Actuators Based on Halogen Bonding.

Shape-changing polymeric materials have gained significant attention in the field of bioinspired soft robotics. However, challenges remain in versatilizing the shape-morphing process to suit different tasks and environments, and in designing systems that combine reversible actuation and self-healing ability. Here, we report halogen-bonded liquid crystal elastomers (LCEs) that can be arbitrarily shape-programmed and that self-heal under mild thermal or photothermal stimulation. We incorporate halogen-bond-donating diiodotetrafluorobenzene molecules as dynamic supramolecular crosslinks into the LCEs and show that these relatively weak crosslinks are pertinent for their mechanical programming and self-healing. Utilizing the halogen-bonded LCEs, we demonstrate proof-of-concept soft robotic motions such as crawling and rolling with programmed velocities. Our results showcase halogen bonding as a promising, yet unexplored tool for the preparation of smart supramolecular constructs for the development of advanced soft actuators.

Optically Controlled Construction of Three-Dimensional Protein Arrays.

Protein crystallization is an important tool for structural biology and nanostructure preparation. Here, we report on kinetic pathway-dependent protein crystals that are controlled by light. Photo-responsive crystallites are obtained by complexing the model proteins with cationic azobenzene dyes. The crystalline state is readily switched to a dispersed phase under ultraviolet light and restored by subsequent visible-light illumination. The switching can be reversibly repeated for multiple cycles without noticeable structure deterioration. Importantly, the photo-treatment not only significantly increases the crystallinity, but creates crystallites at conditions where no ordered lattices are observed upon directly mixing the components. Further control over the azobenzene isomerization kinetics produces protein single crystals of up to ≈50 µm. This approach offers an intriguing method to fabricate metamaterials and study optically controlled crystallization.

Analysis of light diffraction by azobenzene-based photoalignment layers.

Photoalignment materials, such as the azobenzene-based PAAD series studied here, are becoming increasingly important in liquid crystal-based optical devices and displays. Yet their properties and, in particular, their response to light, are still not fully understood. We investigate, experimentally and theoretically, the photoinduced birefringence, the order parameter and the formation of surface relief gratings, as well as the diffraction caused by them. We show that some of the azobenzene PAAD materials are suitable for the formation of surface relief gratings with high modulation depth, while others exhibit strong photoinduced birefringence. The two effects are inversely correlated: the stronger the surface relief grating is, the weaker is photoinduced birefringence. Analytical formulas based on the Raman-Nath approximation and numerical simulations of Maxwell's equations are used to quantify the diffraction caused by the induced diffraction gratings, showing excellent agreement between theory and experiment.

New tricks and emerging applications from contemporary azobenzene research.

Azobenzenes have many faces. They are well-known as dyes, but most of all, azobenzenes are versatile photoswitchable molecules with powerful photochemical properties. Azobenzene photochemistry has been extensively studied for decades, but only relatively recently research has taken a steer towards applications, ranging from photonics and robotics to photobiology. In this perspective, after an overview of the recent trends in the molecular design of azobenzenes, we highlight three research areas where the azobenzene photoswitches may bring about promising technological innovations: chemical sensing, organic transistors, and cell signaling. Ingenious molecular designs have enabled versatile control of azobenzene photochemical properties, which has in turn facilitated the development of chemical sensors and photoswitchable organic transistors. Finally, the power of azobenzenes in biology is exemplified by vision restoration and photactivation of neural signaling. Although the selected examples reveal only some of the faces of azobenzenes, we expect the fields presented to develop rapidly in the near future, and that azobenzenes will play a central role in this development.

Towards low-energy-light-driven bistable photoswitches: ortho-fluoroaminoazobenzenes.

Thermally stable photoswitches that are driven with low-energy light are rare, yet crucial for extending the applicability of photoresponsive molecules and materials towards, e.g., living systems. Combined ortho-fluorination and -amination couples high visible light absorptivity of o-aminoazobenzenes with the extraordinary bistability of o-fluoroazobenzenes. Herein, we report a library of easily accessible o-aminofluoroazobenzenes and establish structure-property relationships regarding spectral qualities, visible light isomerization efficiency and thermal stability of the cis-isomer with respect to the degree of o-substitution and choice of amino substituent. We rationalize the experimental results with quantum chemical calculations, revealing the nature of low-lying excited states and providing insight into thermal isomerization. The synthesized azobenzenes absorb at up to 600 nm and their thermal cis-lifetimes range from milliseconds to months. The most unique example can be driven from trans to cis with any wavelength from UV up to 595 nm, while still exhibiting a thermal cis-lifetime of 81 days.

Multistage Reversible Tg Photomodulation and Hardening of Hydrazone-Containing Polymers.

The glass transition temperature (Tg) of a series of polyacrylate- and polymethacrylate-based polymers having bistable hydrazone photoswitches as pendants increases upon photoisomerization. The ensuing photohardening of the polymeric network was corroborated using nanoindentation measurements. The bistability of the switch allowed us to lock-in and sustain multiple Tg values in the same polymeric material as a function of the hydrazone switch's Z/E isomer ratio, even at elevated temperatures.

Near-Infrared Light-Driven Shape-Morphing of Programmable Anisotropic Hydrogels Enabled by MXene Nanosheets.

Herein, we report near-infrared (NIR) light-driven shape-morphing of programmable MXene-containing anisotropic hydrogel actuators that are fabricated through in situ free-radical copolymerization of a judiciously designed MXene nanomonomer with thermosensitive hydrogel network. A low electric field (few V mm-1 ) was found to enable a spatial distribution of MXene nanosheets and hence introduce anisotropy into the hydrogel network. Programmable anisotropic hydrogel actuators were developed by controlling ITO electrode pattern, direct-current (DC) electric field direction and mask-assisted photopolymerization. As a proof-of-concept, we demonstrate NIR light-driven shape morphing of the MXene-containing anisotropic hydrogel into various shapes and devise a four-arm soft gripper that can perform distinct photomechanical functions such as grasping, lifting/lowering down and releasing an object upon sequential NIR light exposure.

Fast Switching of Bright Whiteness in Channeled Hydrogel Networks.

Beside pigment absorption and reflection by periodic photonic structures, natural species often use light scattering to achieve whiteness. Synthetic hydrogels offer opportunities in stimuli-responsive materials and devices; however, they are not conventionally considered as ideal materials to achieve high whiteness by scattering due to the ill-defined porosities and the low refractive index contrast between the polymer and water. Herein, a poly(N-isopropylacrylamide) hydrogel network with percolated empty channels (ch-PNIPAm) is demonstrated to possess switchable bright whiteness upon temperature changes, obtained by removing the physical agarose gel in a semi-interpenetrating network of agarose and PNIPAm. The hydrogel is highly transparent at room temperature and becomes brightly white above 35 °C. Compared to conventional PNIPAm, the ch-PNIPAm hydrogel exhibits 80% higher reflectance at 800 nm and 18 times faster phase transition kinetics. The nanoscopic channels in the ch-PNIPAm facilitate water diffusion upon phase transition, thus enabling the formation of smaller pores and enhanced whiteness in the gel. Furthermore, fast photothermally triggered response down to tens of milliseconds can be achieved. This unique property of the ch-PNIPAm hydrogel to efficiently scatter visible light can be potentially used for, e.g., smart windows, optical switches, and, as demonstrated in this report, thermoresponsive color displays.

Optically induced crossover from weak to strong coupling regime between surface plasmon polaritons and photochromic molecules.

We demonstrate optically induced crossover from a weak to a strong coupling regime in a single photonic system consisting of propagating surface plasmon polaritons (SPPs) on a planar silver film and ultraviolet (UV)-switchable photochromic molecules. A gradual increase is observed in the vacuum Rabi splitting upon increasing UV exposure, along with intriguing behavior, where the reflectivity initially decreases due to increased losses at the weak coupling regime, and then increases due to the emergence of strongly coupled modes and the associated band gap formation at the resonance frequency of the uncoupled states. This work explicitly demonstrates the optical tunability of the degree of hybridization of the SPP and exciton modes, spanning the range from weak to intermediate and finally to the strong coupling regime.

Design principles for non-reciprocal photomechanical actuation.

Non-reciprocal motions are a sequence of movements exhibiting time-reversal asymmetry. Such movements are common among various natural species, being adopted as a typical strategy for achieving efficient locomotion. Generally, the realization of non-reciprocal motions in man-made robotic devices requires synchronous control of at least two individual actuators, hence posing challenges to soft micro-robotics where the miniaturization limits integration of different mechanical components and the possibility of using onboard batteries. Here, we introduce general concepts for achieving non-reciprocal movements in wirelessly controlled soft actuators made of photomechanically responsive liquid crystal networks. The monolithic actuators are composed of two segments that can be actuated photochemically and photothermally, and the non-reciprocal motion is obtained by a control sequence that temporally modulates light sources of different wavelengths. Through proper selection of photoactive compounds, the number of modulated light sources can be decreased, from three to two, and eventually to one. Finally, we demonstrate non-reciprocal self-oscillation by self-shadowing effect in a flexible strip under a constant light field with no temporal modulation. This study provides general guidelines to light-controlled non-reciprocal actuation, offering new strategies for the control of wireless soft micro-robotics.

Halide Perovskite Nanocrystals for Next-Generation Optoelectronics.

Colloidal perovskite nanocrystals (PNCs) combine the outstanding optoelectronic properties of bulk perovskites with strong quantum confinement effects at the nanoscale. Their facile and low-cost synthesis, together with superior photoluminescence quantum yields and exceptional optical versatility, make PNCs promising candidates for next-generation optoelectronics. However, this field is still in its early infancy and not yet ready for commercialization due to several open challenges to be addressed, such as toxicity and stability. Here, the key synthesis strategies and the tunable optical properties of PNCs are discussed. The photophysical underpinnings of PNCs, in correlation with recent developments of PNC-based optoelectronic devices, are especially highlighted. The final goal is to outline a theoretical scaffold for the design of high-performance devices that can at the same time address the commercialization challenges of PNC-based technology.

Continuously tunable polymer membrane laser.

Thin-film organic distributed feedback (DFB) lasers processed with elastomeric polymers allow fabrication of flexible and continuously tunable coherent light sources. So far, the realized laser devices fall short on broad continuous tuning range. We demonstrate that the addition of plasticizers to the polymer matrix and the minimization of the thickness of the laser can reduce mechanical impact and, thus, extend the wavelength tuning range to the full gain range of the active medium. A contact-transfer method is used to transfer gently the ultra-thin membrane DFB laser to a silicone support. A continuous tuning of the laser wavelength up to 77 nm in the orange-red spectral range of a single laser dye was achieved by mechanical stretching of the supporting film with a DFB membrane laser on top.

The Halogen Bond.

The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design.

Light-Driven, Caterpillar-Inspired Miniature Inching Robot.

Liquid crystal elastomers are among the best candidates for artificial muscles, and the materials of choice when constructing microscale robotic systems. Recently, significant efforts are dedicated to designing stimuli-responsive actuators that can reproduce the shape-change of soft bodies of animals by means of proper external energy source. However, transferring material deformation efficiently into autonomous robotic locomotion remains a challenge. This paper reports on a miniature inching robot fabricated from a monolithic liquid crystal elastomer film, which upon visible-light excitation is capable of mimicking caterpillar locomotion on different substrates like a blazed grating and a paper surface. The motion is driven by spatially uniform visible light with relatively low intensity, rendering the robot "human-friendly," i.e., operational also on human skin. The design paves the way toward light-driven, soft, mobile microdevices capable of operating in various environments, including the close proximity of humans.

On the molecular optical nonlinearity of halogen-bond-forming azobenzenes.

We study hyper-Rayleigh scattering and computed molecular hyperpolarizability in a series of azobenzene chromophores in chloroform and dimethylformamide as solvents. The chromophores form halogen or hydrogen bonds of varying strength with dimethylformamide molecules, differently from what is expected for chloroform. We show that hyperpolarizability is unaffected or sligthly lower with the azobenzene forming the strongest halogen bond. Solid supramolecular polymers with the same chromophores have previously demonstrated clearly higher second-order nonlinear responses when a halogen-bond-accepting polymer is used, the larger increase being associated with the stronger halogen bond. The present study proves that the higher optical nonlinearity in polymers lies in the better ordering of the chromophores instead of changes in molecular hyperpolarizability, highlighting the unique properties of halogen bonding in supramolecular chemistry.

Photoresponsive ionic liquid crystals assembled via halogen bond: en route towards light-controllable ion transporters.

We demonstrate that halogen bonding (XB) can offer a novel approach for the construction of photoresponsive ionic liquid crystals. In particular, we assembled two new supramolecular complexes based on 1-ethyl-3-methylimidazolium iodides and azobenzene derivatives containing an iodotetrafluoro-benzene ring as XB donor, where the iodide anion acted as an XB acceptor. DSC and X-ray diffraction analyses revealed that the preferred stoichiometry between the XB donors and acceptors is 2 : 1, and that the iodide anions act as bidentate XB-acceptors, binding two azobenzene derivatives. Due to the high directionality of the XB, calamitic superanions are obtained, while the segregation occurring between the charged and uncharged parts of the molecules gives rise to a layered structure in the crystal lattice. Despite the fact that the starting materials are non-mesomorphic, the halogen-bonded supramolecular complexes exhibited monotropic lamellar liquid-crystalline phases over broad temperature ranges, as confirmed with polarized optical microscopy. Due to the presence of the azobenzene moieties, the LCs were photoresponsive, and a LC-to-isotropic phase transition could be obtained by irradiation with UV light. We envisage that the light-induced phase transition, in combination with the ionic nature of the LC, provides a route towards light-induced control over ion transport and conductance in these supramolecular complexes.

Surface-Relief Gratings in Halogen-Bonded Polymer-Azobenzene Complexes: A Concentration-Dependence Study.

In recent years, supramolecular complexes comprising a poly(4-vinylpyridine) backbone and azobenzene-based halogen bond donors have emerged as a promising class of materials for the inscription of light-induced surface-relief gratings (SRGs). The studies up to date have focused on building supramolecular hierarchies, i.e., optimizing the polymer-azobenzene noncovalent interaction for efficient surface patterning. They have been conducted using systems with relatively low azobenzene content, and little is known about the concentration dependence of SRG formation in halogen-bonded polymer-azobenzene complexes. Herein, we bridge this gap, and study the concentration dependence of SRG formation using two halogen-bond-donating azobenzene derivatives, one functionalized with a tetrafluoroiodophenyl and the other with an iodoethynylphenyl group. Both have been previously identified as efficient molecules in driving the SRG formation. We cover a broad concentration range, starting from 10 mol % azobenzene content and going all the way up to equimolar degree of complexation. The complexes are studied as spin-coated thin films, and analyzed by optical microscopy, atomic force microscopy, and optical diffraction arising during the SRG formation. We obtained diffraction efficiencies as high as 35%, and modulation depths close to 400 nm, which are significantly higher than the values previously reported for halogen-bonded polymer-azobenzene complexes.

Photoinduced nonlinear optical response in azobenzene-functionalized molecular glass.

We show that mexylaminotriazine molecular glass functionalized with the azobenzene derivative Disperse Red 1 shows equally strong second-order nonlinear optical response as well-known polymers with the same photoactive component. Furthermore, even high chromophore loading does not adversely affect the nonlinear response. This suggests that chromophore-chromophore intermolecular interactions do not greatly limit the response of such molecular glasses, which therefore provide an excellent materials platform for nonlinear optical applications.