Bioinspired smart materials with synergistic allochroic luminescence and complex deformation are expected to play an important role in many areas of science and technology. However, it is still ...challenging to fabricate such soft actuators with high programmability that can be manipulated in situ with high spatial resolution. Herein, we have incorporated terminally functionalized aggregation‐induced emission active tetraphenylethene derivative and photochromic spiropyran moieties into the networks of liquid crystal elastomers through covalent bonding to obtain the synergistic photochromic luminescence and programmable soft actuators. Bio‐mimic functions and light‐induced auxetic metamaterial‐like devices were shown to be feasible based on the combination of assembly and origami‐programming strategy. These bioinspired devices with synergistic photochromic luminescence and complex photodeformation abilities provide an elegant strategy to design multi‐functional liquid crystal actuators.
Inspired by the synergic allochroic and shape‐morphing bio‐functions like caterpillars and cephalopods, photochromic luminescent liquid crystal actuators were prepared. Complex movements and fluorescent colors can be synergically manipulated by light based on the phase transition of liquid crystals and photoresponse of the fluorescent chromophores after the actuators were programmed with hybrid mesogenic alignments.
Overcoming the resistance to apoptosis and immunosuppression of tumor cells is a significant challenge in augmenting the effect of cancer immunotherapy. Pyroptosis, a lytic programmed cell‐death ...pathway unlike apoptosis, is considered a type of immunogenic cell death (ICD) that can intensify the ICD process in tumor cells, releasing dramatically increased tumor‐associated antigens and damage‐associated molecular patterns to promote cancer immunotherapy. Herein, a tumor cell membrane‐targeted aggregation‐induced emission photosensitive dimer is found to be able to achieve highly efficient ICD under the synergistic effect of photodynamic and photothermal therapy. The photosensitive dimer can efficiently produce type‐I reactive oxygen species (ROS) by photodynamic therapy in hypoxic tumor tissue, leading to pyroptosis by direct cell membrane damage, which is further reinforced by its photothermal effect. Furthermore, the enhanced ICD effect based on the dimer can completely eliminate the primary tumor on the seventh day of treatment and can also boost systemic antitumor immunity by generating immune memory, which is demonstrated by the superior antitumor therapeutic effects on both solid tumors and metastatic tumors when healing 4T1 tumor mouse models with poor immunogenicity.
A membrane‐targeted photosensitive dimer, which effectively generates type‐I reactive oxygen species in hypoxic tumor tissue for pyroptosis‐mediated photoimmunotherapy, is successfully developed. Its remarkable photothermal properties accelerate the pyroptosis process, increase DNA damage in tumor cells, generate drastic immunogenic cell death and systemic antitumor immune response, and prevent tumor recurrence and metastasis.
Light‐harvesting systems are an important way for capturing, transferring and utilizing light energy. It remains a key challenge to develop highly efficient artificial light‐harvesting systems. ...Herein, we report a supramolecular co‐assembly based on lower‐rim dodecyl‐modified sulfonatocalix4arene (SC4AD) and naphthyl‐1,8‐diphenyl pyridinium derivative (NPS) as a light‐harvesting platform. NPS as a donor shows significant aggregation induced emission enhancement (AIEE) after assembling with SC4AD. Upon introduction of Nile blue (NiB) as an acceptor into the NPS‐SC4AD co‐assembly, the light‐harvesting system becomes near‐infrared (NIR) emissive (675 nm). Importantly, the NIR emitting NPS‐SC4AD‐NiB system exhibits an ultrahigh antenna effect (33.1) at a high donor/acceptor ratio (250:1). By co‐staining PC‐3 cells with a Golgi staining reagent, NBD C6‐ceramide, NIR imaging in the Golgi apparatus has been demonstrated using these NIR emissive nanoparticles.
Combined harvester: Supramolecular co‐assembly of lower‐rim dodecyl‐modified sulfonatocalix4arene (SC4AD) and naphthyl‐1,8‐diphenyl pyridinium derivatives (NPS) gives a light‐harvesting platform showing significant aggregation induced emission enhancement (AIEE). By using these near‐infrared (NIR) emissive nanoparticles imaging in the Golgi apparatus is possible.
A two‐stage mediated near‐infrared (NIR) emissive supramolecular assembly for lysosome‐targeted cell imaging is presented. 4,4′‐Anthracene‐9,10‐diylbis(ethene‐2,1‐diyl))bis(1‐ethylpyridin‐1‐ium) ...bromide (ENDT) was synthesized as an organic dye with weak fluorescence emission at 625 nm. When ENDT complexes with cucurbit8uril (CB8), this binary supramolecular complex assembles into nanorods with a near‐infrared fluorescence emission (655 nm) and fluorescence enhancement as the first stage. Such supramolecular complexes interact with lower‐rim dodecyl‐modified sulfonatocalix4arene (SC4AD) to form nanoparticles for further fluorescence enhancement as the second stage. Furthermore, based on a co‐staining experiment with LysoTracker Blue, such nanoparticles can be applied in NIR lysosome‐targeted cell imaging.
Supramolecular assemblies were designed with initially weak 625 nm near‐IR emission that was enhanced and shifted to 655 nm in two stages by cucurbit8uril (CB8) and amphiphilic calixarene SC4AD. This system was used for lysosome‐targeted cell imaging.
Developing safe and precise image‐guided photodynamic therapy is a challenge. In this study, the hypoxic properties of solid tumors are exploited to construct a hypoxia‐responsive photosensitizer, ...TPA‐Azo. Introducing the azo group into the photosensitizer TPA‐BN with aggregation‐induced emission quenches its fluorescence. When the nonfluorescent TPA‐Azo enters hypoxic tumors, it is reduced by the overexpressed azoreductase to generate a fluorescent photosensitizer TPA‐BN with an amino group that exhibits fluorescence‐activatable image‐guided photodynamic therapy with dual‐organelle (lipid droplets and lysosomes) targeting. This design strategy provides a basis for the development of fluorescence‐activatable photosensitizers.
When the nonfluorescent hypoxia‐responsive photosensitizer TPA‐Azo enters hypoxic tumors, it is reduced by the overexpressed azoreductase to generate the fluorescent photosensitizer TPA‐BN with the aggregation‐induced emission property, which can realize the fluorescence‐activatable image‐guided photodynamic therapy with dual‐organelle (lipid droplets and lysosomes) targeting.
Abstract
Dissipative self-assembly, which requires a continuous supply of fuel to maintain the assembled states far from equilibrium, is the foundation of biological systems. Among a variety of ...fuels, light, the original fuel of natural dissipative self-assembly, is fundamentally important but remains a challenge to introduce into artificial dissipative self-assemblies. Here, we report an artificial dissipative self-assembly system that is constructed from light-induced amphiphiles. Such dissipative supramolecular assembly is easily performed using protonated sulfonato-merocyanine and chitosan based molecular and macromolecular components in water. Light irradiation induces the assembly of supramolecular nanoparticles, which spontaneously disassemble in the dark due to thermal back relaxation of the molecular switch. Owing to the presence of light-induced amphiphiles and the thermal dissociation mechanism, the lifetimes of these transient supramolecular nanoparticles are highly sensitive to temperature and light power and range from several minutes to hours. By incorporating various fluorophores into transient supramolecular nanoparticles, the processes of aggregation-induced emission and aggregation-caused quenching, along with periodic variations in fluorescent color over time, have been demonstrated. Transient supramolecular assemblies, which act as fluorescence modulators, can also function in human hepatocellular cancer cells.
Twisted toroidal ribbons such as the one-sided Möbius strip have inspired scientists, engineers and artists for many centuries. A physical Möbius strip exhibits interesting mechanical properties ...deriving from a tendency to redistribute the torsional strain away from the twist region. This leads to the interesting possibility of building topological actuators with continuous deformations. Here we report on a series of corresponding bi-layered stripe actuators using a photothermally responsive liquid crystal elastomer as the fundamental polymeric material. Employing a special procedure, even Möbius strips with an odd number of twists can be fabricated exhibiting a seamless homeotropic and homogeneous morphology. Imposing a suitable contraction gradient under near-infrared light irradiation, these ribbons can realize continuous anticlockwise/clockwise in-situ rotation. Our work could pave the way for developing actuators and shape morphing materials that need not rely on switching between distinct states.
The development of controllable artificial light‐harvesting systems based on liquid crystal (LC) materials, i.e., anisotropic fluids, remains a challenge. Herein, an annulene‐based discotic LC ...compound 6 with a saddle‐shaped cyclooctatetrathiophene core has been synthesized to construct a tunable light‐harvesting platform. The LC material shows a typical aggregation‐induced emission, which can act as a suitable light‐harvesting donor. By loading Nile red (NiR) as an acceptor, an artificial light‐harvesting system is achieved. Relying on the thermal‐responsive self‐assembling ability of 6 with variable molecular order, the efficiency of such 6‐NiR system can be controlled by temperature. This light‐harvesting system works sensitively at a high donor/acceptor ratio as 1000 : 1, and exhibits a high antenna effect (39.1) at a 100 : 1 donor/acceptor ratio. This thermochromic artificial light‐harvesting LC system could find potential applications in smart devices employing soft materials.
An annulene‐based discotic liquid crystal (LC) material to construct a tunable light‐harvesting platform is developed. Relying on the thermal‐responsive self‐assembling ability of the LC molecule with variable molecular order, the efficiency of the light‐harvesting system can be controlled at different temperatures when Nile red is introduced as an acceptor. This system exhibits a high antenna effect (39.1) at a 100 : 1 donor/acceptor ratio.
Photoswitchable supramolecular self‐assemblies are promising candidates for intelligent recognition because of their noninvasive and spatial precision. However, the manipulation of the self‐assembly ...and disintegration of multicomponent mixtures with light of different wavelengths remain difficult. Here, an orthogonal three‐wavelength‐controlled two‐stage supramolecular self‐assembly consisting of two photoswitches, diarylethene, and protonated merocyanine is designed, mediated by supramolecular macrocyclic host. Owing to the reversible photo‐transformation of the switches, an optimized approach including three wavelengths irradiation and a thermal relaxation process is developed without mutual interference, realizing interconversion among four self‐assembled states. These self‐assemblies are photodeformable with reversibility, which can be operated in a cellular environment. Taking advantage of the photochromism in both absorption and fluorescence of these self‐assemblies in different behaviors, a visual pattern that can simultaneously display multiple hidden information under dual‐signal emission is created. This work signifies a promising strategy in improving the ability of information encryption and anti‐counterfeiting.
An orthogonal three‐wavelength‐controlled two‐stage supramolecular self‐assembly is developed, which shows photochromic properties of absorption and fluorescence in different behaviors. It allows to create a visual pattern capable of displaying multiple hidden information simultaneously in aqueous solution. This work signifies a promising strategy in improving the ability of information encryption and anti‐counterfeiting in living systems.
In recent years, although light‐driven soft actuators have attracted intense scientific attention and achieved remarkable progress, the design and construction of an intelligent robotic system with ...maneuverability, self‐adaptability, untethered control, and greater freedom of action, in particular the omnidirectional motion capability on a plane, remains challenging. Herein, four types of photo‐thermal fillers and an unprecedented twist‐bend actuation mode is introduced into a liquid crystal elastomer‐based soft robot. The obtained twist‐bend crawling robot not only exhibits in situ rotation, four‐way turning, and four‐way linear motion under light irradiation with four wavelength bands (520, 655, 808, and 980 nm), but also demonstrates the ability to avoid obstacles in complex geographical environments. This work may bring a new perspective for fabrication and development of soft robots that can adapt to dynamic and complex environmental conditions.
A light‐fuelled omnidirectional crawling soft robot is constructed by introducing twist‐bend motion mode. Four less‐interfered photo‐thermal fillers are employed to realize visible/IR wavelength‐selective controllability of the robot. Such twist‐bend crawling robot exhibits in situ rotation, four‐way turning, and four‐way straight moving, and even proves to have the ability to avoid obstacles in complex geographical environments.
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