Untethered Microgrippers for Precision Medicine.

Microgrippers, a branch of micro/nanorobots, refer to motile miniaturized machines that are of a size in the range of several to hundreds of micrometers. Compared with tethered grippers or other microscopic diagnostic and surgical equipment, untethered microgrippers play an indispensable role in biomedical applications because of their characteristics such as miniaturized size, dexterous shape tranformation, and  controllable motion, which enables the microgrippers to enter hard-to-reach regions to execute specific medical tasks for disease diagnosis and treatment. To date, numerous medical microgrippers are developed, and their potential in cell manipulation, targeted drug delivery, biopsy, and minimally invasive surgery  are explored. To achieve controlled locomotion and efficient target-oriented actions, the materials, size, microarchitecture, and morphology of microgrippers shall be deliberately designed. In this review, the authors summarizes the latest progress in untethered micrometer-scale grippers. The working mechanisms of shape-morphing and actuation methods for effective movement are first introduced. Then, the design principle and state-of-the-art fabrication techniques of microgrippers are discussed. Finally, their applications in the precise medicine are highlighted, followed by offering future perspectives for the development of untethered medical microgrippers.

Ionic Covalent Organic Framework as a Dual Functional Sensor for Temperature and Humidity.

Visual sensing of humidity and temperature by solids plays an important role in the everyday life and in industrial processes. Due to their hydrophobic nature, most covalent organic framework (COF) sensors often exhibit poor optical response when exposed to moisture. To overcome this challenge, the optical response is set out to improve, to moisture by incorporating H-bonding ionic functionalities into the COF network. A highly sensitive COF, consisting of guanidinium and diformylpyridine linkers (TG-DFP), capable of detecting changes in temperature and moisture content is fabricated. The hydrophilic nature of the framework enables enhanced water uptake, allowing the trapped water molecules to form a large number of hydrogen bonds. Despite the presence of non-emissive building blocks, the H-bonds restrict internal bond rotation within the COF, leading to reversible fluorescence and solid-state optical hydrochromism in response to relative humidity and temperature.

Surficial Host-Guest Responsive CsPbBr3 Perovskite Nanocrystals for Programmable Multi-Level Information Encryption.

The design of smart stimuli-responsive photoluminescent materials capable of multi-level encryption and complex information storage is highly sought after in the current information era. Here, a novel adamantyl-capped CsPbBr3 (AD-CsPbBr3) perovskite NCs, along with its supramolecular host-guest assembly partner a modified ß-CD (mCD), mCD@AD-CsPbBr3, are designed and prepared. By dispersing these two materials in different solvents, namely, AD-CsPbBr3 in toluene, mCD@AD-CsPbBr3 in toluene, and mCD@AD-CsPbBr3 in methanol, the three solutions exhibit diverse photoluminescence (PL) turn-on/off or PL discoloration response upon supramolecular stimulus. Based on these responses, a proof-of-principle programmable Multi-Level Photoluminescence Encoding System (MPLES) is established. Three types of four-level and three types of three-level information encoding are achieved by the system. A layer-by-layer four-level information encryption and decryption as well as a two-level encrypted 3D code are successfully achieved.

Heterocyclic Hemipiperazines: Multistimuli-responsive Switches and Sensors for Zinc or Cadmium Ions.

Advance in the design of molecular photoswitches - adapters that convert light into changes at molecular level - opens up exciting possibilities in preparing smart polymers, drugs photoactivated inside humans, or light-fueled nanomachines that might in the future operate in our bloodstream.  Hemipiperazines are recently reported biocompatible molecular photoswitches based on cyclic dipeptides. Here we report a multistimuli-responsive hemipiperazine-based switch that reacts on light, solvents, acidity, or metal ions. Its photoequilibration is controlled by the intramolecular hydrogen bonding pattern. The compound can be used as a mid-nanomolar photoswitchable fluorescent sensor for zinc and cadmium ions, applicable to monitor environmental pollution in real time.

Aggregation/Crystallization-Induced Emission in Naphthyridine-Based Carbazolyl-Modified Donor-Acceptor Boron Dyes Tunable by Fluorine Atoms.

Four donor-acceptor boron difluoride complexes based on the carbazole electron donor and the [1,3,5,2]oxadiazaborinino[3,4-a][1,8]naphthyridine acceptor were designed, synthesized, and systematically spectroscopically investigated in solutions, in dye-doped polymer films, and in the solid states. The dyes exhibit an intense blue to red solid-state emission with photoluminescence quantum yields of up to 59 % in pure dye samples and 86 % in poly(methyl methacrylate) films. All boron complexes show aggregation-induced emission and reversible mechanofluorochromism. The optical properties of these dyes and their solid state luminescence can be tuned by substitution pattern, i. e., the substituents at the naphthyridine unit. Exchange of CH3- for CF3-groups does not only increase the intramolecular charge transfer character, but also provides a crystallization-induced emission enhancement.

Microfluidic Approaches for Microactuators: From Fabrication, Actuation, to Functionalization.

Microactuators can autonomously convert external energy into specific mechanical motions. With the feature sizes varying from the micrometer to millimeter scale, microactuators offer many operation and control possibilities for miniaturized devices. In recent years, advanced microfluidic techniques have revolutionized the fabrication, actuation, and functionalization of microactuators. Microfluidics can not only facilitate fabrication with continuously changing materials but also deliver various signals to stimulate the microactuators as desired, and consequently improve microfluidic chips with multiple functions. Herein, this cross-field that systematically correlates microactuator properties and microfluidic functions is comprehensively reviewed. The fabrication strategies are classified into two types according to the flow state of the microfluids: stop-flow and continuous-flow prototyping. The working mechanism of microactuators in microfluidic chips is discussed in detail. Finally, the applications of microactuator-enriched functional chips, which include tunable imaging devices, micromanipulation tools, micromotors, and microsensors, are summarized. The existing challenges and future perspectives are also discussed. It is believed that with the rapid progress of this cutting-edge field, intelligent microsystems may realize high-throughput manipulation, characterization, and analysis of tiny objects and find broad applications in various fields, such as tissue engineering, micro/nanorobotics, and analytical devices.

Morphology-Dependent Aggregation-Induced Emission of Janus Emulsion Surfactants.

We report a novel stimuli-responsive fluorescent material platform that relies on an evocation of aggregation-induced emission (AIE) from tetraphenylethylene (TPE)-based surfactants localized at one hemisphere of biphasic micro-scale Janus emulsion droplets. Dynamic alterations in the available interfacial area were evoked through surfactant-induced dynamic changes of the internal droplet morphology that can be modulated as a function of the balance of interfacial tensions of the droplet constituent phases. Thus, by analogy with a Langmuir-Blodgett trough that enables selective concentration of surfactants at a liquid-gas interface, we demonstrate here a method for controllable modulation of the available interfacial area of surfactant-functionalized liquid-liquid interfaces. We show that a morphology-dependent alteration of the interfacial area can be used to evoke an optical signal, by selectively assembling synthesized TPE-based surfactants on the respective droplet interfaces. A trigger-induced increase in the concentration of TPE-based surfactants at the liquid-liquid interfaces results in an evocation of aggregation-induced emission (AIE), inducing an up to 3.9-fold increase in the measured emission intensity of the droplets.

Stimuli Responsive Features of Organic RTP Materials: An Intriguing Carbazole-Cyclic Triimidazole Derivative.

Stimuli responsive luminescent materials possessing room temperature phosphorescence (RTP) are extremely desirable for various applications. The here investigated derivative of cyclic triimidazole (TT) functionalized with carbazole (Cz), namely TT-Ph-Cz, belongs to this class. TT-Ph-Cz possesses high conformational freedom resulting in rigidochromic and multi-stimuli responsive emissive behavior. It has been isolated as MeOH-solvated and de-solvated forms characterized by distinctive emissive features. In particular, the solvated form, in which hydrogen bonds with MeOH inhibit competitive non-radiative deactivation channels, possesses a higher quantum yield associated with a strong phosphorescence contribution which is preserved in DMSO/water solutions.

Recent Advances in the Preparation of Delivery Systems for the Controlled Release of Scents.

Scents are volatile compounds highly employed in a wide range of manufactured items, such as fine perfumery, household products, and functional foods. One of the main directions of the research in this area aims to enhance the longevity of scents by designing efficient delivery systems to control the release rate of these volatile molecules and also increase their stability. Several approaches to release scents in a controlled manner have been developed in recent years. Thus, different controlled release systems have been prepared, including polymers, metal-organic frameworks and mechanically interlocked systems, among others. This review is focused on the preparation of different scaffolds to accomplish a slow release of scents, by pointing out examples reported in the last five years. In addition to discuss selected examples, a critical perspective on the state of the art of this research field is provided, comparing the different types of scent delivery systems.

Leveraging Crystalline and Amorphous States of a Metal-Organic Complex for Transformation of the Photosalient Effect and Positive-Negative Photochromism.

Uncovering differences between crystalline and amorphous states in molecular solids would both promote the understanding of their structure-property relationships, as well as inform development of multi-functional materials based on the same compound. Herein, for the first time, we report an approach to leverage crystalline and amorphous states of a zero-dimensional metal-organic complex, which exhibited negative and positive photochromism, due to the competitive chemical routes between photocycloaddition and photogenerated radicals. Furthermore, different polymorphs lead to the on/off toggling of photo-burst movement (photosalient effect), indicating the controllable light-mechanical conversion. Three demos were further constructed to support their application in information encryption and anti-counterfeiting. This work provides the proof-of-concept of a state- and polymorph-dependent photochemical route, paving an effective way for the design of new dynamically responsive systems.

Detachable Porous Organic Polymers Responsive to Light and Heat.

Stimuli-responsive porous materials have captured much attention due to the on-demand tunable properties. Most reported stimuli-responsive porous materials are based on molecule isomerism or host-guest interaction, and it is highly desired to develop new types based on different responsive mechanism. Herein, inspired by natural cells which have the ability to fuse and divide induced by external stimulation, we report a new type of stimuli-responsive porous material based on detachment mechanism. A detachable porous organic polymer, namely DT-POP-1, is fabricated from the polymerization of anthracene-containing monomer (AnMon) when irradiated by 365 nm UV light. DT-POP-1 can detach into the monomer AnMon when irradiated with 275 nm UV light or heat. Such polymerization/detachment is reversible. The detachment results in a big difference in porosity and adsorption capacity, making the present detachable porous polymer highly promising in adsorptive separation and drug delivery.

pH Switchable Water Dispersed Photocatalytic Nanoparticles.

Photogeneration of Reactive Oxygen Species (ROS) finds applications in fields as different as nanomedicine, art preservation, air and water depollution and surface decontamination. Here we present photocatalytic nanoparticles (NP) that are active only at acidic pH while they do not show relevant ROS photo-generation at neutral pH. This dual responsivity (to light and pH) is achieved by stabilizing the surface of TiO2 NP with a specific organic shell during the synthesis and it is peculiar of the achieved core shell-structure, as demonstrated by comparison with commercial photocatalytic TiO2 NP. For the investigation of the photocatalytic activity, we developed two methods that allow real time detection of the process preventing any kind of artifact arising from post-treatments and delayed analysis. The reversibility of the pH response was also demonstrated as well as the selective photo-killing of cancer cells at acidic pH.

Double Lock Label Based on Thermosensitive Polymer Hydrogels for Information Camouflage and Multilevel Encryption.

Developing extra safety encryption technologies to prevent information leakage and combat fakes is in high demand but is challenging. Herein, we propose a "double lock" strategy based on both lower critical solution temperature (LCST) and upper critical solution temperature (UCST) polymer hydrogels for information camouflage and multilevel encryption. Two types of hydrogels were synthesized by the method of random copolymerization. The number of -CO-NH2 groups in the network structure of the hydrogels changed the enthalpic or entropic thermo-responsive hydrogels, and ultimately precisely controlled their phase transition temperature. The crosslink density of the polymer hydrogels governs the diffusion kinetics, resulting in a difference in the time for their color change. The combination of multiple LCST and UCST hydrogels in one label realized information encryption and dynamic information identification in the dimensions of both time and temperature. This work is highly interesting for the fields of information encryption, anti-counterfeiting, and smart responsive materials.

Photo-Induced Polymer Cyclization via Supramolecular Confinement of Cyanostilbenes.

Efficient synthesis of cyclic polymers has received much attention in polymer chemistry field. Although photochemical cycloaddition of terminal π-bonded units provides a plausible way toward cyclic polymerization, it remains challenging to avoid side reactions by manipulating the reaction selectivity. Herein supramolecular confinement has been developed as a promising strategy to address this issue, by introducing highly directional hydrogen bonds to the photo-reactive cyanostilbenes. The cyanostilbenes units on both ends of a telechelic macromonomer are orientationally aligned with high local concentrations, yielding [2+2] photo-cycloaddition products upon 430 nm light irradiation. It leads to the formation of cyclic polymers in the self-assembled state, in stark contrast to Z-E isomerization of cyanostilbenes in the monomeric state. Overall, supramolecular confinement effect exemplified in the current study provides new avenues toward cyclic topological polymers with high synthetic efficiency.

Actuation of Liquid Crystalline Elastomers at or Below Ambient Temperature.

Liquid crystal elastomers (LCE) are an emerging class of material actuators. LCE undergo macroscopic dimensional changes when subjected to a stimulus. The large stimuli-response of LCE is associated with thermotropic disruption of order. Historically, comparatively high temperatures are required to disrupt orientation in LCE to achieve meaningful work output. Here, we introduce an approach to prepare LCE via thiol-Michael/thiol-ene reactions that actuate at or below ambient temperature. Alignment was imparted to the LCE by mechanical alignment and 3D printing. The LCE materials detailed here achieve strains of 40 % with a maximum deformation rate of 6.5 % °C-1 . The functional utility of the tunability of the thermotropic response of these materials is illustrated in reconfiguration triggered via body heat and sequential actuation of a multi-material element.

3D Hydrazone-Functionalized Covalent Organic Frameworks as pH-Triggered Rotary Switches.

The property expansion of 3D functionalized covalent organic frameworks (COFs) is important for developing their potential applications. Herein, the first case of 3D hydrazone-decorated COFs as pH-triggered molecular switches is reported, and their application in the stimuli-responsive drug delivery system is explored. These functionalized COFs with hydrazone groups on the channel walls are obtained via a multi-component bottom-up synthesis strategy. They exhibit a reversible E/Z isomerization at various pH values, confirmed by UV-vis absorption spectroscopy and proton conduction. Remarkably, after loading cytarabine (Ara-C) as a model drug molecule, these pH-responsive COFs show an excellent and intelligent sustained-release effect with an almost fourfold increase in the Ara-C release at pH = 4.8 than at pH = 7.4, which will effectively improve drug-targeting. Thus, these results open a way toward designing 3D stimuli-responsive functionalized COF materials and promote their potential application as drug carriers in the field of disease treatment.

Dye-Loaded Mechanochromic and pH-Responsive Elastomeric Opal Films.

In this work, the preparation and fabrication of elastomeric opal films revealing reversible mechanochromic and pH-responsive features are reported. The core-interlayer-shell (CIS) particles are synthesized via stepwise emulsion polymerization leading to hard core (polystyrene), crosslinked interlayer (poly(methyl methacrylate-co-allyl methacrylate), and soft poly(ethyl acrylate-co-butyl acrylate-co-(2-hydroxyethyl) methacrylate) shell particles featuring a size of 294.9 ± 14.8 nm. This particle architecture enables the application of the melt-shear organization technique leading to elastomeric opal films with orange, respectively, green brilliant reflection colors dependent on the angle of view. Moreover, the hydroxyl moieties as part of the particle shell are advantageously used for subsequent thermally induced crosslinking reactions enabling the preparation of reversibly tunable mechanochromic structural colors based on Bragg's law of diffraction. Additionally, the CIS particles can be loaded upon extrusion or chemically by a postfunctionalization strategy with organic dyes implying pH-responsive features. This convenient protocol for preparing multi-responsive, reversibly stretch-tunable opal films is expected to enable a new material family for anti-counterfeiting applications based on external triggers.

Triple-Responsive Polyampholytic Graft Copolymers as Smart Sensors with Varying Output.

Three triggers result in two measurable outputs from polymeric sensors: multiresponsive polyampholytic graft copolymers respond to pH-value and temperature, as well as the type and concentration of metal cations and therefore, allow the transformation of external triggers into simply measurable outputs (cloud point temperature (TCP ) and surface plasmon resonance (SPR) of encapsulated silver nanoparticles). The synthesis relies on poly(dehydroalanine) (PDha) as the reactive backbone and gives straightforward access to materials with tunable composition and output. In particular, a rather high sensitivity toward the presence of Cu2+ , Co2+ , and Pb2+ metal cations is found.

CO2 -Strengthened Double-Cross-Linked Polymer Gels from Frustrated Lewis Pair Networks.

Conventional thermosets consisting of polymer networks with robust and irreversible chemical linkages are incapable of reshaping or reprocessing once formed. In contrast, reversible non-covalent crosslinks can impart structurally flexible and reconfigurable feature to the networks, but at the expense of certain mechanical strength. The integration of fixed covalent bonds and noncovalent bonds into these materials can usually attain enhanced mechanical properties and meanwhile provide dynamic and adaptable functions, such as responsive and healing ability to external stimuli. Here a double-cross-linked frustrated Lewis pair network (FLPN) is developed through a specific three-component reaction among triarylborane, triarylphosphine, and CO2 , which is composed of permanent chemical crosslinks and dynamic CO2 gas-bridged connections. The amount of CO2 added can regulate the density of supramolecular node in such FLPN, so as to control the strength and toughness of the gel material. Moreover, the broken gel can be rapidly healed by CO2 stimulus through the reconstruction of dynamic covalent network. This study will inspire a new way to create gas-based smart materials by incorporating frustrated Lewis pair chemistry into traditional gel system.

High aspect ratio nanotubes assembled from macrocyclic iminium salts.

One-dimensional nanostructures such as carbon nanotubes and actin filaments rely on strong and directional interactions to stabilize their high aspect ratio shapes. This requirement has precluded making isolated, long, thin organic nanotubes by stacking molecular macrocycles, as their noncovalent stacking interactions are generally too weak. Here we report high aspect ratio (>103), lyotropic nanotubes of stacked, macrocyclic, iminium salts, which are formed by protonation of the corresponding imine-linked macrocycles. Iminium ion formation establishes cohesive interactions that, in organic solvent (tetrahydrofuran), are two orders of magnitude stronger than the neutral macrocycles, as explained by physical arguments and demonstrated by molecular dynamics simulations. Nanotube formation stabilizes the iminium ions, which otherwise rapidly hydrolyze, and is reversed and restored upon addition of bases and acids. Acids generated by irradiating a photoacid generator or sonicating chlorinated solvents also induced nanotube assembly, allowing these nanostructures to be coupled to diverse stimuli, and, once assembled, they can be fixed permanently by cross-linking their pendant alkenes. As large macrocyclic chromonic liquid crystals, these iminium salts are easily accessible through a modular design and provide a means to rationally synthesize structures that mimic the morphology and rheology of carbon nanotubes and biological tubules.