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Significant progress in fabricating new multifunctional soft materials and the advances of additive manufacturing technologies have given birth to a new generation of soft robots with complex capabilities, such as crawling, swimming, jumping, gripping, and releasing. Within this vast array of responsive soft materials, hydrogels receive considerable attention due to their fascinating properties, including biodegradable, self-healing, stimuli-responsive, and large volume transformation. Konjac glucomannan (KGM) is an edible polysaccharide that forms a pH-responsive, self-healing hydrogel when crosslinked with borax, and it is the focus of this study. A novel KGM-Borax ink for three-dimensional (3D) printing of free-form structures and soft robots at room temperature is presented. A complete process from ink preparation to the fabrication of a completely cross-linked part is demonstrated. Print setting parameters, rheological properties of the ink and crosslinked gels were characterized. Print quality was found to be consistent across a wide range of print settings. The minimum line width achieved is 650 μm. Tensile testing was carried out to validate the self-healing capability of the KGM-Borax gel. Results show that KGM-Borax has a high self-healing efficiency of 98%. Self-healing underwater was also demonstrated, a rarity for crosslinked gels. The means to form complex structures via 3D printing, reacting to environmental stimuli and the resilience against damage, make this new KGM-Borax gel a promising candidate for the fabrication of the next generation of soft robots.

This article reviews recent progress in the use of stimuli-responsive polymers for soft robotics. First, we introduce different types of representative stimuli-responsive polymers, which include liquid crystal polymers and elastomers, hydrogels, shape memory polymers, magnetic elastomers, electroactive polymers, and thermal expansion actuators. We focus on the mechanisms of actuation and the evaluation of performance and discuss strategies for improvements. We then present examples of soft robotic applications based on stimuli-responsive polymers for bending, grasping, walking, swimming, flying, and sensing control. Finally, we discuss current opportunities and challenges of stimuli-responsive soft robots for future study.

Atherosclerosis (AS), mainly caused by the changed immune system functions and inflammation, is the central pathogenesis of cardiovascular disease, which is a leading cause of death in the world. In modern medicine, the development of carriers precisely delivering the therapeutic agents to the target sites is the primary goal, which could minimize the potential adverse effects and be more effective in treating lesions. Due to the precise location, real-time monitoring, AS microenvironment response, and low toxicity, stimuli-responsive nano-based drug delivery systems (NDDSs) have been a promising approach in AS treatments. Herein, we will systematically summarize the recent advances in stimuli-responsive NDDSs for AS treatment, including internal stimuli (reactive oxygen species, enzyme, shear stress, and pH) and external stimuli (light, ultrasound, and magnetism) responsive NDDSs. Besides, we will also summarize in detail the classification of stimuli-responsive NDDSs for AS, such as organic NDDSs (e.g., lipid-based and polymer-based nanomaterials), inorganic NDDSs (e.g., metal-based nanoparticles and nonmetallic nanomaterials), and composite multifunctional NDDSs. Finally, the critical challenges and prospects of this field will also be proposed and discussed.

Programmable materials have artificially designed physical shapes responding to external stimuli, as well as high design capability and high flexibility. Here, we propose a microfiber-shaped programmable material with an axial pattern of stimuli-responsive (SR) and nonresponsive hydrogels. The SR pre-gel solution was mixed to sodium alginate pre-gel solution for instantaneous gelation with ionic crosslinking and solidified on a nonresponsive hydrogel microfiber with a valve-controlled microfluidic system. A design of microfiber-shaped programmable material (patterned position of SR regions) could be flexibly altered by changing a coded sequence program. We confirmed that the three-dimensional (3D) coil-like structures were self-folded at the patterned SR regions responding to the thermal stimulus and that the chirality of the self-folded 3D coil-like structures depends on the condition of the stimulus to the microfiber. Finally, interaction with objects using the programmable microfiber as a soft actuator was demonstrated. Our microfiber-shaped programmable materials expand possibilities of fiber-based materials in biomimetics and soft robotics fields.

Biomedical luminescence imaging in the near-infrared (NIR, 700-1700 nm) region has shown great potential in visualizing biological processes and pathological conditions at cellular and animal levels, owing to the reduced tissue absorption and scattering compared to light in the visible (400-700 nm) region. To overcome the background interference and signal attenuation during intensity-based luminescence imaging, lifetime imaging has demonstrated a reliable imaging modality complementary to intensity measurement. Several selective or environment-responsive probes have been successfully developed for luminescence lifetime imaging and multiplex detection. This review summarizes recent advances in the application of luminescence lifetime imaging at cellular and animal levels in NIR-I and NIR-II regions. Finally, the challenges and further directions of luminescence lifetime imaging are also discussed.

Designing stimuli-responsive therapeutic scaffolds to deliver hydrophobic chemo drugs with controlled and sustained release at the tumour site would be promising in cancer treatment. In a quest for the stimuli-responsive drug delivery system with sustained release, herein we have fabricated active pharmaceutical ingredient based ionic liquid (IL) based hydrogel with self-healable and injectable properties. The ionic hydrogel makes a localized, long-term co-delivery system with self-healable, injectable, and stimuli-responsiveness. Further, the smart hybrid ionic hydrogel was constructed through encapsulating doxorubicin (DOX) within the 3D matrix of the ionic hydrogel, which responds to an intracellular biological stimulus (e.g., pH and temperature) and releases the DOX in 57 h. Experimental results of IL-IL, IL-DOX interactions are supported through Density Functional Theory (DFT) calculations. In vitro cellular studies revealed that DOX loaded hybrid ionic hydrogel shows a synergistic anticancer effect against MCF-07 cells. These results demonstrate the ability of the ionic hydrogel as a promising candidate for local cancer therapeutics.

Responsive emulsions are the emulsions that can be reversibly switched on-demand between “stable” and “unstable” by environmental stimulus or trigger, which allows a simple and effective adjustment approach to achieve emulsification and demulsification. In recent years, stimuli-responsive emulsions acting as smart soft material are received considerable attention with the advantages of simple manipulation, good reversibility, low cost, easy treatment, and little effect on the system. In this paper, the recent research progress of emulsions that can respond to external stimuli, including pH, light, magnetic field, CO2/N2 and dual responsive are reviewed. Also, the potential applications based on responsive emulsion are discussed, such as catalytic reactions, heavy oil recovery, polymer particles synthesis and optical sensor, aiming to summarize the latest achievements and put forward the possible development trends of responsive emulsions.

The hybridization of mechanically responsive molecular crystals with polymers has proven to be an efficient approach to fabricate smart hybrid materials that can produce multiple motions upon exter...

Reversible tricolored mechanochromism and recyclable mechanoluminescence properties (new shoots) of a reported tetraphenylethene derivative (old roots) were explored.

Background: Metal-organic frameworks (MOFs), as attractive hybrid crystalline porous materials, are being increasingly investigated in biomedical applications owing to their exceptional properties, including high porosity, ultrahigh surface areas, tailorable composition and structure, and tunability and surface functionality. Of interest, in this review, is the design and development of MOF-based drug delivery systems (DDSs) that have excellent biocompatibility, good stability under physiological conditions, high drug loading capacity, and controlled/targeted drug release. Objective: This review highlights the latest advances in MOFs as anticancer drug delivery systems (DDSs) along with insights on their design, fabrication, and performance under different stimuli that are either internal or external. The synthesis methods of MOFs, along with their advantages and disadvantages, are briefly discussed. The emergence of multifunctional MOF-based theranostic platforms is also discussed. Finally, the future challenges facing the developments of MOFs in the field of drug delivery are discussed. Methods: The review was prepared by carrying out a comprehensive literature survey using relevant work published in various scientific databases. Results: Novel MOFs in biomedical applications, especially in drug delivery, have shown great potential. MOF-based DDSs can be classified into normal (non-controllable) DDSs, stimuli-responsive DDSs, and theranostic platforms. The normal DDSs are pristine MOFs loaded with therapeutic agents and offer little to no control over drug release. Stimuli-responsive DDSs offer better spatiotemporal control over drug release by responding to either endogenous (pH, redox, ions, ATP) or exogenous stimuli (light, magnetism, US, pressure, temperature). The theranostic platforms combine stimuli-responsive drug delivery with diagnostic imaging functionality, paving the road for imaging-guided drug delivery. Conclusion: This review presented a summary of the various methods utilized in MOF's synthesis along with the advantages and disadvantages of each method. Furthermore, the review highlighted and discussed the latest developments in the field of MOF-based DDSs and theranostic platforms. The review is focused on the characteristics of MOF-based DDSs, the encapsulation of different anticancer drugs as well as their stimuli-responsive release.

Natural bioactive ingredients have lower bioavailability because of their chemical instability and poor water solubility, which limits their applications in functional foods. Among diverse biopolymers that can be used to construct delivery systems of bioactives, chitosan has attracted extensive attention due to its unique cationic nature, excellent mucoadhesive properties and easy modification. In this review, chitosan and its composites-based food-grade delivery systems as well as the factors affecting their performance are summarized. Modification, crosslinking, combination with other biopolymer or utilization of coating material can effectively overcome the instability of pure chitosan-based carriers under acidic conditions, thereby constructing chitosan and its complex-based carriers with conspicuously improved performance. Furthermore, the applications of chitosan-based delivery systems in nutrition and health as well as their future development trends and challenges are discussed. Functional food ingredients, functional food packaging and biological health are potential applications of chitosan-based food-grade delivery systems. The research trends of nutraceutical delivery systems based on chitosan and its composites include co-delivery of nutrients and essential oils, targeted intestinal delivery, stimulus responsive/sustained release and their applications in real foods. In conclusion, food industry will be significantly promoted with the continuous innovation and development of chitosan-based nutraceutical delivery systems.

A judicious strategy was utilized to envision the substantial regio-positional effects of substituents on the photophysical properties of the 2H-chromen-2-one-3-benzothiazole scaffold-based push-pull framework, named 6-X-CUMs. Among them, 6-NEt2-CUM reveals prominent excited-state intramolecular charge transfer with a large change of dipole moment (Δμ ∼ 18.23 D), hence displaying remarkable emission solvatochromism from the green (536 nm in cyclohexane) to far-red region (714 nm in dimethyl sulfoxide) and a high-temperature sensitivity (-0.23 nm °C-1). These, together with unique basicity and acido-/vaporchromism upon acidification elucidated by NMR and photospectroscopic studies, show stark contrast to the conventional 7-NEt2-CUM. The new series of these tailored 6-X-CUMs represents a new dimension in tailoring the photophysical properties for the development of a promising class of multistimuli-responsive materials.

Although patients benefit from surgical transurethral resection of bladder cancers, some niduses are missed or incompletely resected, and small malignant lesions may recur. Intravesical chemotherapy and immunotherapy are universally accepted as adjuvant treatments after surgery to avoid recurrence and progression. However, these treatments still have limitations, including an insufficient retention period, inefficient permeability of chemotherapeutic agents, and dilution of the agents by urine. Nanostructure-based smart therapeutic platforms can be tailored to be responsive to internal or external stimuli to ameliorate this situation. This unparalleled capability empowers the precise aggregation of stimulus-responsive nanocarriers in the target regions, namely, the tumors, and subsequent release of the anticancer materials. This review summarizes the current nanostructure-based therapeutic platforms, especially stimulus-responsive nanocarriers, and highlights their benefits and limitations in bladder cancer therapy. Novel innovations in nanotechnology have undoubtedly arrived at a new height and have become useful for practical applications. Nanotechnology will positively promote the development of anticancer agents not only for bladder cancer but also for other solid tumors.

Circularly polarized luminescence (CPL) materials have potential applications in 3D optical displays, information security encryption, sensors, and photoelectric devices because of their inherent a...

Nanotechnology has been widely applied to the fabrication of drug delivery systems in the past decades. Recently, with the progress made in microfabrication approaches, nanorobots are steadily becoming a promising means for tumor-targeting drug delivery. In general, nanorobots can be divided into two categories: nanomotors and stimuli-responsive nanorobots. Nanomotors are nanoscale systems with the ability to convert surrounding energies into mechanical motion, whereas stimuli-responsive nanorobots are featured with activatable capacity in response to various endogenous and exogenous stimulations. In this minireview, the dynamic control of nanomotors and the rational design of stimuli-responsive nanorobots are overviewed, with particular emphasis on their contribution to tumor-targeting therapy. Moreover, challenges and perspectives associated with the future development of nanorobots are presented.

Biomimetic membrane materials have been widely explored and developed for drug loading and tissue engineering applications due to their excellent biocompatibility and abundant reaction sites. However, novel cytomembrane mimics have been lacking for a long time. In this study, black phosphorus (BP) was used as the foundation for a new generation of promising cytomembrane mimics due to its multiple similarities to cytomembranes. Inspired by the dual function of endotoxins on membranes, we prepared a BP-based cytomembrane mimic with controllable antibacterial ability via electrostatic interaction between BP and [1-pentyl-1-quaternary ammonium-3-vinyl-imidazole]Br ([PQVI]Br). The release of PQVI could be manipulated in different conditions by adjusting the electrostatic force, thereby achieving controllable antibacterial ability. This report confirms the possibility of using BP as a new material to mimic cytomembranes and provides a new concept of controllable antibacterial action based on endotoxins.

Combination therapy has been designed to overcome the setbacks of traditional chemotherapy in anticancer therapy. Since combination therapy comprises a combination of anticancer agents, the differe...

Summary Halide perovskites have recently shown potential as stimuli-responsive materials (SRMs) for a range of important technologies such as smart windows, memory devices, data storage, and sensors. Here, we overview these emerging SRMs that are based on halide perovskite systems of switchable optical and electrical properties as well as discuss their switching characteristics and practical applications. We summarize the reversible chemical and structural transformations of these materials and categorize them by their switching mechanisms. Furthermore, to guide the community’s search for new designs of stimuli-responsive halide perovskites, we outline several important criteria for effective switchable materials. Finally, we provide our perspective on the current challenges and future developments of these emerging materials.

The objective of the present work was to develop stimuli-responsive PEGylated nanoparticles system comprising of xanthine oxidase, Bleomycin and diallyl trisulfide in order to promote their signifi...

With the emergence of multidrug resistance (MDR) in many pathogens, bacterial infections are becoming a growing threat to public health. The frightening scenario is due largely to the formation of biofilms, in which the bacteria are extremely recalcitrant to the conventional antibiotic regimens. To address the emergence of MDR and biofilm-associated infections, numerous polymer-based materials have been designed and prepared recently. The subject of this perspective is the recent development of polymer-based materials that have been applied to combat multidrug-resistant pathogens, to prevent the formation of biofilms, or enhance the eradication efficacy to mature biofilms via killing biofilm-bacteria or dispersing biofilms. The advantages and shortcomings of these polymer-based materials are discussed, as well as the challenges we are facing in the clinical translation of these systems.

Donor-acceptor Stenhouse adducts (DASAs) are a photo-switch class that undergoes triene cyclisation in response to visible light. Herein, electrochemical oxidation is demonstrated as an effective alternative stimulus for the triene cyclisation commonly associated with photo-switching.

Stimuli-responsive fibers are highly desirable for their potential applications in areas such as anti-counterfeiting, optical memory systems, colorimetric sensing, and bioimaging sensors. An iridescent luminescent fibers that can achieve multi-color with long afterglow and photochromic properties is always required in color-on-demand applications. Here, a set of distinct three-primary colors luminescent fibers based on red-green-blue (RGB) system. Y2O2S:Eu3+, Mg2+, Ti4+ (red), SrAl2O4:Eu2+, Dy3+ (green), Sr2MgSi2O7: Eu2+, Dy3+ (blue) are successfully synthesized. Spiropyran and as-prepared luminescent materials are introduced into PAN fibers by a one-step extrusion wet-spinning process to achieve distinct three-primary colors luminescent photochromic fiber. These as-prepared fibers emit bright lights under excitation of ultraviolet with long afterglow. These fibers exhibit outstanding tensile properties which allow knitting or weaving them into demonstrated functional designs for aesthetic designs and encryption/decryption protocols. Comparing with previous studied stimuli-responsive fibers, our research focus on distinct three-primary colors luminescent photochromic fibers present enormous potential in 3D printing, information encryption, and next generation smart fibers.

Microneedle (MN) patches consisting of miniature needles have emerged as a promising tool to perforate the stratum corneum and translocate biomolecules into the dermis in a minimally invasive manner. Stimuli-responsive MN patches represent emerging drug delivery systems that release cargos on-demand as a response to internal or external triggers. In this review, a variety of stimuli-responsive MN patches for controlled drug release are introduced, covering the mechanisms of action toward different indications. Future opportunities and challenges with respect to clinical translation are also discussed.

Electromerism is a very well-known phenomenon in transition metal chemistry. In main group chemistry, this concept has only started getting attention recently. We report stimuli responsive low-valent silicon compounds exhibiting electromerism. A mixed-valent silaiminyl-silylene 1, [LSi−Si(NDipp)L] (L=PhC(N$^t$Bu)$_2$), was synthesized in a single step from amidinate-chlorosilylene. Compound 1 has two interconnected Si atoms in formally +I and +III oxidation states. Upon treatment with Lewis acidic Cu$^I$X (X=mesityl, Cl, Br, I), electron redistribution occurs resulting in the formation of [{LSi(NDipp)Si(L)}−CuX], in which both silicon atoms are in the +II formal oxidation state. Removal of the copper center from [{LSi(NDipp)Si(L)}−CuX] by using a Lewis basic carbene led to reformation of the precursor [LSi−Si(NDipp)L]. Thus, the process is fully reversible. This showcases the first example of Lewis acid/base-induced reversible electromerism in silicon chemistry.

A pyridyl side arm porphyrin incorporating C[Formula: see text] alkyl chains at the periphery of the porphyrin suitable for surface immobilisation on HOPG has been synthesised and tested for two state switching in solution. Temperature switching, involving reversible complexation of a covalently appended pyridyl side arm to the Zn(II) porphyrin, was comprehensively characterised by using variable temperature 1H NMR (-30 to +100[Formula: see text]C) and UV-vis (10 to 90[Formula: see text]C) in toluene. Molecular modelling assisted in understanding strain within the complex.

Supramolecular self-assemblies and co-assemblies possess multiple noncovalent interactions, highly ordered structures, and multifunctional properties. Yet, the fundamental understanding of their "structure-property relationship" remains very challenging. Herein, two kinetically controlled supramolecular charge transfer (CT) complexes were conceptualized from a trimorphic molecular donor denoted as "twisted aromatic hydrocarbon" (TAH), with p-fluoranil (TFQ) and p-chloranil (TCQ) in water, organic solvent, and solvent-free methods. Elucidating their co-assembling mechanism revealed that segmentation of the TAH with molecules having planar deficient cores spontaneously formed a distinct "H-type mixed stack" and "J-type segregated stack", regulated by blue/red-shifted charge-transfer and π-π stacking including weak C-H···F and C-H···O noncovalent interactions. By utilizing the structural transformational ability of the self-assembled TAH, the mechanistic aspects for the rapid nanoscopic co-assembly formation were precisely demonstrated experimentally and theoretically. The trimorphs and co-crystals of TAH could be disassembled resulting in turn-on emission by applying various external stimuli and being repeatedly reconfigured, thus providing a unique structure-property relationship and new TAH-based materials. This unique concept offers color-specific polymorphism and CT-complex formation strategy involving a simple class of functional materials having cooperative network forming ability using the twisted molecular donor.

Electrospun nanofibrous membranes offer superior properties over other polymeric membranes not only due to their high membrane porosity but also due to their high surface-to-volume ratio. A plethor...

Liquid crystalline epoxy networks (LCENs) are a class of materials that combine the useful benefits of both liquid crystals and epoxy networks exhibiting fascinating thermal, mechanical, and stimuli-responsive properties. They have emerged as a new platform for developing functional materials suitable for various applications, such as sensors, actuators, smart coatings and adhesives, tunable optical systems, and soft robotics. This article provides an overview of LCENs and their composites as functional materials, including their synthesis and characterisation, focusing on structure-processing–property relationships. We provide objective analyses on how materials engineers can use these relationships to develop LCENs with desired functionalities for targeted applications. Emerging areas, including advanced manufacturing and multi-functional design of LCENs are covered to show the overall progress in this field. We also survey the forward-looking status of LCEN research in designing novel materials for future technologies.

The widespread occurrence of infections from multidrug-resistant (MDR) bacteria is a global health problem. It has been amplified over the past few years due to the increase in adaptive traits in bacteria and lack of advanced treatment strategies. Because of the low bioavailability and limited penetration at infected sites, the existing antibiotics often fail to resist bacterial growth. Recently, developed stimuli-responsive drug delivery systems and combinatorial therapeutic systems based on nanoparticles, metal-organic frameworks, hydrogels, and organic chromophores offer the ability to improve the therapeutic efficacy of antibiotics by reducing drug resistance and other side effects. These therapeutic systems have been designed with the relevant chemical and physical properties that respond to specific triggers resulting in spatiotemporal controlled release and site-specific transportability. This review highlights the latest development of single and dual/multistimuli-responsive antibiotic delivery systems for combination therapies to treat MDR bacterial infections and biofilm eradication.

Stimuli-responsive polymer gels have recently attracted great attention due to their heat/solvent resistance, dimensional stability, and unique sensitivity to external stimuli. In this work, we synthesized thiol-functionalized tetraphenylethylene (TPE) and constructed polymer gels through thiol-ene click reaction. The synthetic process of the polymer gels could be monitored by fluorescence emission of TPE moieties based on aggregation-induced emission mechanism. In addition, due to the dual redoxand acid responsiveness of the polymer gels, in the presence of dithiothreitol and trifluoroacetic acid, fluorescence quenching of the polymer gels can be observed. This stimuli-responsive characteristics endows the polymer gels with potential applications in fluorescent sensing and imaging, cancer diagnosis and selfhealing materials.

Stimuli-responsive nanocarriers are gaining much attention due to their versatile multifunctional activities, including disease diagnosis and treatment. Recently, clinical applications of nano-drug delivery systems for cancer treatment pose a challenge due to their limited cellular uptake, low bioavailability, poor targetability, stability issues, and unfavourable pharmacokinetics. To overcome these issues, researchers are focussing on stimuli-responsive systems. Nanocarriers elicit their role through endogenous (pH, temperature, enzyme, and redox) or exogenous (temperature, light, magnetic field, ultrasound) stimulus. These systems were designed to overcome the shortcomings such as non-specificity and toxicity associated with the conventional drug delivery systems. The pH variation between healthy cells and tumor microenvironment creates a platform for the generation of pH-sensitive nano delivery systems. Herein, we propose to present an overview of various internal and external stimuli-responsive behavior-based drug delivery systems. Herein, the present review will focus specifically on the significance of various pH-responsive nanomaterials such as polymeric nanoparticles, nano micelles, inorganic-based pH-sensitive drug delivery carriers such as calcium phosphate nanoparticles, and carbon dots in cancer treatment. Moreover, this review elaborates the recent findings on pH-based stimuli-responsive drug delivery systems with special emphasis on our reported stimuli-responsive systems for cancer treatment.

Nano- and microgels are promising soft polymer materials for different application fields: stabilizers, sensors, catalysts, selective sorbents, drug delivery carriers etc. They are composed of cross-linked polymer chains swollen with a solvent. The building blocks, synthesis approaches and architecture of nano- and microgels are reviewed. The mechanisms of responsiveness to various stimuli are described, examples of applications are provided. Micro- and nanogels are good objects for learning projects and the ideas for learning projects with microgels are described.

A Cp*-Rh based D-shaped binuclear metallacycle and a template-free molecular Borromean ring (BR) were obtained in high yield using the semi-rigid thioether dipyridyl ligand 1,4-bis[(pyridin-4-ylthio)methyl]benzene (Bptmb). The topological transformation from a binuclear metallacycle and a BR to tetranuclear metallacycles was realized via the controlled oxidation of thioethers. The strategy used in this work can be regarded as a new form of stimuli-responsive post-synthesis modification (PSM).