4D-printed shape-programmable [H+]-responsive needles for determination of urea.

Four-dimensional printing (4DP) technologies are revolutionizing the fabrication, functionality, and applicability of stimuli-responsive analytical devices. More practically, 4DP technologies are effective in fabricating devices with complex geometric designs and functions, and the degree of shape programming of 4D-printed stimuli-responsive devices can be optimized to become a reliable analytical strategy. Although shape-programming modes play a critical role in determining the analytical characteristics of 4D-printed stimuli-responsive sensing devices, the effect of shape-programming modes on the analytical performance of 4D-printed stimuli-responsive devices remains an unexplored subject. We employed digital light processing three-dimensional printing (3DP) with acrylate-based photocurable resins and 2-carboxyethyl acrylate (CEA)-incorporated photocurable resins for 4DP of the bending, helixing, and twisting needles. Upon immersion in samples with pH values above the pKa of CEA, the electrostatic repulsion among the dissociated carboxyl groups of polyCEA caused swelling of the CEA-incorporated part and [H+]-dependent shape programming. When coupling with the derivatization reaction of the urease-mediated hydrolysis of urea, the decline in [H+] induced shape programming of the needles, offering reliable determination of urea based on the shape-programming angles. After optimizing the experimental conditions, the helixing needles provided the best analytical performance, with the method's detection limit of 0.9 µM. The reliability of this analytical method was validated by determining urea in samples of human urine and sweat, fetal bovine serum, and rat plasma with spike analyses and comparing these results with those obtained from a commercial assay kit. Our demonstration and analytical results suggest the importance of optimizing the shape-programming modes to improve the analytical performance of 4D-printed stimuli-responsive shape-programming sensing devices and emphasize the benefits and applicability of 4DP technologies in advancing the development and fabrication of stimuli-responsive sensing devices for chemical sensing and quantitative chemical analyses.

Cell membrane camouflaged Cu-doped mesoporous polydopamine for combined CT/PTT/CDT synergistic treatment of breast cancer.

Currently, traditional monotherapy for cancer often results in indiscriminate attacks on the body, leading to the emergence of new health problems. To confront these challenges, multimodal combination therapy has become necessary. However, how to develop new smart nanomaterials through green synthesis methods, delivering drugs while simultaneously synergizing multimodal combination therapies for tumor treatment, remains a topic of great significance. In this study, a biomimetic composite nanomaterial (RM-Cu/P) composed of mesoporous polydopamine (MPDA) as the core and red blood cell membranes (RBCMs) as the shell was synthesized as a drug carrier to deliver doxorubicin (DOX) while achieving synergistic chemotherapy, photothermal and chemodynamic therapy (CT/PTT/CDT). Herein, the nanoparticles were extensively characterized to examine their morphological characteristics, elemental composition, and drug-carrying capacity. Notably, the coating of RBCM reduced the toxicity of the RM-Cu/P@DOX nanoparticles, improved their targeting ability and prolonged their circulation time in vivo. The Cu-doped nanoparticles were capable of initiating a Fenton-like reaction to generate reactive oxygen species (ROS) for CDT, while the photothermal conversion efficiency (η) reached 45.20 % under NIR laser irradiation. Subsequently, the particles were examined by in vivo and in vitro experimental studies in cytotoxicity, cellular uptake, ROS levels, lysosomal escape, and mouse tumor model to evaluate their potential application in antitumor. Compared with monotherapy, the RM-Cu/P@DOX nanoparticles had multiple-stimulation response properties under redox, pH, and NIR, which exhibited the advantage of combined trimodal therapy, resulting in remarkable synergistic antitumor efficacy. In conclusion, this innovative platform exhibited promising applications in smart drug delivery and synergistic treatment of cancer.

A Dynamic H-Bonding Network Enables Stimuli-Responsive Color-Tunable Chiral Afterglow Polymer for 4D Encryption.

The development of stimuli-responsive and color-tunable chiral organic afterglow materials has attracted great attention but remains a daunting challenge. Here, a simple yet effective strategy through the construction of a dynamic H-bonding network is proposed to explore the multi-color stimuli-responsive chiral afterglow by doping a self-designed chiral phosphorescent chromophore into a polyvinyl alcohol matrix. A stimuli-responsive deep blue chiral afterglow system with a lifetime of up to 3.35 s, quantum yield of 25.0%, and luminescent dissymmetry factor of up to 0.05 is achieved through reversible formation and breakdown of the H-bonding network upon thermal-heating and water-fumigating. Moreover, multi-color stimuli-responsive chiral afterglow can be obtained by chiral and afterglow energy transfer, allowing the establishment of afterglow information displays and high-level 4D encryption. This work not only offers a facile platform to develop advanced stimuli-responsive materials but also opens a new avenue for developing next-generation optical information technology with enhanced functionality and responsiveness.

Switching from Molecules to Functional Materials: Breakthroughs in Photochromism With MOFs.

Photochromic materials with properties that can be dynamically tailored as a function of external stimuli are a rapidly expanding field driven by applications in areas ranging from molecular computing, nanotechnology, or photopharmacology to programable heterogeneous catalysis. Challenges arise, however, when translating the rapid, solution-like response of stimuli-responsive moieties to solid-state materials due to the intermolecular interactions imposed through close molecular packing in bulk solids. As a result, the integration of photochromic compounds into synthetically programable porous matrices, such as metal-organic frameworks (MOFs), has come to the forefront as an emerging strategy for photochromic material development. This review highlights how the core principles of reticular chemistry (on the example of MOFs) play a critical role in the photochromic material performance, surpassing the limitations previously observed in solution or solid state. The symbiotic relationship between photoresponsive compounds and porous frameworks with a focus on how reticular synthesis creates avenues toward tailorable photoisomerization kinetics, directional energy and charge transfer, switchable gas sorption, and synergistic chromophore communication is discussed. This review not only focuses on the recent cutting-edge advancements in photochromic material development, but also highlights novel, vital-to-pursue pathways for multifaceted functional materials in the realms of energy, technology, and biomedicine.

Concentration-Switchable Assembly of Carbon Dots for Circularly Polarized Luminescent Amplification in Chiral Logic Gates and Deep-Red Light-Emitting Diodes.

Stimuli-responsive circularly polarized luminescent (CPL) materials are expected to find widespread application in advanced information technologies, such as 3D displays, multilevel encryption, and chiral optical devices. Here, using R-/S-α-phenylethylamine and 3,4,9,10-perylenetetracarboxylic dianhydride as precursors, chiral carbon dots (Ch-CDs) exhibiting bright concentration-dependent luminescence are synthesized, demonstrating reversible responses in both their morphologies and emission spectra. By adjusting Ch-CD concentration, the switchable wavelength is extended over 180 nm (539-720 nm), with the maximum quantum efficiency reaching 100%. Meanwhile, upon increasing Ch-CD concentration, the emission wavelength red-shifts, while the chirality of the assembled nanoribbons is synchronously amplified, ultimately achieving CPL at 709 nm and a maximum luminescence asymmetry factor of 2.18 × 10-2. These values represent the longest wavelength and the largest glum reported for CDs. Considering the remarkable optical properties of the synthesized Ch-CDs, multilevel chiral logic gates are designed, and their potential practical applications are demonstrated in multilevel anti-counterfeiting encryption, flexible electronic printing, and solid-state CPL. Furthermore, deep-red chiral electroluminescence light-emitting diodes (EL-LEDs) are prepared using these Ch-CDs, achieving an external quantum efficiency of 1.98%, which is the highest value reported to date for CDs in deep-red EL-LEDs, and the first report of chiral electronic devices based on CDs.

Advances in stimuli-responsive gold nanorods for drug-delivery and targeted therapy systems.

In recent years, the use of gold nanorods (AuNRs) has garnered considerable attention in biomedical applications due to their unique optical and physicochemical properties. They have been considered as potential tools for the advanced treatment of diseases by various stimuli such as magnetic fields, pH, temperature and light in the fields of targeted therapy, imaging and drug delivery. Their biocompatibility and tunable plasmonic properties make them a versatile platform for a range of biomedical applications. While endogenous stimuli have limited cargo delivery control at specific sites, exogenous stimuli are a more favored approach despite their circumscribed penetration depth for releasing the cargo at the specific target. Dual/multi-stimuli responsive AuNTs can be triggered by multiple stimuli for enhanced control and specificity in biomedical applications. This review provides to provide a summary of the biomedical applications of stimuli-responsive AuNRs, including their endogenous and exogenous properties, as well as their dual/multi-functionality and potential for clinical delivery. This review provides a comprehensive review on the improvement of therapeutic efficacy and the effective control of drug release with AuNRs, highlights AuNRs design strategies in recent years, discusses the advantages or challenges so far in the field of AuNRs. Finally, we have addressed the clinical translation bio-integrated nanoassemblies (CTBNs) in this field.

Recent advances and applications of stimuli-responsive nanomaterials for water treatment: A comprehensive review.

The development of stimuli-responsive nanomaterials holds immense promise for enhancing the efficiency and effectiveness of water treatment processes. These smart materials exhibit a remarkable ability to respond to specific external stimuli, such as light, pH, or magnetic fields, and trigger the controlled release of encapsulated pollutants. By precisely regulating the release kinetics, these nanomaterials can effectively target and eliminate contaminants without compromising the integrity of the water system. This review article provides a comprehensive overview of the advancements in light-activated and pH-sensitive nanomaterials for controlled pollutant release in water treatment. It delves into the fundamental principles underlying these materials' stimuli-responsive behaviour, exploring the design strategies and applications in various water treatment scenarios. In particular, the article indicates how integrating stimuli-responsive nanomaterials into existing water treatment technologies can significantly enhance their performance, leading to more sustainable and cost-effective solutions. The synergy between these advanced materials and traditional treatment methods could pave the way for innovative approaches to water purification, offering enhanced selectivity and efficiency. Furthermore, the review highlights the critical challenges and future directions in this rapidly evolving field, emphasizing the need for further research and development to fully realize the potential of these materials in addressing the pressing challenges of water purification.

Highly Efficient Manganese Bromides with Reversible Luminescence Switching through Amorphous-Crystalline Transition.

While luminescent stimuli-responsive materials (LSRMs) have become one of the most sought-after materials owing to their potential in optoelectronic applications, the use of earth-scarce lanthanides remains a crucial problem to be solved for further development. In this work, two manganese-based LSRMs, (R)-(+)-1-phenylethylammonium manganese bromide, (R-PEA)2MnBr4, and (S)-(-)-1-phenylethylammonium manganese bromide, (S-PEA)2MnBr4, are successfully demonstrated. Both (R-PEA)2MnBr4 and (S-PEA)2MnBr4 show a kinetically stable red-emissive amorphous state and a thermodynamically stable green-emissive crystalline state at room temperature, where the fully reversible transition can be done through melt-quenching and annealing processes. Based on this property, a reusable manganese-halide-based time-temperature indicator is demonstrated for the first time. Furthermore, an X-ray scintillator with a low limit of detection (18.1 nGy/s) and a high spatial resolution limit (30.0 lp/mm) are achieved by exploiting the high transparency of amorphous states. These results uncover the multifunctionality of manganese halides and pave the way for upcoming research.

Dual-locked fluorescent probes for precise diagnosis and targeted treatment of tumors.

Cancer continues to pose a significant threat to global health, with its high mortality rates largely attributable to delayed diagnosis and non-specific treatments. Early and accurate diagnosis is crucial, yet it remains challenging due to the subtle and often undetectable early molecular changes. Traditional single-target fluorescent probes often fail to accurately identify cancer cells, relying solely on single biomarkers and consequently leading to high rates of false positives and inadequate specificity. In contrast, dual-locked fluorescent probes represent a breakthrough, designed to enhance diagnostic precision. By requiring the simultaneous presence of two specific tumor-associated biomarkers or microenvironmental conditions, these probes significantly reduce non-specific activations typical of conventional single-analyte probes. This review discusses the structural designs, response mechanisms, and biological applications of dual-locked probes, highlighting their potential in tumor imaging and treatment. Importantly, the review addresses the challenges, and perspectives in this field, offering a comprehensive look at the current state and future potential of dual-locked fluorescent probes in oncology.

From Simple Probe to Smart Composites: Water-Soluble Pincer Complex With Multi-Stimuli-Responsive Luminescent Behaviors.

Water-soluble smart materials with multi-stimuli-responsiveness and ultra-long room-temperature phosphorescence (RTP) have garnered broad attention. Herein, a water-soluble terpyridine zinc complex (MeO-Tpy-Zn-OAc), featuring a simple donor-π-acceptor (D-π-A) structure is presented, which responds to a variety of stimuli, including changes in solvents, pH, temperature, and the addition of amino acids. Notably, MeO-Tpy-Zn-OAc functions as a fluorescence probe, capable of visually and selectively discriminating aspartate or histidine among other common amino acids in water. Additionally, when incorporated into polyvinyl alcohol (PVA) to form the composite MeO-Tpy-Zn-OAc@PVA, the material exhibits reversible writing, photochromism, and a prolonged RTP with a 14 s afterglow. These unique properties enable the composite to be utilized in potential applications such as secure data encryption and inkless printing.

An Acid-Responsive Fluorescent Molecule for Erasable Anti-Counterfeiting.

A tetraphenylethylene (TPE) derivative, TPEPhDAT, modified by diaminotriazine (DAT), was prepared by successive Suzuki-Miyaura coupling and ring-closing reactions. This compound exhibits aggregation-induced emission enhancement (AIEE) properties in the DMSO/MeOH system, with a fluorescence emission intensity in the aggregated state that is 5-fold higher than that of its counterpart in a dilute solution. Moreover, the DAT structure of the molecule is a good acceptor of protons; thus, the TPEPhDAT molecule exhibits acid-responsive fluorescence. TPEPhDAT was protonated by trifluoroacetic acid (TFA), leading to fluorescence quenching, which was reversibly restored by treatment with ammonia (on-off switch). Time-dependent density functional theory (TDDFT) computational studies have shown that protonation enhances the electron-withdrawing capacity of the triazine nucleus and reduces the bandgap. The protonated TPEPhDAT conformation became more distorted, and the fluorescence lifetime was attenuated, which may have produced a twisted intramolecular charge transfer (TICT) effect, leading to fluorescence redshift and quenching. MeOH can easily remove the protonated TPEPhDAT, and this acid-induced discoloration and erasable property can be applied in anti-counterfeiting.

Silver to Gold Metallic Luster Changes in Stimuli-Responsive Diacetylene Derivatives Uniquely Arranged within Crystals.

Eye-catching metallic luster materials, especially those whose colors can be controlled by external stimuli, have many potential applications. Here, we present a silver luster material that changes color to gold upon UV irradiation. Diacetylene (DA) derivatives with stilbenes introduced via linkers at both ends (DS-DAn (n = 1-6)) exhibited significantly different metallic luster and color change behaviors depending on the linker carbon number (n). The results revealed that the stacked structure of platelet crystals consisting of DS-DA1 with the shortest linker carbon chain exhibited a silver luster and changed its appearance to gold upon UV irradiation; this was an exceptional property of this material. More importantly, we found a unique crystal structure formed by DS-DA1, where the two assembled states coexisted. Partial topochemical polymerization of DA within this unique crystal structure dramatically changed its color from silver to gold. The findings of this study not only contribute to the development of the basic science of DA polymerization but also facilitate the development of new applications of metallic luster materials due to their attractive features that are adaptable to photomask patterning and UV laser lithography.

Research Progress and Emerging Directions in Stimulus Electro-Responsive Polymer Materials.

Stimulus electro-responsive polymer materials can reversibly change their physical or chemical properties under various external stimuli such as temperature, light, force, humidity, pH, and magnetic fields. This review introduces typical conventional stimulus electro-responsive polymer materials and extensively explores novel directions in the field, including multi-stimuli electro-responsive polymer materials and humidity electro-responsive polymer materials pioneered by our research group. Despite significant advancements in stimulus electro-responsive polymer materials, ongoing research focuses on enhancing their efficiency, lifespan, and production costs. Interdisciplinary collaboration and advanced technologies promise to broaden the application scope of these materials, particularly in medical and environmental protection fields, ultimately benefiting society.

A Comprehensive Review of Stimuli-Responsive Smart Polymer Materials-Recent Advances and Future Perspectives.

Today, smart materials are commonly used in various fields of science and technology, such as medicine, electronics, soft robotics, the chemical industry, the automotive field, and many others. Smart polymeric materials hold good promise for the future due to their endless possibilities. This group of advanced materials can be sensitive to changes or the presence of various chemical, physical, and biological stimuli, e.g., light, temperature, pH, magnetic/electric field, pressure, microorganisms, bacteria, viruses, toxic substances, and many others. This review concerns the newest achievements in the area of smart polymeric materials. The recent advances in the designing of stimuli-responsive polymers are described in this paper.

Stimulus-responsive drug delivery nanoplatforms for inflammatory bowel disease therapy.

Inflammatory bowel disease (IBD) manifests as inflammation in the colon, rectum, and ileum, presenting a global health concern with increasing prevalence. Therefore, effective anti-inflammatory therapy stands as a promising strategy for the prevention and management of IBD. However, conventional nano drug delivery systems (NDDSs) for IBD face many challenges in targeting the intestine, such as physiological and pathological barriers, genetic variants, disease severity, and nutritional status, which often result in nonspecific tissue distribution and uncontrolled drug release. To address these limitations, stimulus-responsive NDDSs have received considerable attention in recent years due to their advantages in providing controlled release and enhanced targeting. This review provides an overview of the pathophysiological mechanisms underlying IBD and summarizes recent advancements in microenvironmental stimulus-responsive nanocarriers for IBD therapy. These carriers utilize physicochemical stimuli such as pH, reactive oxygen species, enzymes, and redox substances to deliver drugs for IBD treatment. Additionally, pivotal challenges in the future development and clinical translation of stimulus-responsive NDDSs are emphasized. By offering insights into the development and optimization of stimulus-responsive drug delivery nanoplatforms, this review aims to facilitate their application in treating IBD. STATEMENT OF SIGNIFICANCE: This review highlights recent advancements in stimulus-responsive nano drug delivery systems (NDDSs) for the treatment of inflammatory bowel disease (IBD). These innovative nanoplatforms respond to specific environmental triggers, such as pH reactive oxygen species, enzymes, and redox substances, to release drugs directly at the inflammation site. By summarizing the latest research, our work underscores the potential of these technologies to improve drug targeting and efficacy, offering new directions for IBD therapy. This review is significant as it provides a comprehensive overview for researchers and clinicians, facilitating the development of more effective treatments for IBD and other chronic inflammatory diseases.

Aptamer-controlled stimuli-responsive drug release.

Aptamers have been widely researched and applied in nanomedicine due to their programmable, activatable, and switchable properties. However, there are few reviews on aptamer-controlled stimuli-responsive drug delivery. This article highlights the mechanisms and advantages of aptamers in the construction of stimuli-responsive drug delivery systems. We summarize the assembly/reconfiguration mechanisms of aptamers in controlled release systems. The assembly and drug release strategies of drug delivery systems are illustrated. Specifically, we focus on the binding mechanisms to the target and the factors that induce/inhibit the binding to the stimuli, such as strand, pH, light, and temperature. The applications of aptamer-based stimuli-responsive drug release are elaborated. The challenges are discussed, and the future directions are proposed.

Designing Stimuli-Responsive Supramolecular Gels by Tuning the Non-Covalent Interactions of the Functional Groups.

The physical characteristics of a supramolecular gel are greatly influenced by the nature and arrangement of functional groups in the gelator. This work focuses on the impact of the functional groups, specifically the hydroxyl group, on the stimuli-responsive properties of a gel. We used a C3-symmetric benzene-1,3,5-tricarboxamide (BTA) platform, which was attached to the methyl ester of phenylalanine (MPBTA) and tyrosine (MTBTA). The gelation studies revealed that MPBTA gelled in alcohols, non-polar aromatic solvents, and aqueous mixtures (1:1, v/v) of high-polar solvents, whereas MTBTA gelled only in an aqueous mixture of DMF (1:1, v/v). The mechanical and thermal strength of the gels were evaluated by rheological and Tgel studies, and the results indicated that MPBTA gels were stronger than MTBTA gels. The gels were characterized by powder X-ray diffraction and scanning electron microscopy (SEM). The analysis of stimuli-responsive properties revealed that MPBTA gels were intact in the presence of sodium/potassium salts, but the MTBTA gel network was disrupted. These results indicate that the elegant choice of functional groups could be used to tune the constructive or destructive stimuli-responsive behavior of gels. This study highlights the significant role of functional groups in modulating the stimuli-responsive properties of supramolecular gels.

Novel Carbohydrate Polymer-Based Systems for Precise Drug Delivery in Colon Cancer: Improving Treatment Effectiveness With Intelligent Biodegradable Materials.

Due to their biocompatibility, biodegradability, and controlled release, carbohydrates polymers are crucial to targeted drug delivery systems, notably for colon cancer treatment. This article examines how carbohydrate polymers like chitosan, pectin, guar gum, alginate, hyaluronic acid, dextran, and chondroitin sulfate are used in improved drug delivery. Modifying these polymers improves drug loading, stability, and release patterns, enhancing chemotherapeutic drugs' therapeutic index. Chitosan nanoparticles are pH-responsive, making them perfect for cancer treatment. Pectin's resistance to gastric enzymes and colonic bacteria makes it a promising colon-specific medication delivery agent. The combination of these polymers with nanotechnology, 3D printing, and AI allows the creation of stimuli-responsive systems that release drugs precisely in response to environmental signals like pH, redox potential, or colon enzymatic activity. The review highlights intelligent delivery system design advances that reduce systemic toxicity, improve treatment efficacy, and improve patient adherence. Carbohydrate polymers will revolutionize colon cancer treatment with personalized and accurate alternatives.

Tailoring Core-Shell Metal Coordination for Smart Seed Coatings in Sustainable Agriculture.

The international agriculture and food security sector is grappling with challenges like low crop yields, soil health deficiencies, and inefficient agrochemical use. The application of smart nanotechnology in agriculture, particularly surface functionalization, holds promise but has limited implementation. Engineered nanomaterials used as seed treatments, known as nanopriming, offer a simple technology to improve crop yield and stress tolerance. In this study, a multicomponent platform called Phelm (Phenolic network with a lipid core and metal coordinated shell) is proposed for encapsulating a commercial plant growth regulator, indole-3 acetic acid (IAA). Phelm comprises a hydrophobic solid lipid core, loaded with IAA, and an outer metal coordinated phenolic shell of tannic acid (TA) and Fe3+. The platform aims to treat seeds with encapsulated IAA, which can be controllably released, as well as protect the germination process at high salt concentrations. Phelm showed a remarkable increase in growth parameters of wheat seeds up to 58.6%, despite being irrigated with high concentrations of saltwater (100 mM). These findings suggest that nanopriming of seeds can effectively increase their efficacy even under abiotic stress conditions, which can drastically improve crop yields. Moreover, we envisage that the Phelm core/shell assembly can encapsulate a wide range of agrochemicals and biostimulants to promote sustainable and smart agricultural practices.

Charge-Reversal Nano-Drug Delivery Systems in the Tumor Microenvironment: Mechanisms, Challenges, and Therapeutic Applications.

The charge-reversal nano-drug delivery system (CRNDDS) is a promising system for delivering chemotherapy drugs and has gained widespread application in cancer treatment. In this review, we summarize the recent advancements in CRNDDSs in terms of cancer treatment. We also delve into the charge-reversal mechanism of the CRNDDSs, focusing on the acid-responsive, redox-responsive, and enzyme-responsive mechanisms. This study elucidates how these systems undergo charge transitions in response to specific microenvironmental stimuli commonly found in tumor tissues. Furthermore, this review explores the pivotal role of CRNDDSs in tumor diagnosis and treatment, and their potential limitations. By leveraging the unique physiological characteristics of tumors, such as the acidic pH, specific redox potential, and specific enzyme activity, these systems demonstrate enhanced accumulation and penetration at tumor sites, resulting in improved therapeutic efficacy and diagnostic accuracy. The implications of this review highlight the potential of charge-reversal drug delivery systems as a novel and targeted strategy for cancer therapy and diagnosis.