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Metal‐coordinated supramolecular nanoassemblies have recently attracted extensive attention as materials for cancer theranostics. Owing to their unique physicochemical properties, metal‐coordinated supramolecular self‐assemblies can bridge the boundary between traditional inorganic and organic materials. By tailoring the structural components of the metal ions and binding ligands, numerous multifunctional theranostic nanomedicines can be constructed. Metal‐coordinated supramolecular nanoassemblies can modulate the tumor microenvironment (TME), thus facilitating the development of TME‐responsive nanomedicines. More importantly, TME‐responsive organic–inorganic hybrid nanomaterials can be constructed in vivo by exploiting the metal‐coordinated self‐assembly of a variety of functional ligands, which is a promising strategy for enhancing the tumor accumulation of theranostic molecules. In this review, recent advancements in the design and fabrication of metal‐coordinated supramolecular nanomedicines for cancer theranostics are highlighted. These supramolecular compounds are classified according to the order in which the coordinated metal ions appear in the periodic table. Furthermore, the prospects and challenges of metal‐coordinated supramolecular self‐assemblies for both technical advances and clinical translation are discussed. In particular, the superiority of TME‐responsive nanomedicines for in vivo coordinated self‐assembly is elaborated, with an emphasis on strategies that enhance the accumulation of functional components in tumors for an ideal theranostic outcome. This review summarizes the recent progress made on metal‐coordinated supramolecular nanomedicines for cancer theranostic by classifying the coordination metal ions in the order of periodic table. Especially, the superiority of the tumor‐responsive nanomedicines for in vivo coordinated self‐assembling cancer theranostic is discussed, with an emphasis on how to realize high nanomedicine accumulation on tumor and therefore ideal theranostic outcome.

Aggregation‐induced emission (AIE) is a phenomenon in which fluorescence is enhanced rather than quenched upon molecular assembly. AIE fluorogens (AIEgens) are flexible, conjugated systems that are limited in their dynamics when assembled, which improves their fluorescent properties. This intriguing feature has been incorporated in many different molecular assemblies and has been extended to nanoparticles composed of amphiphilic polymer building blocks. The integration of the fascinating AIE design principle with versatile polymer chemistry opens up new frontiers to approach and solve intrinsic obstacles of conventional fluorescent materials in nanoscience, including the aggregation‐caused quenching effect. Furthermore, this integration has drawn significant attention from the nanomedicine community, due to the additional advantages of nanoparticles comprising AIEgenic molecules, such as emission brightness and fluorescence stability. In this regard, a range of AIEgenic amphiphilic polymers have been developed, displaying enhanced emission in the self‐assembly/aggregated state. AIEgenic assemblies are regarded as attractive nanomaterials with inherent fluorescence, which display promising features in a biomedical context, for instance in biosensing, cell/tissue imaging and tracking, as well as (photo) therapeutics. In this review, we describe recent strategies for the design and synthesis of novel types of AIEgenic amphiphilic polymers via facile approaches including direct conjugation to natural/synthetic polymers, polymerization, post‐polymerization and supramolecular host−guest interactions. Their self‐assembly behavior and biomedical potential will be discussed. The recent advances in the design and synthesis of AIEgenic amphiphilic polymers are discussed. Their self‐assembly leads to particles with very high fluorescence intensity. The versatility of polymer science allows the creation of a wide variety of particles which show much potential for biomedical applications.

Stimuli‐responsive systems play a crucial role in biological processes. Research on supramolecular cages formed via noncovalent interactions contributes to the development of receptors that mimic these natural systems. Recently, anion‐coordination‐driven assembly (ACDA) employing oligourea ligands and trivalent phosphate ions (PO43−) has emerged as a promising strategy for constructing responsive supramolecular architectures. These assemblies are stabilized through multiple hydrogen bonds and are capable of undergoing structural transformations in response to external stimuli, offering a conceptual framework for understanding flexibility and environmental adaptability in biological contexts. This mini‐review highlights the stimuli‐responsive properties of anionic self‐assemblies, with a focus on systems involving oligourea ligands and PO43− ion. Organized by stimulus type, it discusses multistimuli responsiveness, guest‐induced transformations, solvent sensitivity, and light‐responsive behaviors. Current challenges and identifying future opportunities in the study of ACDA‐based stimuli‐responsive systems are discussed. This mini‐review summarizes recent developments in stimuli‐responsive supramolecular assemblies based on anion‐coordination‐driven assembly using oligourea ligands and phosphate anions. The content is organized by stimulus type: multistimuli, guest/template, solvent, and light. This review highlights multistimuli adaptability and structural transformations. Remaining challenges and future directions are also outlined.

Chirality is a fundamental property in nature, which is essential for the existence and survival of living organisms. Smart responsive chiroptical materials have garnered increasing attention due to their unique structural characteristics and potential applications. Among these, azobenzene (Azo), as a typical photoresponsive chromophore, plays a crucial role in constructing and controlling chiral structures. The unique cis‐trans isomerization, liquid crystallinity, and other physicochemical properties allow for a wide range of tunability in stimuli‐responsive chiroptical materials. Herein, we review the research studies in the field of chiral/achiral Azo building blocks for multilevel chiral generation as well as chiral switching, and summarize the recent advances on the applications of the chiral Azo structures from micro to macro levels. Finally, we aim to provide an overview of the potential challenges and new research opportunities for the development of novel smart responsive chiroptical materials. The unique cis‐trans isomerization, liquid crystallinity and other physicochemical properties of azobenzene allow for a wide range of tunability in stimuli‐responsive chiroptical materials, which endows azobenzene chiroptical aggregates with the ability of chirality switches (“on/off,” “inversion” and “amplification” switches) from microscopic to macroscopic scales as well as provides a bright prospect for the further applications of azobenzene chiroptical materials.

Dissipative self‐assembly (DSA) system requires a continuous supply of fuels to maintain the far‐from‐equilibrium assembled state. Living organisms exist and operate far from the thermodynamic equilibrium by continuous consumption of energy taken from the surroundings, so how to realize the construction of the artificial DSA system has attracted much attention by researchers all over the world. Owing to dynamic controllable noncovalent interactions, artificial supramolecular DSA systems have achieved higher functions fueled by various types of energy, such as chemical fuels, light, electric energy, acoustic energy, and mechanical energy. Upon the input of external fuels, nonactive precursors can be activated to form building blocks at higher energy levels and then self‐assemble into transient supramolecular structures. As the proceeding of deactivation reaction, the building blocks with higher energy level dissipate back to the initial precursors, resulting in the disassembly process, to complete a full cycle. In this review, we summarize the recent advances of artificial supramolecular DSA systems on its construction strategies and energy‐fueled regulation approaches. The applications of supramolecular DSA systems in luminescence modulating, information encryption, self‐regulating gels, drug delivery, and catalysis are also discussed. We hope that this review article will facilitate further understanding and development of DSA systems. Dissipative self‐assembly system leads to far‐from‐equilibrium materials. In this review, we summarize chemical, light, electricity, mechanical energy, and acoustic energy fueled supramolecular dissipative self‐assembly systems, and their applications on luminescence modulation, self‐erasable materials, self‐regulating hydrogels, controllable delivery system, and dynamic catalysis.

New concept for the development of supramolecular assemblies from intricate interactions between different classes of biomacromolecules (polysaccharides, proteins and lipids) is yet to come, due to their intrinsic chemical and structural complexity and incompatibility. Herein, we report an interaction mechanism among multiple biomacromolecules, and the structural and digestive properties of their assemblies using amylose (AM), lauric acid (LA), and β‐lactoglobulin (βLG) as exemplars. AM, LA, and βLG interact to form a water‐soluble ternary complex through van der Waals forces between AM and LA and high affinity binding between AM and βLG, which can further assemble into uniform‐sized, semi‐crystalline nanospheres under certain thermodynamic conditions. These nanospheres are substantially resistant to amylolysis, thus can be well utilized by gut microbiota, including increasing short‐chain fatty acid levels and shaping bacterial communities. Illustrating the complexation of AM, LA, and βLG and their assemblies from disorder to order, this work offers potential rationale of assemblies for multiple biomacromolecules driven by non‐covalent interactions and substantial potentials for supramolecular biomaterials development. On the basis of revealing the ternary interaction mechanism of multiple biomacromolecules (amylose [AM], lauric acid [LA], and β‐lactoglobulin [βLG]) through experiments and simulation calculations, a thermally controlled hierarchical strategy was firstly reported for self‐assembly of AM–LA–βLG complex into uniform‐sized nanospheres with well‐defined crystalline structure and stability. These nanospheres were substantially resistant to amylolysis and presented great fermentation functions by gut microbiota, including production of short‐chain fatty acids and regulating the bacterial composition and diversity.

Controllable construction of diversiform topological morphologies through supramolecular self‐assembly on the basis of single building block is of vital importance, but still remains a big challenge. Herein, a bola‐type supra‐amphiphile, namely DAdDMA@2β‐CD, is rationally designed and successfully prepared by typical host–guest binding β‐cyclodextrin units with an aggregation‐induced emission (AIE)‐active scaffold DAdDMA. Self‐assembling investigation reveals that several morphologies of self‐assembled DAdDMA@2β‐CD including leaf‐like lamellar structure, nanoribbons, vesicles, nanofibers, helical nanofibers, and toroids, can be straightforwardly fabricated by simply manipulating the self‐assembling solvent proportioning and/or temperature. To the best of knowledge, this presented protocol probably holds the most types of self‐assembling morphology alterations using a single entity. Moreover, the developed leaf‐like lamellar structure performs well in mimicking the light‐harvesting antenna system by incorporating with a Förster resonance energy transfer acceptor, providing up to 94.2% of energy transfer efficiency. Diversiform topological morphologies including leaf‐like lamella, nanoribbons, vesicles, nanofibers, helical nanofibers, and toroids are straightforwardly realized through supramolecular self‐assembly of a novel aggregation‐induced emission (AIE)‐active supra‐amphiphile under different solvent proportioning and/or temperature. The fabricated supramolecular aggregates perform well in mimicking the light‐harvesting antenna system.

The emergence of aggregation‐induced emission luminogens (AIEgens) has attracted substantial scientific attention. However, their antitumor efficacy in photodynamic therapy (PDT) is significantly restricted by the poor water solubility and limited treatment depth. Therefore, a novel AIEgens‐involved therapeutic platform with good permeability and bioavailability is urgently required. Herein, supramolecular chemistry is combined with the AIEgen bis‐pyrene (BP) to construct a peptide–AIEgen hybrid nanosystem (PAHN). After intravenous injection, the versatile nanoplatform not only improved the hydrophilicity of BP but also achieved stratified targeting from tumor to mitochondrial and induced mitochondrial dysfunction, thus activating caspase‐3 upregulation. Then, sonodynamic therapy (SDT), an alternative modality with high tissue penetrability, is performed to evoke reactive oxygen species (ROS) generation for BP. More importantly, since the hydrophilic shell is separated from the nanosystem by the specific cleavage of caspase‐3, the resulting decrease in hydrophilicity induced tight self‐aggregation of PAHN residues in situ, further allowing more absorbed energy to be used for ROS generation under ultrasound irradiation and enhancing SDT efficacy. Moreover, severe oxidative stress resulting from ROS imbalance in the mitochondria initiates the immunogenic cell death process, thus evoking antitumor immunogenicity. This PAHN provides prospective ideas into AIE‐involved antitumor therapy and design of peptide‐AIEgens hybrids. Inspired by the characteristics of aggregation‐induced emission luminogens (AIEgens), a peptide‐AIEgen hybrid nanosystem (PAHN) with a unique strategy of “stratified targeting” and “in situ self‐aggregation” is designed for synergistic enhanced sonodynamic therapy (SDT). The specific cleavage of caspase‐3 induces tight self‐aggregation of PAHN, further allowing more absorbed energy used for reactive oxygen species generation and enhancing mitochondria‐mediated oxidative stress.

Supramolecular assembly is a versatile bottom‐up strategy for creating advanced functional materials. Metallic platinum–platinum (Pt···Pt) interactions provide a distinctive driving force for supramolecular assembly due to their strong, directional, and long‐range nature. Despite their importance, the microscopic dynamics underlying the self‐assembly of Pt(II) complexes remain challenging to probe experimentally. Molecular dynamics (MD) simulations can capture these processes at atomic resolution, but extracting kinetic pathways is complicated by the indistinguishability and permutation of identical monomers within self‐assembled structures. In this study, we employ GraphVAMPnet, a deep learning framework based on graph neural networks (GNN), on extensive MD simulations of amphiphilic PtB complexes during the early stage of self‐assembly. GraphVAMPnet inherently accounts for permutational, rotational, and translational invariance, making it well‐suited for analyzing self‐assembly dynamics. Our analysis reveals three slow collective variables (CVs) that govern PtB self‐assembly. The slowest mode (CV1) separates two distinct kinetic growth routes: an incremental growth mechanism, in which single monomers join existing aggregates with predominantly antiparallel packing between two adjacent PtB complexes (CV3), and a hopping growth mechanism, in which clusters of smaller size merge via heterogeneous collisions, yielding a mix of antiparallel and parallel packing arrangements (CV2). Further energetic analysis indicates that incremental growth is favored, potentially leading to the well‐ordered nanosheet morphologies observed experimentally. Our findings provide molecular‐level insight into PtB self‐assembly pathways and showcase the capability of GraphVAMPnet in dissecting the complex dynamics of supramolecular assembly. GraphVAMPnet, a graph neural network–based deep learning framework, successfully overcomes the permutation challenge in analyzing molecular dynamics trajectories of self‐assembly of PtB complexes. It accurately identifies three slow collective variables and reveals two competing kinetic pathways—incremental and hopping growth—governing Pt(II) supramolecular assembly.

The synthesis of hollow fullerene‐like cages has always been an attractive goal for researchers. Nevertheless, such molecular design blueprints are often hampered by the unmet customization of assembly strategy and suitable five‐membered ring molecular tiles for building spheres. Herein, a novel spherical molecular cage V60‐MOP is successfully built by connecting 12 homo‐metallic pentagonal {V5S} tiles with benzene‐1,3,5‐tricarboxylate (BTC) ligands through coordination‐driven self‐assembly and exhibits a similar geometry to the C60 molecule. As far as is known, this {V5S} cluster with the shape of a hollow pentagram is entirely new and is first discovered in metal–organic polyhetra (MOPs). The other two pentagonal motifs are also customized by inserting [VO5] or [MoO5] in the center of {V5S} through in situ modification, which also led to another isomorphic V72‐MOP and V60Mo12‐MOP fullerene‐like cages. The three spherical cages reported above all exhibit regular icosahedral symmetry. Notably, a fascinating structure V66‐MOP is constructed from two different pentagonal motifs {V5S} and {VV5S}, with reduced symmetry, although the molecule remains a sphere in appearance, which is rare in fullerene‐shaped structures. In addition, the series of fullerene‐like V‐MOPs are active in the oxidation of sulfides to produce sulfoxides or sulfones with high conversion.