The management of bacterial plant diseases is impeded by biofilm fortifications and the poor foliar affinity of conventional antimicrobials. Supramolecular assemblies have recently emerged as promising biofilm-eradicating agents with enhanced surface adhesion. Yet, supramolecular polymers, although endowed with comparable or even greater potential, remain largely untapped in this arena. Herein, we introduce NOP@CB[8], a flower-like supramolecular polymer self-assembled in water from a de novo designed cationic pyridinium salt (NOP) and cucurbit[8]uril (CB[8]). Acting as a multifunctional agent, NOP@CB[8] disrupts bacterial membranes, perturbs redox equilibrium, disintegrates biofilms, and concurrently enhances foliar affinity. These combined attributes endow NOP@CB[8] with potent in vivo efficacy, exhibiting protective and curative efficacies of 56.1% and 51.2%, respectively, at 200µg mL-1 against rice bacterial leaf blight, thereby surpassing both free NOP (47.9%/43.1%) and thiodiazole copper (TC, 36.2%/33.7%). Remarkably, NOP@CB[8] delivers high control efficacy with uncompromised safety toward both target and non‑target organisms, even demonstrates enhanced safety in zebrafish relative to free NOP. Extending its scope to citrus and kiwifruit cankers, NOP@CB[8] achieves approximately 80% protective and over 60% curative efficacy, consistently outperforming NOP and TC. Together, this study delineates a green alternative for crop protection and a conceptual framework for next-generation functional supramolecular polymers.

Despite the crucial roles of glycan structures in glycosylated macromolecules such as proteoglycans in the extracellular matrix, their regulatory mechanism is still poorly understood, due to the complex structures and dynamic interactions of polysaccharides. Here, supramolecular polymers were employed as simplified mimics for fibrous proteoglycans to investigate the regulatory role of the glycans. We constructed a series of glycopeptides based on the precise linear tetrasaccharide structure (CT) from chondroitin. Experimental and computational results indicated that glycopeptides containing triphenylalanine and chondroitin tetrasaccharide (CT-3F) could assemble into tetra-stranded nonhelical fibers. Compared with the glycopeptide fiber of nonlinear sialyllactose (SL-3F), the linear geometry of CT resulted in fewer hydrogen bonds than nonlinear SL, and consequently different flexibility of the corresponding supramolecular glycopolymers which was supported by the change of measured persistence length and bending modulus. Importantly, flexibility of CT-3F fibers from glycan geometry could significantly enhance their interaction with preosteoblastic cells and osteogenic gene expression. These results reveal an unexplored dimension of complex oligosaccharides and provide an alternative pathway for tuning the properties of supramolecular polymers and even related biomaterials.

Fungal enzyme-driven precipitation polymerization: Trapping estrogenic chemicals to block vegetable contamination.

Long-lived triplet excitons in polymers are crucial for driving oxygen reduction reaction (ORR) in photocatalytic H2O2 production, but their formation is typically limited by weak spin-orbit coupling (SOC) and a large singlet-triplet splitting energy (ΔEST). Here we present a "dual-polarized" strategy in a novel donor-acceptor (D-A) polymer (MQDP) containing S═N─C and C═N─C linkages. MQDP polymer was prepared via supramolecular precursor polymerization of acenaphthenequinone (AQ), dibenzothiophene-5-oxide (DPO), and melem (ME). Compared to the single-polarized analogue MQP (τp = 672 µs), the dual-polarized units in MQDP enhance SOC and reduce ΔEST, thereby generating multiple singlet-to-triplet intersystem crossing (ISC) transfer channelsto produce long-lived triplet excitons (τp = 868 µs). In addition, the dual-polarized MQDP enriches surface-active sites for O2 adsorption, effectively reducing the energy barrier for ORR. The MQDP achieves a remarkable H2O2 generation rate of 15.38 mmol g-1 h-1 under visible light irradiation and ambient air, nearly 1.9 times higher than that of MQP (8.13 mmol g-1 h-1). These findings demonstrate the effectiveness of the dual-polarized design in tuning exciton dynamics and surface reactivity of D-A polymers for enhanced photocatalysis.

ABSTRACT Long‐lived triplet excitons in polymers are crucial for driving oxygen reduction reaction (ORR) in photocatalytic H 2 O 2 production, but their formation is typically limited by weak spin‐orbit coupling (SOC) and a large singlet–triplet splitting energy (Δ E ST ). Here we present a “dual‐polarized” strategy in a novel donor–acceptor (D–A) polymer (MQDP) containing S═N─C and C═N─C linkages. MQDP polymer was prepared via supramolecular precursor polymerization of acenaphthenequinone (AQ), dibenzothiophene‐5‐oxide (DPO), and melem (ME). Compared to the single‐polarized analogue MQP ( τ p = 672 µs), the dual‐polarized units in MQDP enhance SOC and reduce Δ E ST , thereby generating multiple singlet‐to‐triplet intersystem crossing (ISC) transfer channels to produce long‐lived triplet excitons ( τ p = 868 µs). In addition, the dual‐polarized MQDP enriches surface−active sites for O 2 adsorption, effectively reducing the energy barrier for ORR. The MQDP achieves a remarkable H 2 O 2 generation rate of 15.38 mmol g −1 h −1 under visible light irradiation and ambient air, nearly 1.9 times higher than that of MQP (8.13 mmol g −1 h −1 ). These findings demonstrate the effectiveness of the dual‐polarized design in tuning exciton dynamics and surface reactivity of D–A polymers for enhanced photocatalysis.

We describe a modular, diverse, and customizable supramolecular-materials platform that can deliver nucleic acids in vitro and in vivo. The chemistries deployed enable the generation of multiple supramolecular polycations, which can associate with RNA to form polyelectrolyte complexes, but which have the unique feature of reversible cross-links, via host-guest interactions of monomers that display aromatic amino acid termini with cucurbit[8]uril (CB[8]). Families of supramolecular polymers can be prepared by simple variation in monomer structure, enabling the tuning of properties. We demonstrate that these supramolecular polyelectrolyte complexes with RNA can be prepared easily via automatable procedures to generate nanoparticles that meet Critical Quality Attributes for manufactured RNA vaccines and therapeutics. We show that these materials can deliver RNA to a range of cell types, displaying reporter-protein expression at levels equivalent to, or greater than, commercial transfection reagents, with no acute adverse phenotypic effects. Finally, we demonstrate the success of our materials platform across a range of nucleic acid types, with expression of mRNA within tumors of an orthotopic Triple-Negative Breast Cancer mouse model, knockdown of a kinase implicated in cancer progression via siRNA, and effective protection against H1N1 influenza virus challenge in mice following injections of self-amplifying RNA.

ABSTRACT Emerging stretchable fully π‐conjugated polymers (FπCPs) films are promising functional layers in flexible optoelectronic devices. However, simultaneous enhancement of the stretchability and optoelectronic properties of FπCPs films via traditional chain‐softness modification or physical blending approaches is challenging due to the inherently weak interchain charge‐transportation and morphological stability of these films, hindering their wide application in flexible electronics. Herein, we establish a new semiconductor supramolecular polymer (SSP) plasticizing strategy to simultaneously enhance the optoelectronic, morphological, and stretchable properties of FπCPs films for flexible polymer light‐emitting diodes (PLEDs). Two fundamental requirements were proposed—fluid monomer (EODBC) to obtain plasticizing and supramolecular π‐conjugated monomer (FMIPF6) to achieve excellent optoelectronic characteristics—to prepare model‐matched SSP plasticizers (EODBC‐FMIPF6). Interestingly, F8BT blending films present a uniform morphology with efficient emission. Therefore, the stretchability and charge transport behavior of FπCPs films can be improved simultaneously via SSP plasticization due to the synergistic effect of hierarchical structure and optoelectronic properties of SSP plasticizers, increasing the external quantum efficiency of PLEDs by approximately 13%. Finally, flexible PLEDs based on stretchable F8BT blending films were fabricated to confirm the effectiveness of our strategy. Our results show that dual‐functional fluid SSP may be used as novel plasticizers to manufacture stretchable FπCPs for flexible electronics.

A notable characteristic of living organisms is their capacity to adapt to environmental changes and transform external signals into distinct responsiveness, facilitating the execution of diverse functions with motility as a key parameter. To better mimic such lifelike behavior, researchers have developed various supramolecular assembled systems with responsive behavior toward a variety of stimuli. However, exploiting motion along length scales and achieving collective control over the responsiveness to multiple stimuli in supramolecular systems is still challenging. Here we present the development of molecular motor based supramolecular polymers that are responsive toward multi-stimulus and exhibit multi-state assembly and chirality. Taking advantages of aldehyde functionalized motors, we realized photo-responsive supramolecular polymers featuring boosted photo-efficiency, near quantitative photoconversions, programmable behavior and responsiveness to multiple stimuli in a reversible manner in aqueous media. The various stimuli including light and different chemicals could act on the motor building blocks and subsequently trigger the transformation of the supramolecular polymers toward reversible polymerization, direct post-functionalization and chirality modulation. The interplay between the rotary molecular motion and the supramolecular systems assembly process, taking advantage of different external stimuli to govern the assembly state, provides a basis for multi-responsive supramolecular materials.

Achieving efficient synergy between covalent and supramolecular polymers is an effective strategy for developing novel polymeric materials. However, realizing this synergy through rational chemical design to efficiently integrate both types of polymers within a single polymer network remains a significant challenge. Here, we achieve efficient synergy between covalent and supramolecular polymer chains by inducing entanglement of unsymmetrical topological nodes. Benefiting from the molecular entanglement strategy, this synergistic network effectively integrates the stability of a covalent polymer and the dynamics of a supramolecular polymer. While maintaining the integrity of the network, the reversible host-guest recognition in the supramolecular polymer dissipates the applied energy, thus allowing the mechanical properties of the entire network to be regulated. Besides, the host-guest recognition pairs can serve as splicing points for integrating additional polymers, transforming the topologically entangled covalent-supramolecular synergistic polymer platform into a multifunctional platform that accommodates a variety of polymers, significantly increasing the diversity of their structures and properties. These findings may spur further innovations in the field of polymers in general, as well as promote a deeper understanding of dynamic chemistry.

The smooth decarboxylation under basic conditions of activated carboxylic acids (ACAs) is exploited to achieve a transient supramolecular polymer based on hydrogen bonds reinforced by electrostatic interactions. In particular, it is proved that when the aliphatic α,ω-diamine 3, namely, 1,8-diamino-3,6-dioxaoctane, reacts with an equimolar amount of the activated dicarboxylic acid 1H2, i.e., a difunctional derivative of 2-cyano-2-phenylpropanoic acid, a supramolecular polymer of the kind -AB─BA─AB- is immediately formed in chloroform solution. The A─A and B─B monomers are held together by salt bridges (hydrogen bonds reinforced by electrostatic interactions) between ammonium and carboxylate functions. The larger the concentration of the added materials, the higher the polymerization degree (DP) of the polymer. Under the given experimental protocol, such a polymer disaggregates over time due to decarboxylation, and at the end of the process, only diamine 3 and waste product 4, which cannot interact with one another anymore, remain in the solutions. DOSY spectra recorded at different reaction times definitely demonstrate the phenomenology described above. The trend of the degree of polymerization as a function of monomer concentration has been clarified in the light of the ring-chain equilibrium theory. The application of the theory enables the accurate evaluation of the distribution of linear and cyclic oligomers as well as the critical concentration, ccrit, above which polymerization rapidly becomes more extensive due to the saturation of macrocyclic species. Notably, the ACA is not used just as a stimulus for a dissipative system, but as one of its structural components.

Supramolecular polymers are a class of dynamic materials with varied applications in material science and biomaterials. The quality and nature of solvent are often used to control various aspects of supramolecular polymerization. A vast majority of monomers or building blocks are known to assemble in a single solvent, which promotes intermolecular interactions. A small fraction of monomers requires a combination of solvent and anti-solvent to promote colloidal assembly. In the past decade, examples are emerging in which the solvents seem to exhibit specific roles in controlling the assembly, beyond the conventional solvent/anti-solvent modes. In this perspective, we discuss recent examples in which solvents seem to play an unconventional role in dictating supramolecular polymerization. Often, the unique assembly behavior is attributed to the thermodynamics of binary mixture governing the solvation. We envisage that the specific interaction between the monomer and solvent warrants a careful consideration, in addition to the solvent-solvent interactions to account for the perceived special effects of the solvents.

A novel Co(II)-Fe(II)-Ru(II)-based heterometallic supramolecular polymer for electrochemical detection of sulfite: Kinetic and mechanistic studies

Chirality is recognized as a vital factor in generating strong spin selectivity in organic π-conjugated systems. In recent years, chiral polymers and supramolecular assemblies have attracted interest as potential spin-filtering materials because of the chirality-induced spin-selectivity (CISS) effect. However, despite their potential applications in spintronics, the CISS effect in metal-free supramolecular architectures remains relatively less explored. In this work, we have investigated metal-free supramolecular materials based on chiral naphthalenediimide (NDI) moieties for potential applications of the CISS effect. Our results highlight the crucial role of electron spin in governing spin-selective charge transport, as well as in boosting oxygen reduction and evolution reactions. Notably, the CISS effect enables chiral analogues to exhibit superior catalytic behavior, reflected in higher current densities and more positive onset potentials, clear evidence of spin-dependent processes. Overall, this work demonstrates the substantial promise of metal-free chiral organic materials for spintronics applications, opening new avenues for device design and advanced functionalities.

Supramolecular polymers are dynamic aggregates whose properties arise from their constitutive bonds, based on reversible, non-covalent interactions. A central aspect in the design and function of these materials is the cooperativity of polymerization, by which the addition of monomers becomes increasingly favorable as the polymer grows. Cooperativity strongly influences both the structure and collective behavior of supramolecular materials, with significant implications for their properties. Understanding the origins and consequences of cooperativity is crucial for the rational design of new functional supramolecular polymer systems. Herein, we systematically explore the cooperativity of supramolecular polymer systems via Molecular Dynamics simulations, powered by On-the-fly Probability Enhanced Sampling, to accurately characterize the free energy landscape associated with polymerization. We validate our approach via ad hoc, minimalistic coarse-grained models of cooperative and non-cooperative self-assembling monomers. We then apply our analysis to ureidopyrimidinone (UPy) supramolecular polymers, widely used in biohydrogel design. Our work provides detailed insights into the UPy polymerization process and how cooperativity can emerge from the hierarchical character of its supramolecular structure. The results underscore the importance of an extensive molecular simulation approach to obtain a quantitative characterization of the self-assembly thermodynamics, which is crucial to guide the rational development of next-generation supramolecular materials.

The formation of catenanes through dynamic covalent reaction of self-assembling precursors in one pot offers a powerful route to complex interlocked architectures, yet the mechanistic insight remains underexplored. Here, we elucidate the nucleation-elongation mechanism in the one-pot synthesis of topologically distinct catenanes, using dimeric (DCC) and trimeric cage-catenanes (TCC) as model systems. Unlike conventional supramolecular polymerization, catenation exhibits topology-dependent pathways: DCC formation is driven by the strong templating effect of its monomeric unit MC-1, while TCC assembly proceeds with several pathways in parallel, via cooperative binding of partially catenated intermediates. Kinetic profiling of the catenation reveals sigmoidal growth with distinct induction periods, where longer induction period correlates with more challenging nucleation. Seeded growth experiments demonstrate that preformed nuclei (e.g., MC-1 for DCC) bypass kinetic barriers, remarkably reducing its induction period, akin to seeded supramolecular polymerization. Our work bridges the gap between supramolecular polymerization and mechanical bonding for interlocked structures, offering a hint for the rational synthesis of structures with sophisticated topology.

ABSTRACT This work studies the impact of quenching the living polymerization of polytetrahydrofuran (PTHF) with imidazole and imidazole derivatives. Both nitrogen atoms of imidazole rapidly react to form imidazolium‐functionalized‐PTHF. Imidazolium formation could not be fully suppressed even with a large excess of imidazole quenching agent. To achieve imidazole terminated polymers, quenching with 1,1′‐carbonyldiimidazole followed by hydrolysis proved to be an effective and efficient route. Imidazole terminated PTHF was then demonstrated to have utility in coordinating with copper and zinc metal ions to form supramolecular polymers of higher effective molecular weight.

Non-traditional luminescent polymers exhibit significant advantages in bio-diagnostics and intelligent materials but suffer from low luminescence efficiency and limited functionality. Inspired by the excited-state proton transfer mechanism mediated by dense hydrogen bonds in jellyfish fluorescent proteins, we propose a strategy using dynamic quadruple hydrogen bonding ureidopyrimidinone motifs to create highly efficient luminescent polymers. By modulating the aggregated structure of the supramolecular units, proton transfer between paired motifs is activated, thereby achieving a high photoluminescent quantum yield up to 52% in supramolecular polyurethane. Ultrafast spectroscopy directly revealed this intermolecular proton transfer, while solid-state NMR spectroscopy confirmed the essential role of quadruple hydrogen bonds. The dynamically switchable hydrogen bonding structure endows the material with multifunctional integration, including strong fluorescence properties, high toughness, self-healing, reprocessability, and stimulus responsiveness. This research not only introduces a pioneering approach for advancing high-performance light-emitting materials but also enhances the prospects for their practical applications.

Sulfonylureas are hypoglycemic agents used in type 2 diabetes mellitus, although their low water solubility implies high therapeutic doses. Inclusion complexes with β-cyclodextrin (β-CD), a cyclic oligosaccharide featuring a hydrophobic interior and hydrophilic exterior, offer a supramolecular polymer capable of encapsulating drugs, improving solubility and stability. We explore how substituent size and interaction type influence the stability of β-CD complexes with p-toluenesulfonylurea, tolbutamide, and tolazamide. Using molecular dynamics simulations, clustering analysis, and quantum chemistry calculations at the M06-2X-D3/ACP-6-31G(d) + SMD level of theory, we identified the most stable binding modes. Boltzmann populations of complexes revealed a single dominant conformation for p-toluenesulfonylurea (∼97%), two major coexisting conformations for tolbutamide (75/25%), and two near-equal conformations for tolazamide (56/43%). Predominant conformations adopted by guest molecules are in line with experimental reports. Binding free energies, determined via molecular mechanics Poisson-Boltzmann surface area analysis, for p-toluensulfonylurea, tolbutamide and tolazamide in β-CD inclusion complexes, averaged -10.75, -13.42, and -12.84 kcal mol-1, respectively. Interaction energies increased with bulkier substituents, though this was partially offset by higher deformation costs. Analyses of ρ(r) showed that stabilization arises from networks of spatially distributed weak interactions rather than from strong directional intermolecular hydrogen bonds. These findings offer a detailed view of β-CD host-guest recognition within a carrier context, guiding the design of β-cyclodextrin-based systems to improve the formulation, stability, and therapeutic effectiveness of drugs in type 2 diabetes mellitus.

Curvature has recently emerged as a key structural parameter that dictates the pathway and topology of supramolecular polymerization. We previously showed that scissor-shaped azobenzene dyads, dimerized through a xylylene spacer bearing long alkyl chains, undergo folding-induced self-assembly to yield curvature-derived architectures such as nanorings and nanotubes. Here we extend this scaffold to a bulkier chromophore and demonstrate that the curvature-directed pathway is preserved. Dimerization of tetraphenylporphyrin on the scissor-shaped backbone yields a molecule that, in nonpolar solvents, exhibits a split, bathochromically shifted Soret band. This finding suggests intra- and intermolecular J-type exciton coupling during folding-induced supramolecular polymerization. AFM revealed the formation of helically coiled supramolecular polymers (helicoids). These helicoids evolve into nanotubes over time; applying sonication beforehand induces fragmentation that closes the curved segments into discrete toroids.

Dynamic Supramolecular Polymer Networks Constructed by Synergistic Dual Host-Guest Interactions