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Supramolecular polymer networks exhibit unique and tunable thermodynamic and dynamic properties that are attractive for a wide array of applications, such as adhesives, rheology modifiers, and compatibilizers. Coherent states (CS) field theories have emerged as a powerful approach for describing the possibly infinite reaction products that result from associating polymers. Up to this point, CS theories have focused on relatively simple polymer architectures. In this work, we develop an extension of the CS framework to study polymers with reversible bonds distributed along the polymer backbone, opening a broad array of new materials that can be studied with theoretical methods. We use this framework to discern the role of reactive site placement on sol–gel phase behavior, including the prediction of a microstructured gel phase that has not been reported for neutral polymer gels. Our results highlight the subtleties of thermodynamics in supramolecular polymers and the necessity for theories that capture them. [ABSTRACT FROM AUTHOR]

Mastering the manipulation of the electron spin plays a crucial role in comprehending the behavior of organic materials in several applications, such as asymmetric catalysis, chiroptical switches, and electronic devices. A promising avenue for achieving such precise control lies in the Chiral Induced Spin Selectivity (CISS) effect, where electrons with a favored spin exhibit preferential transport through chiral assemblies of specific handedness. Chiral supramolecular polymers emerge as excellent candidates for exploring the CISS effect due to their ability to modulate their helical structure through noncovalent interactions. In this context, systems capable of responding to external stimuli are particularly intriguing, sometimes even displaying chirality inversion. This study unveils spin selectivity in chiral supramolecular polymers, derived from single enantiomers, through scanning tunneling microscopy conducted in scanning tunneling spectroscopy mode. Following two distinct sample preparation protocols for each enantiomer, we generate supramolecular polymers with opposite handedness and specific spin transport characteristics. Our primary focus centers on chiral π-conjugated building blocks, with the aim of advancing novel systems that can inspire the organic spintronics community from a supramolecular chemistry level. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Polycatenane gels have attracted extensive attention due to their high degree of freedom and mobility. However, the syntheses of poly[2]catenane gels reported to date all rely on the polymer as the backbone. Herein, we prepared poly[2]catenane gels based on entirely sequential assembly of small molecules. Monomer M1 with two unclosed rings was first prepared, which self‐assembled to form supramolecular polymers (SPs) via hydrogen bonding and π‐π interactions. Upon adding small molecule monomers M2 and M3 with aldehyde groups, ring closing of SPs occurred because the amino groups in the SPs reacted with M2 to form imine bonds. In addition, M3, which had twice the number of aldehyde groups as M2, enabled SPs to ring‐close, causing the proceeding of crosslinking process at the same time. Thus linear SPs were transformed into poly[2]catenane gel networks. Due to the presence of hydrogen bonds in the poly[2]catenane gel, the gel also possessed stimulus responsiveness and self‐healing properties. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Polycatenane gels have attracted extensive attention due to their high degree of freedom and mobility. However, the syntheses of poly[2]catenane gels reported to date all rely on the polymer as the backbone. Herein, we prepared poly[2]catenane gels based on entirely sequential assembly of small molecules. Monomer M1 with two unclosed rings was first prepared, which self‐assembled to form supramolecular polymers (SPs) via hydrogen bonding and π‐π interactions. Upon adding small molecule monomers M2 and M3 with aldehyde groups, ring closing of SPs occurred because the amino groups in the SPs reacted with M2 to form imine bonds. In addition, M3, which had twice the number of aldehyde groups as M2, enabled SPs to ring‐close, causing the proceeding of crosslinking process at the same time. Thus linear SPs were transformed into poly[2]catenane gel networks. Due to the presence of hydrogen bonds in the poly[2]catenane gel, the gel also possessed stimulus responsiveness and self‐healing properties. [ABSTRACT FROM AUTHOR]

Tubular self‐assembled architectures are highly appealing supramolecular objects that participate in diverse essential biological processes. Controlling with precision their dimensions, and in particular their pore diameter, is a key objective to develop the full applied potential of these structures. Here, using a strategy that relies on the controlled supramolecular polymerization of Watson–Crick H‐bonded macrocycles, we target the assembly of 3 sets of nanotubes in which pore diameter is finely controlled from 1.8, to 3.2 and to 4.3 nm. This is simply done by elongating the oligo(phenylene‐ethynylene) block placed in between guanine and cytosine nucleobases in the monomer. Moreover, this structural change leads to a gradual reduction in the chelate cooperativity of the cyclization process and, at the same time, to an enhancement in the tendency of the macrocycles to stack, which critically influences the coupling between these consecutive supramolecular processes. [ABSTRACT FROM AUTHOR]

Dynamic covalent bonds endow liquid crystal elastomers (LCEs) with network rearrangeability, facilitating the fixation of mesogen alignment induced by external forces and enabling reversible actuation. In comparison, the bond exchange of supramolecular interactions is typically too significant to stably maintain the programmed alignment, particularly under intensified external stimuli. Nevertheless, remaking and recycling of supramolecular interaction‐based polymer networks are more accessible than those based on dynamic covalent bonds, as the latter are difficult to completely dissociate. Thus, preparing an LCE that possesses both supramolecular‐like exchangeability and covalent bond‐level stability remains a significant challenge. In this work, we addressed this issue by employing metal‐ligand bonds as the crosslinking points of LCE networks. As such, mesogen alignment can be repeatedly encoded through metal‐ligand bond exchange and stably maintained after programming, since the bond exchange rate is sufficiently slow when the programming and actuation temperatures are below the bond dissociation temperature. More importantly, the metal‐ligand bonds can be completely dissociated at high temperatures, allowing the LCE network to be dissolved in a solvent and reshaped into desired geometries via solution casting. Building on these properties, our LCEs can be fabricated into versatile actuators, such as reversible folding origami, artificial muscles, and soft robotics. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal Chemical Society Reviews. It includes a tutorial review on recent progress in solar-driven CO2 reduction, as well as several review articles on topics such as dendritic fibrous nanosilica, bioinspired oil-water separation, nanoscale chemical characterization, solar-driven water splitting, C-H functionalization, enzyme-responsive optical probes, aggregation-induced emission polymers, active template synthesis, insights into pH effect on hydrogen electrocatalysis, supramolecular-macrocycle-based cocrystals, and advanced electrolytes for aqueous zinc-ion batteries. The journal is published by The Royal Society of Chemistry, which is a leading chemistry community that reinvests its profits back into the chemistry community. [Extracted from the article]

Supramolecular polymers are typical self-assemblies, in which repeating monomer units are bonded together with dynamic and reversible noncovalent interactions. Supramolecular polymers can combine the advantages of polymer science and supramolecular chemistry. Aggregation-induced emission (AIE) means that a molecule remains faintly emissive in the dispersed state but intensively luminescent in a highly aggregated state. AIE has brought new opportunities and further development potential to the field of polymeric chemistry. The integration of AIE luminogens with supramolecular interactions can provide new vitality for supramolecular polymers. Therefore, it is essential for scientists to understand the preparation and applications of AIE-active supramolecular polymers. This review focuses on the recent advanced progress in the preparation of AIE-active supramolecular polymers. In addition, we summarize the newly developed supramolecular polymers with an AIE nature and their applications in chemical sensing, and in vitro and in vivo imaging, as well as the visualization of their structure and properties. Finally, the development trends and challenges of AIE-active supramolecular polymers are prospected. [ABSTRACT FROM AUTHOR]

We herein report five coordination polymers (CPs) and two supramolecular cages based on [MS4Cux]x−2 (M = W, Mo, x = 1, 2, ... 6) units and N-containing ligands, 9,10-di(1H-imidazol-1-yl)anthracene (dia), 1,6-di(1H-imidazol-1-yl)pyrene (dip), and 1,1′,1′′-(benzene-1,3,5-triyltris(methylene))tris(1,4-diazabicyclo[2.2.2]octan-1-ium) bromide (bmd), and 1,1′,1′′-((2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene))tris(1,4-diazabicyclo[2.2.2]octan-1-ium) (mbmd). Compounds 1 and 2 both contain the penta-nuclear [(WS4)Cu4]2+ cluster unit. The four Cu+ atoms were arranged in a distorted tetrahedron and rectangle around the (WS4)2− core in 1 and 2, respectively, affording a 3-connected unit in 1 and a 2-connected unit in 2. Compounds 3, 4 and 5 were built with the tri-topic organic ligand bmd; 3 and 4 contain penta-nuclear [WS4Cu4]2+ units, and 5 contains the hexa-nuclear [MoS4Cu5]3+ unit. However the connectives of the cluster units in 3, 4 and 5 and the final helical chain structures were similar. Compound 6 contains a tetra-nuclear [WS4Cu3I3]2− unit and positively charged mbmd ligand. The mbmd ligand was in a cis-conformation leading to a supramolecular cage, which accommodated an I− anion as guest. Compound 7 is isostructural to 6 but contains a [WS4Cu3Cl3]2− cluster unit, mbmd ligand and a Br− free anion. This work demonstrates that the number and arrangement of Cu+ around the (MS4)2− core can be varied with the synthesis conditions, affording heterothiometallic [(MS4)Cux]x−2 cluster units of versatile geometries and connectivities for building CPs. [ABSTRACT FROM AUTHOR]

Soft actuators that mimic the softness and deformability of living organisms have great potential for use in various fields. For most soft actuators, achieving both reprogrammable shape and high work capacity is crucial but challenging. These properties are mutually exclusive for liquid crystal elastomers (LCEs), an important type of soft actuators. Herein, a room‐temperature shape‐programmable LCE capable of high‐energy actuation is developed. Our approach utilizes hydrogen bonds to stabilize the aligned liquid crystal phases. The slow recovery of H‐bonds at room temperature provides a specific processing window, during which the sample shape can be programmed after the thermal treatment. The temperature‐dependent rearrangement of hydrogen bonds allows for fabrication of actuators with customized shapes in a facile do‐it‐yourself manner. Additionally, the integration of strong covalent cross‐links is vital for holding structural integrity. The combination of non‐covalent and covalent cross‐linking significantly improves the mechanical properties, enabling the actuators to perform reversible actuation with a work capacity (440 kJ m−3) higher than that of traditional LCEs (<100 kJ m−3). This study provides a turnkey strategy to address the conflict between shape reprogrammability and work capacity, advancing the development of soft actuators. [ABSTRACT FROM AUTHOR]

Developing advanced engineering polymers that combine high strength and toughness represents not only a necessary path to excellence but also a major technical challenge. Here for the first time a rigid‐flexible interlocking polymer (RFIP) is reported featuring remarkable mechanical properties, consisting of flexible polyurethane (PU) and rigid polyimide (PI) chains cleverly woven together around the copper(I) ions center. By rationally weaving PI, PU chains, and copper(I) ions, RFIP exhibits ultra‐high strength (twice that of unwoven polymers, 91.4 ± 3.3 MPa), toughness (448.0 ± 14.2 MJ m−3), fatigue resistance (recoverable after 10 000 cyclic stretches), and shape memory properties. Simulation results and characterization analysis together support the correlation between microstructure and macroscopic features, confirming the greater cohesive energy of the interwoven network and providing insights into strengthening toughening mechanisms. The essence of weaving on the atomic and molecular levels is fused to obtain brilliant and valuable mechanical properties, opening new perspectives in designing robust and stable polymers. [ABSTRACT FROM AUTHOR]

Circularly polarized luminescent (CPL) materials have garnered tremendous attention owing to their expanded optical properties beyond emission wavelength and intensity. Among these, the emerging circularly polarized organic ultralong room‐temperature phosphorescence (CP‐OURTP) materialsdemonstrating elegant and distinct features are of significant importance for their extended emission lifetime, which represent a novel frontier in research with promising scientific and technological applications across diverse fields. This review systematically outlines the traditional strategies to achieve CP‐OURTP including organic crystals, copolymerization, host–guest doping, a combination of the copolymerization and host–guest doping, spinning and twisting technology, and supramolecular polymer assembly. Importantly, the recent significant progress of CP‐OURTP in the chiral soft materials, such as liquid crystals (LCs) involving lyotropic LCs (cellulose nanocrystals, CNCs) and chiral thermotropic LCs (cholesteric LCs and chiral LC elastomers), is showcased. Finally, the practical applications of CP‐OURTP materials are summarized, and the review concludes with the perspectives on the current challenges and future opportunities for CP‐OURTP materials. This review aims to inspire the further innovations in the fabrication of advanced CP‐OURTP materials and enrich their promising applications. [ABSTRACT FROM AUTHOR]

With exceptional photochromic and photoluminescent properties, spiropyrans have demonstrated significant potential for advanced information encryption and anti‐counterfeiting applications. However, its inherent water insolubility leads to incompatibility with aqueous polymers, and even more, its ease of leaching from the matrix hinders the formation of stable stimuli‐responsive platforms through direct blending with all polymers. Here, the fabrication of amphiphilic spiropyran‐octapeptide molecules is reported that can spontaneously self‐assemble into highly water‐dispersible supramolecular nanofibers in water. These assemblies exhibit universal polymer matrix compatibility while retaining the rapid photo‐responsiveness of spiropyrans. The formation of strong interactions between the supramolecular assembly and polymer chains ensures the long‐term stability of the resultant stimuli‐responsive materials in aqueous environments. These platforms fully preserve the base polymers’ processing properties, with silk fibroin as the matrix offering exceptional opportunities for constructing photo‐responsive platforms in various forms (e.g., films, gels, fibers, and coatings) with multiple functionalities using diverse solution processing techniques. Integrating distinct photochromic and photoluminescent responses within a single format without interference, combined with environmental stability and processing flexibility, enables the creation of dual‐mode, high‐security encryption devices for diverse application scenarios. The outlined strategy provides innovative concepts for developing high‐performance, versatile intelligent systems utilizing stimulus‐responsive molecules. [ABSTRACT FROM AUTHOR]

Variable stiffness materials have shown considerable application in soft robotics. However, previously reported materials often struggle to reconcile high stiffness, stretchability, toughness, and self‐healing ability, because of the inherently conflicting requisite of these properties in molecular design. Herein, we propose a novel strategy that involves incorporating acid‐base ionic pairs capable of from strong crosslinking sites into a dense and robust hydrogen‐bonding network to construct rigid self‐healing polymers with tunable stiffness and excellent toughness. To demonstrate these distinct features, the polymer was employed to serve as the strain‐regulation layers within a fiber‐reinforced pneumatic actuator (FPA). The exceptional synergy between the configuration versatility of FPA and the dynamic molecular behavior of the supramolecular polymers equips the actuator with simultaneous improvement in motion dexterity, multimodality, loading capacity, robustness, and durability. Additionally, the concept of integrating high dexterity at both macro‐ and micro‐scale is prospective to inspire the design of intelligent yet robust devices across various domains. [ABSTRACT FROM AUTHOR]

Adhesives have been widely used to splice and repair materials to meet practical needs of humanity for thousands of years. However, developing robust adhesives with balanced adhesive and cohesive properties still remains a challenging task. Herein, we report the design and preparation of a robust mechanically interlocked [an]daisy chain network (DCMIN) adhesive by orthogonal integration of mechanical bonds and 2‐ureido‐4[1H]‐pyrimidone (UPy) H‐bonding in a single system. Specifically, the UPy moiety plays a dual role: it allows the formation of a cross‐linked network and engages in multivalent interactions with the substrate for strong interfacial bonding. The mechanically interlocked [an]daisy chain, serving as the polymeric backbone of the adhesive, is able to effectively alleviate applied stress and uphold network integrity through synergistic intramolecular motions, and thus significantly improves the cohesive performance. Comparative analysis with the control made of the same quadruple H‐bonding network but with non‐interlocked [an]daisy chain backbones demonstrates that our DCMIN possesses superior adhesion properties over a wide temperature range. These findings not only contribute to a deep understanding of the structure‐property relationship between microscopic mechanical bond motions and macroscopic adhesive properties but also provide a valuable guide for optimizing design principles of robust adhesives. [ABSTRACT FROM AUTHOR]

Porous titanium addresses the longstanding orthopedic challenges of aseptic loosening and stress shielding. This work expands on the evolution of porous Ti with the manufacturing of hierarchically porous, low stiffness, ductile Ti scaffolds via direct-ink write (DIW) extrusion and sintering of inks containing Ti and NaCl particles. Scaffold macrochannels were filled with a subtherapeutic dose of recombinant bone morphogenetic protein-2 (rhBMP-2) alone or co-delivered within a bioactive supramolecular polymer slurry (SPS) composed of peptide amphiphile nanofibrils and collagen, creating four treatment conditions (Ti struts: microporous vs. fully dense; BMP-2 alone or with SPS). The BMP-2-loaded scaffolds were implanted bilaterally across the L4 and L5 transverse processes in a rat posterolateral lumbar fusion model. In-vivo bone growth in these scaffolds is evaluated with synchrotron X-ray computed microtomography (µCT) to study the effects of strut microporosity and added biological signaling agents on the bone formation response. Optical and scanning electron microscopy confirms the ∼100 µm space-holder micropore size, high-curvature morphology, and pore fenestrations within the struts. Uniaxial compression testing shows that the microporous strut scaffolds have low stiffness and high ductility. A significant promotion in bone formation was observed for groups utilizing the SPS, while no significant differences were found for the scaffolds with the incorporation of micropores. By 2050, the anticipated number of people aged 60 years and older worldwide is anticipated to double to 2.1 billion. This rapid increase in the geriatric population will require a corresponding increase in orthopedic surgeries and more effective materials for longer indwelling times. Titanium alloys have been the gold standard of bone fusion and fixation, but their use has longstanding limitations in bone-implant stiffness mismatch and insufficient osseointegration. We utilize 3D-printing of titanium with NaCl space holders for large- and small-scale porosity and incorporate bioactive supramolecular polymers into the scaffolds to increase bone growth. This work finds no significant change in bone ingrowth via space-holder-induced microporosity but significant increases in bone ingrowth via the bioactive supramolecular polymers in a rat posterolateral fusion model. [Display omitted] [ABSTRACT FROM AUTHOR]

Nonlinear supramolecular polymers (NLSPs) exhibit the merits of reversibility and tunability, along with a unique topological structure. These features contribute to the creation of novel supramolecular polymer species and drive advancements in macromolecular engineering, making NLSPs a promising direction for generating highly functional and complex structures with diverse applications. This article reviews recent advances in NLSPs, including star, brush, hyperbranched, dendritic, cross-linked, and cyclic topological supramolecular polymers, from three key perspectives: controlled synthesis, tunable self-assembly, and functional applications. Firstly, the direct and indirect synthesis strategies used to construct various NLSPs are discussed. Subsequently, the regulation methods of supramolecular self-assembly based on NLSPs are rationalized by considering internal structure parameters and external environmental responses. Finally, comprehensive summaries of the potential applications of NLSPs in biomedical materials, photoelectric materials, self-healing materials, degradable and recycling materials, as well as catalytic materials, are provided. These applications highlight the versatility and promise of NLSPs across various industries. This article addresses key scientific problems and existing challenges in this field. With the rapidly growing area of NLSPs, it is anticipated that they will shape the future of supramolecular chemistry and polymer science, and hold great promise for research fields such as chemical engineering, biomedicine, and the environment. [ABSTRACT FROM AUTHOR]

The use of the consistency index, as determined from fitting rheological data to the Herschel–Bulkley model, is described such that it may yield systematic trends that allow a very convenient description of the dissipative flow properties of linear and branched (bio)polymers in general, both in molecular and weakly associated supramolecular solutions. The effects of charge-mediated interactions by the systematic variation of the ionic strength and hydrogen bonding by a systematic variation in pH, using levels that are frequently encountered in systems used in practice, is investigated. These effects are then captured using the associated changes in the intrinsic viscosity to highlight the above-mentioned trends, while it also acts as an internal standard to describe the data in a concise form. The trends are successfully captured up to 100 times the polymer coil overlap and 100,000 times the solvent viscosity (or consistency index). These results therefore enable the rapid characterization of biopolymer systems of which the morphology remains unknown and may continue to remain unknown due to the wide-ranging monomer diversity and a lack of regularity in the structure, while the macromolecular coil size may be determined readily. [ABSTRACT FROM AUTHOR]

Supramolecular polymer networks (SPNs) are celebrated for their dynamic nature, yet they often exhibit inadequate mechanical properties. Thus far, the quest to bolster the mechanical resilience of SPNs while preserving their dynamic character presents a formidable challenge. Herein, we introduce [2]rotaxane into SPN to serve as another cross-link, which could effectively enhance the mechanical robustness of the polymer network without losing the dynamic properties. Compared with SPN, the dually cross-linked network (DPN) demonstrates superior breaking strength, Young's modulus, puncture force and toughness, underscoring its superior robustness. Furthermore, the cyclic tensile tests reveal that the energy dissipation capacity of DPN rivals, and in some cases surpasses, that of SPN, owing to the efficient energy dissipation pathway facilitated by [2]rotaxane. In addition, benefiting from stable topological structure of [2]rotaxane, DPN exhibits accelerated recovery from deformation, indicating superior elasticity compared to SPN. This strategy elevates the performance of SPNs across multiple metrics, presenting a promising avenue for the development of high-performance dynamic materials. [ABSTRACT FROM AUTHOR]

Supramolecular polymers, as a type of dynamic polymers, are subordinate to the interdisciplinary field of polymer chemistry and supramolecular chemistry, whose development has greatly promoted the prosperity of new materials. Notably, molecular weight is one of the most important parameters of supramolecular polymers, which affects the physical/chemical properties and processing applications of materials. Developing new methods for characterizing the molecular weight of supramolecular polymers is crucial for advancing the development of supramolecular polymers. In this review, we elaborate and summarize three strategies for characterizing the molecular weight of supramolecular polymers that recently reported by our research group according to the characteristics of supramolecular polymers, including (1) the molecular weight distinction corresponding to variable fluorescence colors, (2) matching different molecular weights with different fluorescence lifetime, (3) transforming supramolecular polymers into mechanically interlocked polymers or covalent polymers. Besides, we also discuss the limitations of current methods for characterizing supramolecular polymers. We hope that this review can promote the development of supramolecular polymers and significantly inspire to exploit new methods to characterizing molecular weight of supramolecular polymers. [ABSTRACT FROM AUTHOR]

Conductive polymer hydrogels (CPHs) are gaining considerable attention in developing wearable electronics due to their unique combination of high conductivity and softness. However, in the absence of interactions, the incompatibility between hydrophobic conductive polymers (CPs) and hydrophilic polymer networks gives rise to inadequate bonding between CPs and hydrogel matrices, thereby significantly impairing the mechanical and electrical properties of CPHs and constraining their utility in wearable electronic sensors. Therefore, to endow CPHs with good performance, it is necessary to ensure a stable and robust combination between the hydrogel network and CPs. Encouragingly, recent research has demonstrated that incorporating supramolecular interactions into CPHs enhances the polymer network interaction, improving overall CPH performance. However, a comprehensive review focusing on supramolecular CPH (SCPH) for wearable sensing applications is currently lacking. This review provides a summary of the typical supramolecular strategies employed in the development of high‐performance CPHs and elucidates the properties of SCPHs that are closely associated with wearable sensors. Moreover, the review discusses the fabrication methods and classification of SCPH sensors, while also exploring the latest application scenarios for SCPH wearable sensors. Finally, it discusses the challenges of SCPH sensors and offers suggestions for future advancements. [ABSTRACT FROM AUTHOR]

Clusterization‐triggered emissive (CTE) materials have attracted great attention in recent years. The regulation of the emission property of materials with CTE property through supramolecular interactions is an excellent strategy for the construction of smart fluorescent materials. In this work, we have prepared a regulatable supramolecular polymer network with CTE properties through pillararene‐based host−guest interactions. The pillar[5]arene‐grafted poly(methyl methacrylate) (PMMA) showed a classic CTE character. After adding Brooker's merocyanine‐grafted polymer to the solution of the pillar[5]arene‐containing PMMA, the supramolecular polymer network gel formed by the host−guest interactions between pillararene and Brooker's merocyanine guest. This supramolecular network showed brighter fluorescence than the pillar[5]arene‐grafted PMMA in the solid state. In addition, the fluorescence emission of the supramolecular network can be further regulated by pH conditions. After adding an acid, the Brooker's merocyanine‐containing guest polymer was protonated, and the supramolecular network changed to a protonated network through host−guest interactions between protonated Brooker's merocyanine guest and pillararene. Interestingly, the fluorescence was quenched when the supramolecular network turned into the protonated network. After adding a base, the protonated network can convert back to the original network, along with recovery of the fluorescence. Therefore, the regulation of the fluorescence of the supramolecular polymer materials with CTE was successfully realized by pillararene‐based host−guest interactions. Furthermore, this tailorable fluorescent supramolecular polymer network system was applied as an information encryption material. [ABSTRACT FROM AUTHOR]

Supramolecular polymers (SPs) are constructed through non‐covalent interactions. The dynamic or reversible nature of SPs endows them unique physical and chemical properties, such as self‐adaptive and stimuli‐response abilities. The topological structures of SPs play an important role in determining the physicochemical properties and functionality. Hyperbranched polymers (HBPs) are highly branched 3D macromolecules with linear, dendritic, and terminal units, which makes them versatile candidates for the construction of SPs with fascinating architectures. The resultant HBP‐based SPs perfectly integrated the dynamic/reversible nature of SPs and the 3D topological features and multifunctionality of HBP polymers. To date, various types of HBP‐based SPs and their assemblies have been constructed, and their potential applications have been explored as well. This article overviews the current progress on self‐assembly of HBP‐based SPs. The strategies for construction of HBP‐based SPs and their assemblies are discussed. Typical potential applications of the assemblies of HBP‐based SPs are also introduced. [ABSTRACT FROM AUTHOR]

Porous frameworks with controlled pore structure and tunable aperture are greatly demanded. However, precise synthesis of this kind of materials is a formidable challenge. Herein, we report the fabrication of two‐dimensional (2D) supramolecular polymer frameworks using a precisely synthesized rod‐like helical polyisocyanide as link. Four three‐arm star‐shaped polyisocyanides with the degree of the polymerization of 10, 20, 30 and 40, and having 2‐ureido‐4[1H]‐pyrimidinone (UPy) terminals were synthesized. 2D‐Crystalline polymer frameworks with apertures of 5.3, 10.1, 13.9, and 19.1 nm were respectively obtained through intermolecular hydrogen bonding interaction between the terminal Upy units. The pore aperture is dependent on the length of polyisocyanide backbone. Thus, well‐defined supramolecular polymer frameworks with controlled and uniform hexagonal pores were obtained, as proved by small‐angle X‐ray scattering (synchrotron radiation facility), atomic force microscopy, and Brunauer–Emmett–Teller analyses. The frameworks with uniform large pore aperture were used to purify nanomaterials and immobilize biomacromolecules. For instance, the membranes of the polymer frameworks could size‐fractionation of silver nanoparticles into uniform nanoparticles with very low dispersity. The frameworks with large aperture facilitated the inclusion of myoglobin and enhanced the stability and catalytic activity. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal CrystEngComm, which focuses on the design and understanding of solid-state and crystalline materials. The issue includes various articles and papers on topics such as organic charge transfer complexes, metal organic frameworks, mechanical properties of cocrystals, and scintillation crystals. The journal is published by The Royal Society of Chemistry, a leading chemistry community that reinvests its profits back into the chemistry community. [Extracted from the article]

Proton supply is as critical as O2 activation for artificial photosynthesis of hydrogen peroxide (H2O2) via two‐electron oxygen reduction reaction (2e− ORR). However, proton release via water dissociation is frequently hindered because of the sluggish water oxidation reaction (WOR), extremely limiting the efficiency of photocatalytic H2O2 production. To tackle this challenge, carboxyl‐enriched supramolecular polymer (perylene tetracarboxylic acid—PTCA) is elaborately prepared by molecular self‐assembly for overall photosynthesis of H2O2. Interestingly, the interconversion between carboxyl as Brønsted acid and its conjugated base realizes rapid proton circulation. Through this efficient tandem proton transfer process, the spatial effect of photocatalytic reduction and oxidation reaction is greatly enhanced with reduced reaction barrier. This significantly facilitates 2e− photocatalytic ORR to synthesize H2O2 and in the meanwhile promotes 4e− photocatalytic WOR to evolve O2. Consequently, the as‐developed PTCA exhibits a remarkable H2O2 yield of 185.6 μM h−1 in pure water and air atmosphere under visible light illumination. More impressively, an appreciable H2O2 yield of 78.6 μM h−1 can be well maintained in an anaerobic system owing to in situ O2 generation by 4e− photocatalytic WOR. Our study presents a novel concept for artificial photosynthesis of H2O2 via constructing efficient proton transfer pathway to enable rapid proton circulation. [ABSTRACT FROM AUTHOR]

[Display omitted] Supramolecular polymer bottlebrushes (SPBs) consist in the 1D self-assembly of building blocks composed of a self-assembling core with pendant polymer arms. Kinetic hurdles often hinder their stimuli-responsiveness in solution. Changing the nature of the solvent should alleviate these hurdles by modulating the self-association strength, leading to stimuli-responsive SPBs. The SPBs were formed, in various solvents, by hydrogen bond-driven self-assembly of an azobenzene-bisurea decorated with poly(ethylene oxide) polymer arms. The photo-isomerization of the azobenzene unit was studied by UV/visible spectroscopy and proton NMR spectroscopy, whereas the consequences on supramolecular self-assembly were studied by small angle neutron and X-ray scattering. In water, the assembly was previously shown to be driven by both hydrogen-bonds and strong hydrophobic effects, the latter rendering the system kinetically frozen and the disassembly irreversible. Here we show that in organic solvents such as toluene or chloroform, reversible light-responsive dissociation is achieved. Solvophobic effects in these solvents are expected to be much weaker than in water, which probably allows reversibility of the light-response in the former solvents. The key role of the solvent on the reversibility of the process opens up new perspectives for the design of stimuli-responsive SPBs and their applications in various fields. [ABSTRACT FROM AUTHOR]

During the construction of supramolecular polymers of smaller nanoparticles/nanoclusters bearing hierarchy and homochirality, the mechanism understanding via intuitive visualization and precise cross-scale chirality modulation is still challenging. For this goal, a cooperative self-assembly strategy is here proposed by using ionic complexes with uniform chemical composition comprising polyanionic nanocluster cores and surrounded chiral cationic organic components as monomers for supramolecular polymerization. The single helical polymer chains bearing a core-shell structure at utmost length over 20 μm are demonstrated showing comparable flexibility resembling covalent polymers. A nucleation-elongation growth mechanism that is not dealt with in nanoparticle systems is confirmed to be accompanied by strict chiral self-sorting. A permeable membrane prepared by simple suction of such supramolecular polymers displays high enantioselectivity (e.e. 98% after four runs) for separating histidine derivatives, which discloses a benefiting helical chain structure-induced functionalization for macroscopic supramolecular materials in highly efficient racemate separation. Understanding the mechanism for supramolecular polymer assembly from nanoclusters bearing hierarchy and homochirality is challenging. Here, the authors report a cooperative self-assembly strategy using ionic complexes with chiral surfactants through a nucleation-elongation growth mechanism with chiral self-sorting and prepare a permeable membrane for the separation of histidine derivatives. [ABSTRACT FROM AUTHOR]

Many stimuli‐responsive materials harness the reversible association of supramolecular binding motifs to enable advanced functionalities such as self‐healing, switchable adhesion, or mechanical adaptation. Despite extensive research into the structure–property relationships of these materials, direct correlations between molecular‐level changes in supramolecular binding and macroscopic material behaviors have mostly remained elusive. Here, we show that this challenge can be overcome with supramolecular binding motifs featuring integrated binding indicators. We demonstrate this using a novel motif that combines a hydrogen‐bonding ureido‐4‐pyrimidinone (UPy) with two strategically placed pyrene fluorophores. Dimerization of this motif promotes pyrene excimer formation, facilitating the straightforward optical quantification of supramolecular assembly under various conditions. We exploit the new motif as a supramolecular cross‐linker in poly(methyl acrylate)s to probe the extent of (dis)assembly as a function of cross‐linker content, processing history, and applied stimuli. We demonstrate that the stimuli‐induced dissociation of hydrogen‐bonding linkages strongly depends on the initial cross‐link density, which also dictates whether the force‐induced dissociation in polymer films correlates with the applied stress or strain. Thus, beyond introducing a robust tool for the in situ study of dynamic (dis)assembly mechanisms in supramolecular systems, our findings provide new insights into the mechanoresponsive behavior of such materials. [ABSTRACT FROM AUTHOR]

Metallo‐supramolecular polymer networks (MSPNs) are fabricated from the crosslinking of polymers by discrete supramolecular coordination complexes. Due to the availability of various coordination complexes, e. g., 2D macrocycles and 3D nanocages, the MSPNs have been recently developed with broadly tunable visco‐elasticity and enriched functions inherited from the coordination complexes. The coordination complexes possess enriched topologies and unique structural relaxation dynamics, rendering them the capability to break the traditional tradeoffs of polymer systems for the design of materials with enhanced mechanical performance. The structure‐property relationship studies are critical for the material‐by‐design of MSPNs, while the spatiotemporal investigations are desired for the exploration of dynamics information. The work summarizes recent studies on the unique ligand‐exchange kinetics and the multi‐level structural relaxation dynamics of MSPNs. The MSPNs' mechanical properties can be quantitatively correlated with the dynamics for understanding the structure‐property relationship. This concept will not only serve to attract more researchers to engage in the study of the structure‐activity relationship of MSPNs but also inspire innovative research findings pertaining to the application of MSPNs. [ABSTRACT FROM AUTHOR]

A supramolecular zwitterionic hydrogel based on polyacrylamide/carboxylated cellulose nanofibers/betaine citrate is constructed. The non-covalent interactions within the supramolecular zwitterionic hydrogels results in the formation of inter-crosslinked polymer networks. The strong coordination between betaine citrate with negative loading groups and zinc ions leads to rapid transfer of zinc ions by molecular slippage inside the polymer, which improved the transfer kinetics of zinc ions. Meanwhile, anchoring of various polar groups in the supramolecular zwitterionic hydrogel on the surface of the zinc anode provides active sites for the rapid and uniform deposition of zinc ions. [Display omitted] • Molecular slip mechanisms enhance the diffusion kinetics of Zn2+. • Zwitterionic coordination effect improves deposition kinetics. • Polar group anchoring effects protect zinc anodes. • Zn mental battery exhibits outstanding cycle performance. The severe hydrogen evolution reaction and parasitic side reaction on Zn anode are the key issues which hinder the development of aqueous Zn-based energy storage devices. Herein, a polyacrylamide/carboxylated cellulose nanofibers/betaine citrate supramolecular zwitterionic hydrogels with molecular slip effects are proposed for enhancing Zn2+ diffusion and protecting Zn anodes. Non-covalent interactions within supramolecular hydrogels forms the skeleton for molecular slip and the strong coordination of carboxyl and amino groups with Zn2+ further facilitates the rapid Zn2+ transfer. Additionally, anchoring carboxyl and amino groups at the anode promotes the uniform deposition of Zn2+and protects Zn anode. On the basis of molecular slip mechanism and anchoring effect in the supramolecular zwitterionic hydrogels, Zn||Zn symmetric batteries undergo 800 h of stable electroplating stripping at a depth of discharge of 80 %. Zn||Cu asymmetric batteries exhibit an impressive average coulombic efficiency of 99.4 % over a remarkable span of 900 cycles at a current density of 15 mA cm−2. Furthermore, Zn||NH 4 V 4 O 10 batteries successfully undergo over 1,000 cycles at a current density of 0.5 A g−1. Intrinsic ion diffusion mechanism of supramolecular hydrogel electrolytes provides an original strategy for the application of high-performance Zn-based energy storage devices. [ABSTRACT FROM AUTHOR]

The integration of polymers, supramolecular macrocycles and aggregation‐induced emission (AIE) molecules provides numerous possibilities for constructing various functional supramolecular systems. Herein, we constructed supramolecular assembled systems based on discrete macrocyclic polymer hosts via the cooperation of hydra‐headed macrocycles containing two or three pillar[5]arene units (defined as P2, P3), the block polymer F127 and AIE molecules (alkyl‐cyano modified tetraphenylethene, alkyl‐triazole‐cyano modified 9,10‐distyrylanthracene, defined as TPE‐(CN)4 and DSA‐(TACN)2). Compared with the binary assembly between hydra‐headed hosts or F127 and AIE molecules, cascaded supramolecular assembly‐induced emission enhancement (SAIEE) in aqueous solution was achieved in discrete macrocyclic polymer‐based supramolecular assembled systems. Considering the cascaded SAIEE performance, we have successfully applied discrete macrocyclic polymer‐based supramolecular assembled systems to bioimaging and constructed an artificial light‐harvesting system (LHs) to explore more potential applications. The supramolecular assembly form of discrete macrocyclic polymers hosts and AIE molecules proposed in this work provides new inspiration for the construction and application of high‐performance supramolecular luminescent systems. [ABSTRACT FROM AUTHOR]

The self‐assembly behavior of a heptanediamide derivative that contains a four‐ring fused π‐skeleton on its central methylene carbon atom has been examined. This molecule, which also contains two octyl chains, gelated the nonpolar solvent methylcyclohexane through the formation of fibrous nanostructures with hydrogen‐bonding networks through a cooperative nucleation–elongation process. The supramolecular polymerization is accompanied by bathochromic shifts of both the absorption and fluorescence bands while maintaining a fluorescence quantum yield comparable to that of the monomeric state. Theoretical calculations provided an energetically stable structure, in which the π‐skeletons are stacked with an offset of more than 8.0 Å, replicating the experimentally observed absorption change due to exciton coupling. Moreover, a slow transition with an inversion of the chiral arrangement of the π‐conjugated moieties was induced by replacing the octyl chains with chiral alkyl chains. Our molecular‐design strategy was further applied to a five‐ring fused π‐skeleton, which also forms an offset π‐stacking arrangement and exhibits more effective chiral exciton coupling in the aggregated state. [ABSTRACT FROM AUTHOR]

In the last decades, chemists have developed methods to synthesize helical molecular architectures using a combination of covalent and non‐covalent interactions. Very recently, the new class of completely covalent, one‐handed helical ladder polymers has vigorously emerged. Such polymers can be rationally and programmably obtained through an approach guided by the principles of chirality‐assisted‐synthesis (CAS) and making use synergically of two disciplines that have so far rarely interacted: non‐planar chiral π‐conjugated synthons and ladder polymer chemistry. The precise programmability of the 3D structure and new mechanical and chiroptical properties will lead to potential applications in areas such as enantiorecognition, catalysis, spintronics and chiral‐related optoelectronics. This minireview examines the emerging field of one‐handed helical ladder polymers, analyzing their synthesis, applications, and limitations. [ABSTRACT FROM AUTHOR]

The document is the contents list for an issue of the journal Chemical Communications. It includes the titles and authors of various articles and features that will be included in the issue. The articles cover a range of topics in the field of chemistry, including recent advances in biosensing systems, continuous flow synthesis, electrochemical construction, and more. The journal is published by The Royal Society of Chemistry, a leading chemistry community. [Extracted from the article]

Metallo-supramolecular polyelectrolytes (MEPE) have a variety of attractive properties concerning electrochromism, spin-crossover, rheology, and cell differentiation. Previous studies suggest that these polynuclear structures can be regarded as an assembly of individual subunits and mononuclear complexes can act as models. In this study, we synthesize a monotopic and a ditopic terpyridine ligand with pyridinium units as well as the corresponding iron and ruthenium MEPEs and their mononuclear counterparts. UV-vis studies show that the mononuclear complexes have similar absorption properties to MEPEs. Furthermore, all complexes and MEPEs exhibit electrochromic behavior. Yet only the MEPEs can be deposited on different substrates using a layer-by-layer approach which makes them attractive for applications as electrochromic devices. However, the low solubility particularly of the ruthenium MEPE, renders characterization in solution impractical. Hence, the use of mononuclear complexes with similar monotopic ligands as presented herein can act as a first instance to evaluate the properties of corresponding MEPEs, facilitating the development of metallo-supramolecular materials. [ABSTRACT FROM AUTHOR]

Singlet‐to‐triplet intersystem crossing (ISC) in organic molecules is intimately connected with their geometries: by modifying the molecular shape, symmetry selection rules pertaining to spin‐orbit coupling can be partially relieved, leading to extra matrix elements for increased ISC. As an analog to this molecular design concept, the study finds that the lattice symmetry of supramolecular polymers also defines their triplet formation efficiencies. A supramolecular polymer self‐assembled from weakly interacting molecules is considered. Its 2D oblique unit cell effectively renders it as a coplanar array of 1D molecular columns weakly bound to each other. Using momentum‐resolved photoluminescence imaging in combination with Monte Carlo simulations, the study found that photogenerated charge carriers in the supramolecular polymer predominantly recombine as spin‐uncorrelated carrier pairs through inter‐column charge transfer states. This lattice‐defined recombination pathway leads to a substantial triplet formation efficiency (≈60%) in the supramolecular polymer. These findings suggest that lattice symmetry of micro‐/macroscopic structures relying on intermolecular interactions can be strategized for controlled triplet formation. [ABSTRACT FROM AUTHOR]

Dynamic covalent polymers (DCPs) that strike a balance between high performance and rapid reconfiguration have been a challenging task. For this purpose, a solution is proposed in the form of a new dynamic covalent supramolecular motif—guanidine urea structure (GUAs). GUAs contain complex and diverse chemical structures as well as unique bonding characteristics, allowing guanidine urea supramolecular polymers to demonstrate advanced physical properties. Noncovalent interaction aggregates (NIAs) have been confirmed to form in GUA‐DCPs through multistage H‐bonding and π‐π stacking, resulting in an extremely high Young's modulus of 14 GPa, suggesting remarkable mechanical strength. Additionally, guanamine urea linkages in GUAs, a new type of dynamic covalent bond, provide resins with excellent malleability and reprocessability. Guanamine urea metathesis is validated using small molecule model compounds, and the temperature dependent infrared and rheological behavior of GUA‐DCPs following the dissociative exchange mechanism. Moreover, the inherent photodynamic antibacterial properties are extensively verified by antibacterial experiments. Even after undergoing three reprocessing cycles, the antibacterial rate of GUA‐DCPs remains above 99% after 24 h, highlighting their long‐lasting antibacterial effectiveness. GUA‐DCPs with dynamic nature, tuneable composition, and unique combination of properties make them promising candidates for various technological advancements. [ABSTRACT FROM AUTHOR]

Liquid crystals have been extensively used in various applications, such as optoelectronic devices, biomedical applications, sensors and biosensors, and packaging, among others. Liquid crystal polymers are one type of liquid crystal material, combining their intrinsic properties with polymeric flexibility for advanced applications in displays and smart materials. For instance, liquid crystal polymers can serve as drug nanocarriers, forming cubic or hexagonal mesophases, which can be tailored for controlled drug release. Further applications of liquid crystals and liquid crystal polymers include the preparation of membranes for separation processes, such as wastewater treatment. Furthermore, these materials can be used as ion-conducting membranes for fuel cells or lithium batteries due to their broad types of mesophases. This review aims to provide an overall explanation and classification of liquid crystals and liquid crystal polymers. Furthermore, the great potential of these materials relies on their broad range of applications, which are determined by their unique properties. Moreover, this study provides the latest advances in liquid crystal polymer-based membranes and their applications, focusing especially on fuel cells. Moreover, future directions in the applications of various liquid crystals are highlighted. [ABSTRACT FROM AUTHOR]

It remains a huge challenge to efficiently recycle the printed circuit boards (PCBs) because of the diversity and complexity of the PCBs in terms of material composition. The recycling of PCBs highly depends on the design of the polymers that make up the polymer substrates and conductive pastes. Herein, closed‐loop recyclable plastics for use as the polymer substrates and for the preparation of the conductive pastes are fabricated by dynamically cross‐linking phenylboronic acid‐functionalized poly(methylmethacrylate) (PMMA‐B) and poly(urea‐urethane) (PUU‐B) with boroxines. The closed‐loop recyclable plastic, which is denoted as PMMA‐PUU exhibits a breaking strength of 71.0 MPa and Young's modulus of 1.8 GPa. Because of the dynamic nature of boroxines, the PMMA‐PUU0.6 plastic can be depolymerized in the N, N‐dimethylacetamide/ethanol mixture solvent. The depolymerized PMMA and PUU can be efficiently recovered in high yields and purity through their solubility differences in selective solvents. Conductive pastes suitable for printing of electrical circuits are fabricated through complexation of Ag particles with PMMA‐PUU. PCBs composed of PMMA‐PUU substrates and PMMA‐PUU‐based conductive pastes are flexible, healable, and recyclable. The closed‐loop recycling of the PCBs enables the collection of highly purified Ag particles, PMMA‐B, and PUU‐B monomers even when the PCBs are mixed with polymer wastes. [ABSTRACT FROM AUTHOR]

The polymorphic behavior of conjugated polymers enables tunable optoelectronic properties, but their transport mechanism remains elusive due to the inherent complexity and uncontrollability of polymorphic self‐assembly behaviors and electronic processes at various length scales, alongside the ambiguous relationship between solution and solid states. Herein, precise control of multi‐level supramolecular self‐assembly of a polymorphic conjugated polymer, N‐PDPP4T‐HD with two distinct semi‐crystalline aggregated phases (β1 and β2) via solvent engineering is demonstrated. β1 forms 1D worm‐like nanostructures in solution, whereas β2 generates 2D nanoscale lamellar configuration, confirmed by experimental observation and molecular dynamic simulation. Such solution‐state features are inherited in the solid state (1D nanofibers for β1 and 2D granular‐like structures for β2). X‐ray characterizations reveal larger crystalline domains on the nanometer scale, reduced π‐stacking distance on the Ångstrom scale, and diminished paracrystallinity disorder for solid‐state β2. Going beyond conventional DC transistor characterizations, contact‐free ultrafast terahertz spectroscopy to unveil AC short‐range, intrinsic transport properties is employed. Longer charge carrier scattering time and thus intrinsic mobility of β2 result in threefold higher short‐range photoconductivity than β1. This work establishes the “solution structure – solid structure – local transport” relation in polymorphic conjugated polymers and provides new opportunities for high‐performance plastic electronic devices. [ABSTRACT FROM AUTHOR]

The design of robotic soft matter capable of emulating the complex movements of living organisms such as mechanical actuation, shape transformation, and autonomous translation remains a grand challenge in soft materials science. Functionalized hydrogels are excellent candidates for such materials since they can operate in water and are highly responsive to their environment, but their response times can be slow. This work investigates fast photoactuation of hybrid bonding hydrogels composed of peptide amphiphile (PA) supramolecular nanofibers bonded covalently to merocyanine‐based (MCH+) photoresponsive networks. By incorporating ionizable acrylic acid (AA) co‐monomers in these networks, photoactuation at nearly neutral pH is observed, which in turn enables a new mechanism to accelerate the response by triggering the bundling of supramolecular nanofibers by rapid proton exchange reactions. Furthermore, this rapid response and its consequent large shape transformations lead to hydrogels capable of spontaneously tracking external light sources inspired by pedicellariae, defensive organs present in echinoderms like the starfish and the sea urchin. This work suggests that hybrid bonding polymers (HBPs), which leverage the interplay between supramolecular assemblies and covalent networks, offer novel strategies to design rapidly actuating soft robotic materials. [ABSTRACT FROM AUTHOR]

A microwave technique was used to prepare a superabsorbent polymer (SAP) by grafting two hydrophilic monomers onto a polysaccharide substrate. The monomers used were acrylic acid (AA) or acrylamide (AM) and were grafted onto a pullulan (PUL) substrate to form PUL-g-AA (SAP1) and PUL-g-AM (SAP2), respectively. The monomers (AM/AA) were grafted together onto a PUL substrate to form PUL-g-(AM/AA) (SAP3). Grafting parameters such as grafting efficiency with the percentage, the conversion of monomer into polymer, gel content, water retention, water adsorption capacity, and swelling kinetics were determined. Additionally, the effect of environmental pH (2, 4, 7, 9, and 12) and sodium dodecylbenzene sulfonate (SDBS) surfactant was evaluated, where 1, 2, 3, 4, and 5 mM of SDBS was added to form SAP4 to SAP8. The FTIR results show that AM was grafted onto PUL through an aliphatic C-N bond, while AA grafting occurred through a single C-C bond. The grafting efficiency with AM was higher than with AA, as well as showing a superior gel content. Water absorbance capacity and water retention increased with the grafting of AA and AM together for SAP3. The highest absorbent capacity, water retention, gel content, and grafting parameters values were obtained with a 3 mM SDBS content and a pH of 7. The swelling kinetics showed that the increases in the theoretical and experimental swelling equilibriums were 72% and 82%, respectively, for SAP6 compared to the values of these parameters for SAP3. The water absorption capacity of the hydrogel increases upon increasing the pH to 7 and then gradually decreases. XRD demonstrated the improved crystallinity and crystalline size of the hydrogel after grafting polymerization of AM/AA onto PUL, in addition to enhanced thermal stability. On the contrary, FE-SEM demonstrated that SDBS improves the porosity and pore size of the hydrogel surface with SAP6. [ABSTRACT FROM AUTHOR]

When encountering heavy oil reservoirs during drilling, due to the change in pressure difference inside the well, heavy oil will invade the drilling fluid, and drilling fluid will spill into the reservoir along the formation fractures, affecting the drilling process. A supramolecular polymer gel-based temporary plugging agent was prepared using acrylamide (AM), butyl acrylate (BA), and styrene (ST) as reacting monomers, N, N-methylenebisacrylamide (MBA) as a crosslinking agent, ammonium persulfate (APS) as an initiator, and poly(vinyl alcohol) (PVA) as a non-covalent component. A supermolecular polymer gel with a temperature tolerance of 120 °C and acid solubility of 90% was developed. The experimental results demonstrated that a mechanically robust, thermally stable supramolecular polymer gel was successfully synthesized through the copolymerization of AM, BA, and ST, as well as the in situ formation hydrogen bonding between poly (AM-co-BA-co-ST) and PVA, leading to a three-dimensional entangled structure. The gel-forming solution possessed excellent gelling performance even in the presence of a high content of salt and heavy oil, demonstrating superior resistance to salt and heavy oil under harsh reservoir conditions. High-temperature and high-pressure plugging displacement experiments proved that the supramolecular polymer gel exhibited high pressure-bearing capacity, and the blocking strength reached 5.96 MPa in a wedge-shaped fracture with a length of 30 cm. Furthermore, the dissolution rate of the supramolecular polymer gel was as high as 96.2% at 120 °C for 48 h under a 15% HCl solution condition. [ABSTRACT FROM AUTHOR]

Amino acid-derived self-assembled nanofibers comprising supramolecular chiral hydrogels with unique physiochemical characteristics are highly demanded biomaterials for various biological applications. However, their narrow functionality often limits practical use, necessitating the development of biomaterials with multiple features within a single system. Herein, chiral co-assembled hybrid hydrogel systems termed LPH-EGCG and DPH-EGCG were constructed by co-assembling L/DPFEG gelators with epigallocatechin gallate (EGCG) followed by cross-linking with polyvinyl alcohol (PVA) and hyaluronic acid (HA). The developed hybrid hydrogels exhibit superior mechanical strength, self-healing capabilities, and adhesive properties, owing to synergistic non-covalent interactions. Integrating hydrophilic polymers enhances the system's capacity to demonstrate favorable swelling characteristics. Furthermore, the introduction of EGCG facilitated the hybrid gels to display notable antibacterial properties against both Gram-positive and Gram-negative bacterial strains, alongside showcasing strong antioxidant capabilities. In vitro investigation demonstrated enhanced cell adhesion and migration with the LPH-EGCG system in comparison to DPH-EGCG, thus emphasizing the promising prospects of these hybrid hydrogels in advanced tissue engineering applications. [ABSTRACT FROM AUTHOR]

Biochemical systems make use of out‐of‐equilibrium polymers generated under kinetic control. Inspired by these systems, many abiotic supramolecular polymers driven by chemical fuel reactions have been reported. Conversely, polymers based on transient covalent bonds have received little attention, even though they have the potential to complement supramolecular systems by generating transient structures based on stronger bonds and by offering a straightforward tuning of reaction kinetics. In this study, we show that simple aqueous dicarboxylic acids give poly(anhydrides) when treated with the carbodiimide EDC. Transient covalent polymers with molecular weights exceeding 15,000 are generated which then decompose over the course of hours to weeks. Disassembly kinetics can be controlled using simple substituent effects in the monomer design. The impact of solvent polarity, carbodiimide concentration, temperature, pyridine concentration, and monomer concentration on polymer properties and lifetimes has been investigated. The results reveal substantial control over polymer assembly and disassembly kinetics, highlighting the potential for fine‐tuned kinetic control in nonequilibrium polymerization systems. [ABSTRACT FROM AUTHOR]

Self‐assembly of chromophoric systems is a prerequisite to create well‐ordered, processable nanomaterials with multiple functionalities. In the past two decades, the field of functional organic materials has primarily focused on systems featuring only one type of dye/π‐conjugated unit. Consequently, many reports with mechanistic insights on the self‐assembly of the dyes featuring different molecular packing have been reported. Subsequently, we have witnessed several attempts to organize the multi‐chromophoric systems in solution and solid‐state via different approaches using self‐assembly as a tool. Incorporation of more than one dye is important in creating materials with tuneable optoelectronic properties. Consequently, self‐assembly of more than one chromophoric systems have been investigated to some extent. This review aims to discuss the self‐assembled materials derived from discrete π‐conjugated systems comprising more than one dye units connected through covalent bonding (multi‐chromophoric systems). Molecular design of various multi‐chromophoric systems leading to the formation of crystals, liquid crystals and supramolecular polymers have been correlated with corresponding properties. We envisage that classification of self‐assembled multi‐chromophoric systems, with a note on tuneable optoelectronic properties, can provide a deeper understanding on the molecular design strategies, which is important in the fabrication of functional organic materials with optimum performances. [ABSTRACT FROM AUTHOR]

The directional and dynamic hydrogen bonds are of vital importance for both nucleic acids and proteins, but they naturally apply strong multiple hydrogen bonds in pendant groups and weak single hydrogen bond in the backbone. The hierarchy and orthogonality of multiple and single hydrogen bonds in biological systems inspire to elegantly tailor the supramolecular polymeric materials for robust mechanical properties. Herein, this work has fabricated dynamic ultrastrong and tough supramolecular materials through bioinspired rational design of strong multiple hydrogen bonds in pendant groups and weak single hydrogen bond in the backbone. Based on quadruple hydrogen bonds of ureidopyrimidinone and single hydrogen bond of amide, the supramolecular polymer with optimized hierarchical hydrogen bonds possesses high tensile strength and strong toughness of 30.6 MPa and 74.0 MJ m−3, respectively. Meanwhile, the dynamic dissociation and reformation of the hierarchical hydrogen bonds endow the supramolecular polymer with efficient crack resistance, self‐healing, recyclability, and high energy dissipation. Flexible and self‐healing conductors can be prepared by blending the supramolecular polymer with liquid metal in a simple manner. Therefore, this work expects that the plenty of hydrogen bonding pairs in the supramolecular toolkit provide many opportunities to produce robust and tough supramolecular polymeric materials without covalent crosslinking. [ABSTRACT FROM AUTHOR]

Using microflow space, a catalytic effect was achieved for supramolecular polymerization. With increasing reactivity at the polymer end, the selective connection of active monomers formed new block domains, avoiding fast homo-assembly. Binding of less-reactive monomers at the polymer end overcame steric bulkiness, affording a stable supramolecular diblock copolymer (SdiBCP). [ABSTRACT FROM AUTHOR]

Supramolecular polymers with circularly polarized luminescence (CPL) have promoted future intelligence development of polymer‐based materials for flexible display. However, preparing polymer‐based CPL materials with simultaneous enhanced luminescence dissymmetry factor (|glum|) and mechanical performance for industrial applications remains challenging. This work develops an eco‐friendly preparation method for preparing CPL elastomers from supramolecular polyurethanes bearing chiral fluorescent S (or R)‐1,1′‐Bi(2‐naphthol) (BINOL) groups in a solvent‐free system. Surprisingly, a polymer system containing 0.0028 mol% of chiral BINOL unit is sufficient to emit the significant CPL‐activity with a |glum| value of 2.30 × 10−2, appear a good mechanical toughness of 56.28 ± 3.9 MJ·m−3, thereby exhibit multiple flexible anti‐counterfeiting behaviors. The long‐range ordered microphase arrangement in polyurethanes is the key to improving both mechanical properties and |glum|. This is attributed to in‐situ additive polymerization of BINOL‐based isocyanate prepolymer and macromolecular polyols induced helical supramolecular structure, afforded solid‐state films with flexibility and chiral amplification. Furthermore, these results from Circular dichroism, CPL, Fourier transform infrared, X‐ray diffraction analyses, and atomic force microscope confirm the formation of long‐range ordered microphase arrangement through the synergistic effect of hydrogen bonding and π–π interactions. This work offers significant insights into the construction of CPL elastomers for developing novel flexible display materials. [ABSTRACT FROM AUTHOR]