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The topology of polymers plays an essential role in their chemical, physical and biological properties. However, their effects on chirality-related functions remain unclear. Here, we reported the topology-controlled chirality expression in the chiral supramolecular system for the first time. Two topological supramolecular polymers, hyperbranched (HP) and linear (LP) supramolecular polymers produced by the host–guest interactions of branched and linear monomers, respectively, exhibited completely different chirality expressions despite the same molecular chirality of their monomers. Significantly, due to the branch points and strong steric hindrance existing in HP, cis-HP showed an enhanced and sign-inverted Cotton effect in the n–π* bands compared with cis-LP, as a result that the distinctive chirality induction and transfer were controlled by the topological skeletons. This topology-controlled chirality induction and transfer in the photoswitchable supramolecular polymers not only enables us to elucidate the in-depth effects of topology on the chiral expression in biopolymers but also inspires the design of chiroptical and bioinspired materials.

Supramolecular polymers have great application potential in oilfield production. Therefore, according to the characteristics and production requirements of low-permeability oilfields, developing new supramolecular functional units will be a research trend in the future. In this work, a cyclodextrin-modified Trimellitic acid (TA- β -CD) molecule was designed as the new supramolecular functional units. Then, molecular dynamics (MD) simulations and quantum chemistry (QC) calculations were employed to investigate the TA- β CD and poly acrylamide (pAM-Ad) assembly mechanism, intermolecular interaction and dynamic characteristics. It is found that polyacrylamide supramolecular polymer exists in the form of molecular coils in water. Through the molecular recognition and molecular docking of β -CD and Ad molecules, different molecular coils were linked together by Ad -β -CD supramolecular assembly. Finally, three-dimensional network structure was formed, which greatly increased the viscosity of the system. During this mechanism, the TA -β CD behaves as a "two-way connector", becoming the connection point of the three-dimensional space network. Based on our results, the general rules of supramolecular flooding can be summarized at the molecular level, which helps screen out efficient supramolecular polymers units. [Display omitted] [ABSTRACT FROM AUTHOR]

The morphology of supramolecular polymer aggregates evolved during normal aging from thin 25-nm-wide nanoribbons into 1-µm-wide nanoribbons and nanotubes thanks to hydrophobic interactions between phenylalanine residues exposed on the edges of nanoribbons. [Display omitted] • Benzene-1,3,5-tricarboxamide decorated with diphenylalanine self-assemble into micrometer-long nanoribbons immediately after dissolution. • Nanoribbons interact laterally via "sticky edges" and gradually merge over the entire length. • After reaching a critical width nanoribbons self-merge, irreversibly forming nanotubes. • Mechanical perturbations cause nanotube fracture and fragmentation similar to analogous inorganic materials. During the aging of supramolecular systems, new stable materials with different morphologies, molecular packing, and hierarchical organization may form from the initial assembly. Understanding the mechanisms and pathways accompanying age-related changes may allow for the controlled synthesis of multiple materials from a single molecule in a nature-inspired manner. Herein, we demonstrate the multi-stage evolution of a single solution of C3-symmetric peptide amphiphile containing diphenylalanine fragment and benzyl-1,3,5-tricarboxamide core. Transmission electron microscopy reveals the rapid formation of 20–40 nm wide nanoribbons in an aqueous solution within 60 s after preparation. The lateral edges of nanoribbons contain solvent-exposed aromatic residues that tend to merge via an unconventional edge-to-edge zipping mechanism, leading to the nanoribbon's growth in width. After reaching a critical width and flexibility, "sticky edges" on the same nanoribbon may merge via a self-zipping mechanism, forming rigid nanotubes. Eventually, mechanical perturbations cause buckling and fracture of nanotubes into shorter nanotubes via flexural or tensile failure. This work reports new evolution pathways in soft 2D assemblies and introduces solution ageing as a promising method to control morphology of peptide amphiphiles. [ABSTRACT FROM AUTHOR]

Supramolecular chemistry enables the manipulation of functional components on a molecular scale, facilitating a “bottom-up” approach to govern the sizes and structures of supramolecular materials. Using dynamic non-covalent interactions, supramolecular polymers can create materials with reversible and degradable characteristics and the abilities to self-heal and respond to external stimuli. Pillar[n]arene represents a novel class of macrocyclic hosts, emerging after cyclodextrins, crown ethers, calixarenes, and cucurbiturils. Its significance lies in its distinctive structure, comparing an electron-rich cavity and two finely adjustable rims, which has sparked considerable interest. Furthermore, the straightforward synthesis, uncomplicated functionalization, and remarkable properties of pillar[n]arene based on supramolecular interactions make it an excellent candidate for material construction, particularly in generating interpenetrating supramolecular polymers. Polymers resulting from supramolecular interactions involving pillar[n]arene find potential in various applications, including fluorescence sensors, substance adsorption and separation, catalysis, light-harvesting systems, artificial nanochannels, and drug delivery. In this context, we provide an overview of these recent frontier research fields in the use of pillar[n]arene-based supramolecular polymers, which serves as a source of inspiration for the creation of innovative functional polymer materials derived from pillar[n]arene derivatives.

Abstract Supramolecular polymers are materials that exhibit a range of functionalities and thus find wide applicability. In this study, two natural low‐molecular‐weight compounds, thioctic acid (TA) and phytic acid (PA), are used to fabricate polymeric supramolecular structures. The coexistence of dynamically covalently linked poly(TA) and hydrogen bond linked poly(PA) moieties result in copolymeric materials with different dynamic features. The obtained poly(TA‐PA)s show rapid and strong adhesion on a variety of natural and artificial surfaces, with high 180° peeling, lap‐shear, and pull‐off strengths over wide temperature (−18 °C to 60 °C) and humidity (20−99%) ranges. The poly(TA‐PA)s also display good stability and adhesion in the presence of water, even show stable and long‐lasting underwater adhesion. Hence, the synthesized poly(TA‐PA)s, which have high water resistance, are suitable for use as sealing materials in various applications, thus highlighting the applicability of supramolecular polymer materials in underwater surface coatings and adhesion.

The infections and diseases caused by harmful bacteria are regarded as the worldwide health-threatening issue. The most antibiotics-based delivery systems restricted the controlled drug release at specific infection sites due to the stable chemical conjugation, thus largely compromising the treatment effectiveness. Herein, we report the construction of light controlled drug-based supramolecular polymer (LDSP), which is endowed the “switch on” function for realizing the controllable antibiotics released in specific sites. LDSP was first formed based on the host-guest interaction between β-cyclodextrin units grafted hyaluronic acid chain (HA-CD) and azobenzene moiety linked by two enoxacin units (Azo-(Eno)2), and could further self-assemble into light controlled drug-based supramolecular polymer self-assemblies (LDSPSAs). Under the UV light irradiation, the “switch on” function of LDSPSAs could be effectively turned on at the specific infected tissues due to the smartly dissociated host-guest interaction, facilitating the controlled release of the hydrophobic Azo-(Eno)2 to interact with bacteria for efficient antibacterial effect. The biological evaluation demonstrated that LDSPSAs achieved good antibacterial efficiency and well biosafety.

Supramolecular polymers (SPs) exhibit intriguing benefits in functional soft materials due to their dynamic bonding feature. However, most SPs can only exist in the solution state and fail to form bulk materials, which limits their applications. Here, we report the fabrication of semi‐solid bulk SP materials by using polyoxometalate (POM) nanoclusters as supramolecular cross‐linkers to solidify a deep eutectic solvent (DES). The abundant protons and strong hydrogen bonds afforded by POMs enable these SP materials as superprotonic conductive electrolytes with sufficient mechanical strength, showing a proton conductivity more than 1×10−4 S cm−1 and a breaking strength exceeding 1 MPa at room temperature. Moreover, the thermodynamic reversibility of the SP electrolytes allows them to form a stable electrode‐electrolyte interface by a facile melt‐infiltration strategy upon mild heating, which leads to improved performance in supercapacitors. This work presents an innovative DES/POM hybrid system as a promising platform to develop functional supramolecular materials for energy and electronic applications. [ABSTRACT FROM AUTHOR]

High molecular polymers have been widely studied and applied in the field of enhanced oil recovery (EOR). At present, the focus of research has been changed to the design of polymer networks with unique properties such as anti-temperature and anti-salinity, good injection and so on. Supramolecular polymers have high viscoelasticity as well as excellent temperature, salt resistance and injection properties. Can supramolecular polymers become another material choice for polymer flooding to enhance oil recovery? The present review aims to systematically introduce supramolecular polymers, including its design strategy, interactions and rheological properties, and address three main concerns: (1) Why choose supramolecular polymers? (2) How do we synthesize and characterize supramolecular polymers in the field of oilfield chemistry? (3) What has been the application progress of supramolecular polymers in improving oil recovery? The introduction of a supramolecular interaction system provides a new idea for polymer flooding and opens up a new research direction to improve oil recovery. Aiming at the "reversible dynamic" supramolecular polymers, the supramolecular polymers are compared with the conventional covalent macromolecular polymer networks, and the challenges and future research directions of supramolecular polymers in EOR are discussed. Finally, the author's viewpoints and perspectives in this emerging field are discussed. [ABSTRACT FROM AUTHOR]

Supramolecular polymers exhibit well‐controlled dynamics with fascinating capacity for remodeling, self‐healing, and stimuli‐responsiveness. Supramolecular kinetics of non‐covalent bonds is a dominant control handle among the relevant factors to tailor dynamics of supramolecular polymers. This Review focuses on elucidating how supramolecular kinetics dictates the polymer dynamics in supramolecular polymer systems. The ways to tailor supramolecular kinetics are firstly examined as prerequisites for structure‐activity study of supramolecular polymers. We next discuss the role of supramolecular kinetics in supramolecular polymers under different polymer architectures by the combination of both of theoretical and experimental studies. Finally, we conclude by discussing the existing challenges and opportunities in the current studies. [ABSTRACT FROM AUTHOR]

Supramolecular gels of low molecular weight molecules have created enthusiasm among researchers for their tremendous applications as sensors and in the field of biomedical applications and electro‐optics for decades. Among them, gels derived from perylene diimide derivatives in organic non‐polar solvents are rarely reported. This review has gathered all information about these organogels and summarized them based on the substituents and the self‐assembly mechanism in various organic solvents. It has been found that perylene diimide derivatized molecules undergo hydrogen or non‐hydrogen bonding directed π–π stacking to build up three‐dimensional fibrous network structures, which later proved as gels by various characterization techniques. [ABSTRACT FROM AUTHOR]

Among the enticing issues of chiral origins are: how chirality is born from the initial achiral units and the mechanisms for the transfer of chiral information. In this work, by combining a physical vortex and chiral seeds, a general process is revealed to generate chiral supramolecular polymers from achiral C3‐symmetric molecules. The symmetry‐broken assemblies from the achiral molecules could work as chiral seeds to initiate the polymerization of either homologous or heterologous achiral monomers. Concomitantly, the fragmentation of the polymer caused by the vortex during the nucleation‐elongation stages is shown to enlarge the domains of the chiral nuclei and then guide the polymer to grow into the predominant helicity with a high reactivity ratio. Moreover, the chiral structural information can be stored in different forms of assemblies. These new polymerization modes will provide guidance for the preparation of chiral materials. [ABSTRACT FROM AUTHOR]

Highlights: Rational design of 3D flexible free-standing membrane catalysts with protonation between supramolecular polymers and nitrogen-deficient carbon nitride nanotubes frameworks via facile bottom-up self-conversion approach. PEMAC@NDCN demonstrates the lowest reversible oxygen bifunctional activity of 0.61 V with exceptional long-lasting durability, surpassing the commercial and reported champion oxygen catalysts. Engineering catalytically active cathode materials enabled all-temperature flexible Zn–air batteries with high electrochemical and mechanical performances (temperature of − 40 to 70 °C) under harsh operations. Rational construction of flexible free-standing electrocatalysts featuring long-lasting durability, high efficiency, and wide temperature tolerance under harsh practical operations are fundamentally significant for commercial zinc–air batteries. Here, 3D flexible free-standing bifunctional membrane electrocatalysts composed of covalently cross-linked supramolecular polymer networks with nitrogen-deficient carbon nitride nanotubes are fabricated (referred to as PEMAC@NDCN) by a facile self-templated approach. PEMAC@NDCN demonstrates the lowest reversible oxygen bifunctional activity of 0.61 V with exceptional long-lasting durability, which outperforms those of commercial Pt/C and RuO2. Theoretical calculations and control experiments reveal the boosted electron transfer, electrolyte mass/ion transports, and abundant active surface site preferences. Moreover, the constructed alkaline Zn–air battery with PEMAC@NDCN air–cathode reveals superb power density, capacity, and discharge–charge cycling stability (over 2160 cycles) compared to the reference Pt/C + RuO2. Solid-state Zn–air batteries enable a high power density of 211 mW cm−2, energy density of 1056 Wh kg−1, stable charge–discharge cycling of 2580 cycles for 50 mA cm−2, and wide temperature tolerance from − 40 to 70 °C with retention of 86% capacity compared to room-temperature counterparts, illustrating prospects over harsh operations. [ABSTRACT FROM AUTHOR]

Co-crystal structure of inclusion complex based on macrocyclic host of octabromo-functionalized pillar[5]arene (PilBr8) and guest 1-bromooctane (OctBr) molecule is discussed. The host-guest interactions are achieved by efficient C–H⋅⋅⋅O and C–H⋅⋅⋅π nonbonding interactions. The packing pattern of the crystal structure shows the inclusion-complex [PilBr8⊃OctBr] formed one-dimensional supramolecular polymer network driven by Br⋅⋅⋅H and Br⋅⋅⋅Br non-bonding interactions. Hirshfeld surface analysis revealed that the guest molecule plays an important role in formation of self-assembled linear supramolecular polymer trough head-to-tail halogen bond (Br⋅⋅⋅H). Co-crystal of inclusion complex based on bromo-functionlized pillar[5]arene with 1-bromooctane displays the assembly of linear supramolecular polymer promoted by halogen-bonding interactions. [ABSTRACT FROM AUTHOR]

Hydrogen bonding is the most common noncovalent reversible interaction leading to supramolecular polymeric assemblies. Shabbir et al. (Macromolecules 48:5988–5996, 2015) reported both linear and nonlinear rheological data for a model system consisting of pure poly(n-butyl acrylate) (PnBA) homopolymer and three PnBA-poly(acrylic acid) (PnBA-PAA) copolymers with different numbers of acrylic acid (AA) side groups. Hydrogen bonds between the AA groups not only cause the storage and loss modulus to shift in the direction of a power law scaling of 0.5 in the terminal relaxation regime, but also the elongational viscosity shows increasing strain hardening with a strongly nonlinear dependence on the number of hydrogen bonding groups. Based on the "Sticky Rouse" model and a constitutive equation of the Doi-Edwards type with consideration of chain stretch, we model the effect of hydrogen bonding on the elongational viscosity of the PnBA-AA copolymers. We show that the elongational viscosity data are consistent with a Sticky Rouse relaxation modulus of the AA associations characterized by a constant modulus G A and a constant sticker life time τ A , while the complexity of the hydrogen assemblies as quantified by the Sticky Rouse time increases with the concentration of AA groups from the order of seconds (3% AA) to hours (6%AA) and to 1 day (13%AA), and leads to extreme strain hardening. The elongational stress shows a steady state at large strains and the stretch reaches a limiting value independent of strain rate. At the highest concentration of AA groups investigated (38%AA), the PnBA-AA copolymer is a weak gel fracturing at a critical strain, and the sticker life time loses its significance. The effect of the Sticky Rouse time on self-healing is discussed. [ABSTRACT FROM AUTHOR]

A polymerizable diacetylene gelator, containing urea and urethane groups, that congeals various non-polar solvents was synthesized. The gelator molecules self-assemble forming non-covalent polymers through intermolecular hydrogen bonding, as evidenced from FT-IR and concentration-dependent 1H NMR spectroscopy. The self-assembly positions the diyne units of adjacent molecules at proximity and in a geometry suitable for their topochemical polymerization. UV irradiation of the gel resulted in topochemical polymerization, transforming the non-covalent polymer to a covalent polymer, in situ, in the gel state. The polymerization was confirmed by characterizing the polydiacetylene (PDA) using UV-Vis and Raman spectroscopy. Time-dependent rheological studies revealed gradual strengthening of the gel with the duration of irradiation, suggesting that the degree of polymerization increases with the duration of irradiation. The PDA formed is a semiconductor, which might be useful for various applications., (© 2024 Wiley‐VCH GmbH.)

Lithium (Li) metal batteries have the advantage of high energy density, but the Li dendrites risk piercing the separator and causing a short circuit in the battery. Replacing the liquid electrolytes with gel electrolytes is considered an effective strategy to solve the issues. Herein, a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)-based gel electrolyte, improved with multifunctional supramolecular polymer (MSP), was prepared to enhance the cycling stability and energy density of quasi-solid-state Li metal batteries. The MSP addictive constructs a cross-linked network structure with PVDF-HFP matrix and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) through hydrogen bonding, improving the mechanical strength of the composite gel electrolyte (PH-10%MSP-GE) to against the growth of Li dendrites. Moreover, the pre-lithiated sulfonic acid groups, conductive polyether groups of MSP, and the attraction of TFSI - anions, promote the Li-ion transportation of the composite gel electrolyte. Finally, the Li||Li symmetric cell cycle stably for over 450 h. The Li||LiFePO 4 full cell demonstrates a high energy density and excellent cycling stability for over 600 cycles, with a capacity retention rate of up to 98.7%. This work provides valuable insights into the preparation of multifunctional composite gel polymer electrolytes and competitive quasi-solid-state Li metal batteries., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Inc.)

This Review introduces the research directions for the synthesis of supramolecular fullerene polymers. First, the discovery of host‐guest complexes of pristine fullerenes is briefly outlined. We focus on progress in supramolecular fullerene polymers directed by the use of calix[5]arene‐fullerene interactions, which comprise linear, networked, helical arrays of fullerenes in supramolecular ensembles. The unique self‐sorting behavior of right‐handed and left‐handed helical supramolecular fullerene arrays is discussed. Thereafter, an extensive investigation of the calix[5]arene‐fullerene interaction for control over the chain structures of covalent polymers is introduced. [ABSTRACT FROM AUTHOR]

This article reports supramolecular polymerization of two bis‐amide functionalized naphthalene‐diimide (NDI) building blocks (NDI−L and NDI−C) in two solvents, namely n‐heptane (Hep) and methylcyclohexane (MCH). NDI−L and NDI−C differ only by the peripheral hydrocarbon wedges, consisting of linear C7 chains or cyclic methylcyclohexane rings, respectively. UV/Vis and FTIR spectroscopy studies reveal distinct internal order and H‐bonding pattern for NDI−L and NDI−C aggregates irrespective of the solvent system, indicating the dominant role of the intrinsic packing parameters of the individual building block, possibly influenced by the peripheral steric crowding. However, NDI−L produces a significantly stronger gel in Hep compared to MCH as evident from the rheological and thermal properties. In contrast, NDI−C exhibits a clear preference for MCH, producing gel with moderate strength but in Hep it fails to produce 1D morphology or gelation. All‐atom molecular dynamics (MD) simulation studies corroborate with the experimental observation and provide the rationale for the observed solvent‐shape effect by revealing a quantitative estimate regarding the thermodynamics of self‐assembly in these four combinations. Such clear‐cut shape‐matching effect (between the peripheral hydrocarbon wedge and the solvent system) unambiguously support a direct participation of the solvent molecules during supramolecular polymerization and presence of a closely‐adhered solvent shell around the supramolecular polymers, similar to the first layer of water molecules around the protein surface. Solvent induced CD experiments support this hypothesis as induced CD band was observed only from a chiral co‐solvent of matching shape. This is reconfirmed by the higher de‐solvation temperature of the shape‐matching NDI/solvent system combination compared to the shape mis‐match combination in variable temperature UV/Vis experiments, revealing transformation to a different aggregate at higher temperatures rather than disassembly to the monomer for all four combinations. [ABSTRACT FROM AUTHOR]

Supramolecular polymers are widely utilized and applied in self-assembly or self-healing materials, which can be repaired when damaged. Normally, the healing process is classified into two types, including extrinsic and intrinsic self-healable materials. Therefore, the aim of this work is to review the intrinsic self-healing strategy based on supramolecular interaction or non-covalent interaction and molecular recognition to obtain the improvement of mechanical properties. In this review, we introduce the main background of non-covalent interaction, which consists of the metal–ligand coordination, hydrogen bonding, π–π interaction, electrostatic interaction, dipole–dipole interaction, and host–guest interactions, respectively. From the perspective of mechanical properties, these interactions act as transient crosslinking points to both prevent and repair the broken polymer chains. For material utilization in terms of self-healing products, this knowledge can be applied and developed to increase the lifetime of the products, causing rapid healing and reducing accidents and maintenance costs. Therefore, the self-healing materials using supramolecular polymers or non-covalent interaction provides a novel strategy to enhance the mechanical properties of materials causing the extended cycling lifetime of products before replacement with a new one. [ABSTRACT FROM AUTHOR]

A series of AA/BB types of cyclodextrin‐based supramolecular polymers (CD‐SP 1, 2, 3, and 4) have been constructed and characterized, which employed as ligands to accelerate the copper(I)‐catalyzed azide alkyne cycloaddition (CuAAC) using the conventional Sharpless–Fokin catalyst (CuSO4 + Na ascorbate) for the first time. Among them, the bridged‐maleic‐2‐β‐CD (CD = cyclodextrin)@bridged‐maleic‐2‐Ada (Ada = adamantane) (CD‐SP 4) self‐assembly shows more effective catalytic activity for CuAAC of azide and acetylene at 40 mol ppm of Cu(I) in water with excellent yields and remarkable TON (turnover number) values (up to 23,750). CD‐SP 4 can be fully recycled, and the catalyst can be reused efficiently for 10 times with negligible loss of catalyst activity. Therefore, it may extend the potential applications of cyclodextrin‐based supramolecular polymers in green chemical synthesis. [ABSTRACT FROM AUTHOR]

[Display omitted] • Resonance Rayleigh scattering spectrometry can determine glycyrrhizic acid rapidly. • Methyl violet or neutral red with water can form supramolecular polymers. • Supramolecular polymers can produce resonance Rayleigh scattering intensity. • Adding glycyrrhizic acid further weakened resonance Rayleigh scattering intensity. • Glycyrrhizic acid and cationic dyes form ion-association complexes in acidic media. This study used cationic dyes methyl violet (MV) and neutral red (NR) as probes, based on dual-wavelength overlapping resonance Rayleigh scattering (RRS), and designed two highly sensitive methods for the determination of the natural sweetener glycyrrhizic acid (GZA). In the Clark-Lubs buffer solution, when only MV or NR was present in the solution, they formed supramolecular polymers through hydrogen bonding. When adding GZA at different concentrations, the formation of ionic association complexes led to a subsequent decrease in RRS intensity at two wavelengths in the MV − GZA system and NR − GZA system, and the amount of the decline was proportional to the GZA concentration. The linear ranges were determined as 0.1 − 0.6 mg/L and 0.1 − 0.7 mg/L, with correlation coefficients of 0.9972 and 0.9996, and limits of detection were 0.052 mg/L and 0.016 mg/L, respectively. For this study, reaction conditions were optimized, potential interfering substances were investigated, and the mechanisms behind RRS generation and intensity decrease were discussed. The proposed methods were sensitive, fast, time-saving and efficient, and have been successfully applied to licorice and dried ginger decoction analysis, yielding satisfactory results. [ABSTRACT FROM AUTHOR]

In this study, ultra-robust, nonfluorinated, and sub-zero temperature self-healing superhydrophobic coatings are fabricated by spray-coating imine-bond crosslinked polydimethylsiloxane-based supramolecular polymers (I-PDMS) and SiO 2 nanoparticles (NPs). Due to the synergy between I-PDMS binding and SiO 2 NPs reinforcement, the resulting I-PDMS/SiO 2 coatings can maintain their superhydrophobicity after sandpaper abrasion, sand impacting, hand tapping, and foot trampling and showed the best mechanical robustness among reported superhydrophobic coatings. Furthermore, due to the low glass-transition temperature of I-PDMS monomers and the dynamic nature of the imine bonds, the I-PDMS/SiO 2 coatings can spontaneously restore their damaged superhydrophobicity at − 30 °C through the free energy-driven diffusion of I-PDMS monomers. The I-PDMS/SiO 2 coatings can be used as friction layers for triboelectric nanogenerators (TENGs), which provide them with long-lasting waterproofing and self-cleaning capabilities, thus preventing their output performance from being degraded due to water infiltration and dust accumulation. Due to the excellent mechanical strength of the I-PDMS/SiO 2 coatings, the resulting self-healing superhydrophobic TENGs can generate electrical energy from repetitive motions such as hand tapping or foot trampling, which has not been possible in other reported superhydrophobic TENGs. [Display omitted] • Self-healing superhydrophobic coatings are prepared using supramolecular polymers. • The coatings are ultra-robust against various mechanical damages. • The coatings can spontaneously self-heal at sub-zero temperatures. • Self-healing superhydrophobic TENGs based on the coatings are obtained. • The TENGs can long-lasting harvest energy from human motions. [ABSTRACT FROM AUTHOR]

Herein, we present a mussel-inspired supramolecular polymer coating to improve the an-ti-corrosion and self-healing properties of an AZ31B magnesium alloy. A self-assembled coating of polyethyleneimine (PEI) and polyacrylic acid (PAA) is a supramolecular aggregate that takes advantage of the weak interaction of non-covalent bonds between molecules. The cerium-based conversion layers overcome the corrosion problem between the coating and the substrate. Catechol mimics mussel proteins to form adherent polymer coatings. Chains of PEI and PAA interact electrostatically at high density, forming a dynamic binding that causes strand entanglement, enabling the rapid self-healing properties of a supramolecular polymer. The addition of graphene oxide (GO) as an anti-corrosive filler gives the supramolecular polymer coating a superior barrier and impermeability properties. The results of EIS revealed that a direct coating of PEI and PAA accelerates the corrosion of magnesium alloys; the impedance modulus of a PEI and PAA coating is only 7.4 × 103 Ω·cm2, and the corrosion current of a 72 h immersion in a 3.5 wt% NaCl solution is 1.401 × 10−6 Ω·cm2. The impedance modulus of the addition of a catechol and graphene oxide supramolecular polymer coating is up to 3.4 × 104 Ω·cm2, outperforming the substrate by a factor of two. After soaking in a 3.5 wt% NaCl solution for 72 h, the corrosion current is 0.942 × 10−6 A/cm2, which is superior to other coatings in this work. Furthermore, it was found that 10-micron scratches were completely healed in all coatings within 20 min, in the presence of water. The supramolecular polymer offers a new technique for the prevention of metal corrosion.

The self‐assembly of small molecules into supramolecular polymers can be analogous to the formation of classical solid‐state crystals depending on the mechanism of polymerization. Taking inspiration from the field of materials science, complex supramolecular polymer nanostructures can be formed by carefully controlling nucleation and growth processes. Exploration of the energy landscapes in supramolecular polymers can also lead to the discovery of polymorphs where a single monomer can self‐assemble into different supramolecular polymers with distinct molecular packing arrangements. This mini‐review focuses on recent developments where the manipulation of nucleation and growth processes were used to develop novel supramolecular copolymers and explore polymorphism in supramolecular materials, highlighting examples of such systems composed of small organic molecules and peptides. © 2022 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Industrial Chemistry. [ABSTRACT FROM AUTHOR]

Three novel orange emission supramolecular phosphorescent polymers (SPPs) with cationic iridium complex have been developed for polymer light-emitting diodes (PLEDs) through efficient self-assembly. The supramolecular assembly process was monitored by 1H nuclear magnetic resonance (1H NMR) and viscosity measurement. These SPPs give orange phosphorescence with a peak at about 595 nm and display good thermal properties with a glass-transition temperature (Tg) about 90 °C. The single-emissive-layer PLEDs with charged SPPs exhibited the highest device efficiency of 2.81 cd A−1 with the Commission Internationale de L'Eclairage coordinates of (0.58, 0.40). The present work reported the charged SPPs self-assembled by the cationic iridium complex for the first time and provided a new guide to develop orange emitters for solution-processable optoelectronic devices. [ABSTRACT FROM AUTHOR]

The development of reliable methods for the rapid and selective detection of nitro-explosive were vital concern for national security due to the increasing use of explosive materials in terrorism, military operation safety, industrial and environmental safety control. Here a novel cross-linked supramolecular polymer network (SPN5) was efficiently constructed by pillar[5]arene-based host–guest interactions, which can be used for nitro explosives o-DNB and p-DNB detection. The limits of detection (LODs) of SPN5 for o-DNB and p-DNB were determined as 7.90 × 10−7 M and 4.40 × 10−7 M, respectively. Moreover, the detection of o-DNB and p-DNB was also realized in a thin film consisting of the SPN5. This work provided a novel strategy for efficient detection of explosives. [ABSTRACT FROM AUTHOR]

Efficient and long‐range exciton transport is critical for photosynthesis and opto‐electronic devices, and for triplet‐harvesting materials, triplet exciton diffusion length (LD) and coefficient (D) are key parameters in determining their performances. Herein, we observed that PtII and PdII organometallic nanowires exhibit long‐range anisotropic triplet exciton LD of 5–7 μm along the M−M direction using direct photoluminescence (PL) imaging technique by low‐power continuous wave (CW) laser excitation. At room temperature, via a combined triplet–triplet annihilation (TTA) analysis and spatial PL imaging, an efficient triplet exciton diffusion was observed for the PtII and PdII nanowires with extended close M−M contact, while is absent in nanowires without close M−M contact. Two‐dimensional electronic spectroscopy (2DES) and calculations revealed a significant contribution of the delocalized 1/3[dσ*(M−M)→π*] excited state during the exciton diffusion modulated by the M−M distance. [ABSTRACT FROM AUTHOR]

The detection of volatile aliphatic aldehydes is of significance because of their chemical toxicity, physical volatility and widespread applications in chemical industrial processes. In this work, the direct detection of aliphatic aldehydes is tackled using a pillar[5]arene‐based fluorescent supramolecular polymer with vaporchromic behavior. Thin films with strong orange‐yellow fluorescence are prepared by coating the linear supramolecular polymer on glass sheets. When the thin films are exposed to aliphatic aldehydes with different carbon chain lengths, they can selectively sensing n‐butyraldehyde (C4) and caprylicaldehyde (C8), accompanied by fluorescence quenching, indicating that the supramolecular polymer is a highly selective vapochromic response material for aliphatic aldehydes with long alkyl chains. [ABSTRACT FROM AUTHOR]

The host immune response to an implanted biomaterial, particularly the phenotype of infiltrating macrophages, is a key determinant of biocompatibility and downstream remodeling outcome. The present study used a subcutaneous rat model to compare the tissue response, including macrophage phenotype, remodeling potential, and calcification propensity of a biologic scaffold composed of glutaraldehyde‐fixed bovine pericardium (GF‐BP), the standard of care for heart valve replacement, with those of an electrospun polycarbonate‐based supramolecular polymer scaffold (ePC‐UPy), urinary bladder extracellular matrix (UBM‐ECM), and a polypropylene mesh (PP). The ePC‐UPy and UBM‐ECM materials induced infiltration of mononuclear cells throughout the thickness of the scaffold within 2 days and neovascularization at 14 days. GF‐BP and PP elicited a balance of pro‐inflammatory (M1‐like) and anti‐inflammatory (M2‐like) macrophages, while UBM‐ECM and ePC‐UPy supported a dominant M2‐like macrophage phenotype at all timepoints. Relative to GF‐BP, ePC‐UPy was markedly less susceptible to calcification for the 180 day duration of the study. UBM‐ECM induced an archetypical constructive remodeling response dominated by M2‐like macrophages and the PP caused a typical foreign body reaction dominated by M1‐like macrophages. The results of this study highlight the divergent macrophage and host remodeling response to biomaterials with distinct physical and chemical properties and suggest that the rat subcutaneous implantation model can be used to predict in vivo biocompatibility and regenerative potential for clinical application of cardiovascular biomaterials. [ABSTRACT FROM AUTHOR]

For the creation of next‐generation organic electronic materials, the integration of π‐systems has recently become a central theme. Such functional materials can be assembled by supramolecular polymerization when aromatic π‐systems are used as monomers, and the properties of the resulting supramolecular polymer strongly depend on the electronic structure of the monomers. Here, we demonstrate the construction of a supramolecular polymer consisting of an antiaromatic π‐system as the monomer. An amide‐functionalized NiII norcorrole derivative formed a one‐dimensional supramolecular polymer through π‐π stacking and hydrogen‐bonding interactions, ensuring the persistency of the conducting pathway against thermal perturbation, which results in higher charge mobility along the tightly bound linear aggregates than that of the aromatic analogue composed of ZnII porphyrins. [ABSTRACT FROM AUTHOR]

Unique relationships between hierarchically organized biological nanostructures and functions have motivated chemists to construct sophisticated artificial nanostructured systems from small and simple synthetic molecules through self‐assembly. As one of such sophisticated systems, we have investigated scissor‐shaped photochromic dyads that can hierarchically self‐assemble into discrete nanostructures showing photoresponsive properties. We synthesized various azobenzene dyads and found that these dyads adopt intramolecularly folded conformation like a closed scissor, and then self‐assemble into toroidal nanostructures by generating curvature. The toroids further organize into nanotubes and further into helical supramolecular fibers depending on the nature of alkyl substituents. All of these nanostructures can be dissociated and reorganized through the photoisomerization of azobenzene units. On the other hand, the introduction of stilbene chromophores instead of azobenzenes leads to one‐dimensional supramolecular polymerization, which upon the intramolecular photocyclization of stilbene chromophores shifts to curved self‐assembly leading to helicoidal fibers with distinct supramolecular chirality. [ABSTRACT FROM AUTHOR]

Supramolecular polymers, which are chain-like aggregates of monomers connected by noncovalent interactions, possess some unique chemical and physical properties and functions. In the past thirty years, great achievements have been made in the field of supramolecular polymers. So far, there are some critical issues in this research field, including the development of the driving forces and design strategies for supramolecular polymerization, and supramolecular building blocks and functions of supramolecular polymers. Recently, for the first time, Meijer et al in Eindhoven University of Technology and Yamaguchi et al in Nagoya University incorporated the frustrated Lewis pair (FLP) into the design of supramolecular polymers. By developing FLP building blocks based on planar triarylborane and triarylamine, the supramolecular polymers were constructed based on noncovalent interactions of B−N coordination, and these polymers exhibited the unique fluorescence properties with the long lifetime and circularly polarized nature. Furthermore, Yamaguchi et al disclosed a novel supramolecular polymerization method through the design of the double-trap metastable state enabled by intramolecular hydrogen bonds and intermolecular B−N coordination, achieving dynamic and controllable supramolecular polymerization. These studies thus developed new driving forces and building blocks for supramolecular polymerization, and also provided novel design strategies for supramolecular polymerization and new functions of supramolecular polymers. [ABSTRACT FROM AUTHOR]

Supramolecular adhesives that enable debonding on-demand are of significant research interest for the development of adaptive and smart materials, yet, biodegrable supramolecular adhesives have been rarely exploited. Herein, telechelic, three-armed and four-armed CO2-based polyols with close molecular weights and various CO2 content (or carbonate unite content) have been synthesized via a zinc-cobalt double metal cyanide complex catalyzed ring-opening copolymerization of CO2 and propylene oxide, and further exploited as sustainable and biodegradable building blocks for supramolecular polymers (SMPs) with 2-ureido-4[1H]-pyrimidinone (UPy) motifs. Notably, the orthogonal modulation of the CO2 content and the topology of CO2-based polyols provide a unique opportunity to fine-tune the surface energy as well as the cohesive strength of the resulting CO2-based SMPs. Notably, a three-armed SMP with 44% CO2 (3UPy-CO2-44%) can well balance the trade-off between surface energy and cohesive strength, therefore bestowing a high adhesive strength of 7.5 and 9.7 MPa towards stainless steel and wood substrates respectively by testing the corresponding single lap joints. Moreover, the light-responsive adhesion property of 3UPy-CO2-44% has been demonstrated exemplarily by blending with a UV sensitizer. [ABSTRACT FROM AUTHOR]

Supramolecular polymers with different functionalities have been continuously developed in the past decade because of their indispensable role in soft materials. However, pure organic supramolecular polymers with stable room temperature phosphorescence (RTP) emission were very rarely reported for the difficulties of synthesis and achieving RTP in solution. Herein, soluble helical supramolecular polymers with circularly polarized room-temperature phosphorescence were developed via a facile host-guest strategy. Through assembly, a transition from pure fluorescence to almost pure RTP emission was achieved. Adjusting the asymmetry of guest could easily control the chiroptical property of supramolecular polymers. This work provides new opportunities for the design and development of intelligent soft functional soft materials. [ABSTRACT FROM AUTHOR]

Synthesis of one‐dimensional nanofibers with distinct topological (higher‐order structural) domains in the same main chain is one of the challenging topics in modern supramolecular polymer chemistry. Non‐uniform structural transformation of supramolecular polymer chains by external stimuli may enable preparation of such nanofibers. To demonstrate feasibility of this post‐polymerization strategy, we prepared a photoresponsive helically folded supramolecular polymers from a barbiturate monomer containing an azobenzene‐embedded rigid π‐conjugated scaffold. In contrast to previous helically folded supramolecular polymers composed of a more flexible azobenzene monomer, UV‐light induced unfolding of the newly prepared helically folded supramolecular polymers occurred nonuniformly, affording topological block copolymers consisting of folded and unfolded domains. The formation of such blocky copolymers indicates that the photoinduced unfolding of the helically folded structures initiates from relatively flexible parts such as termini or defects. Spontaneous refolding of the unfolded domains was observed after visible‐light irradiation followed by aging to restore fully folded structures. [ABSTRACT FROM AUTHOR]

The growing demands of supramolecular hyperbranched polymers integrating noncovalent interaction and unique topological structure merits had received considerable interest in the fabrication of novel materials for advanced applications. Herein, we prepared A2B6-type POSS-containing supramolecular hyperbranched polymers with multiple morphologies including lamellar-like, branched, hollow, core-shell and porous spherical structures through regulating self-assembling monomer concentrations and solvent polarities. The incorporation of appropriate emulative guest molecules would further trigger morphological transformations (such as vesicles and spherical micelles) by synergistic effects of unique POSS aggregation ability, supramolecular complexations and hydrophilic-hydrophobic interactions. Thus, this facile and universal strategy may enable a modular nanofabrication of supramolecular hyperbranched polymers with diversiform topological structure and sophisticated multifunctionality for their potential applications. [ABSTRACT FROM AUTHOR]

This paper briefly introduces the basic concepts of supramolecular polymers，aiming at the problems encountered by covalent polymers in the process of oil displacement in low permeability reservoirs with low recovery factor・ The application of supramolecular polymer in oil displacement process is reviewed ・ The application and development of the new supramolecular polymer flooding technology in the process of enhancing low permeability recovery were prospected. [ABSTRACT FROM AUTHOR]

Self-immolative chemistries that respond in an irreversible manner to external stimuli are highly attractive to permanently degrade filamentous supramolecular biomaterials. Within the monomer, a balance needs to be struck between its capacity to be supramolecularly polymerized and degraded at an appropriate rate for a given application. Herein, we unravel the structure-property-function relationships of a library of squaramide-based bolaamphiphiles bearing a central disulfide-based self-immolative spacer to construct supramolecular polymers responsive to chemical stimuli in aqueous solutions. We examine the impact of changing the alkyl domain length (2 to 12 methylene units) on the formation of supramolecular filaments and their rate of degradation in response to a biological antioxidant, glutathione. A minimum of an octyl spacer is required to robustly form supramolecular polymers that can be irreversibly degraded through a cyclization-elimination reaction of the self-immolative spacer triggered by thiol-disulfide exchange. Further increasing the peripheral alkyl chain length to a decyl spacer increases the ordered packing of the amphiphiles, hindering their chemical degradation. This study provides a framework to design chemically responsive filamentous supramolecular polymers based on bolaamphiphiles that can be irreversibly degraded in aqueous solutions for their eventual application as biomedical materials., (© 2024 The Author(s). ChemBioChem published by Wiley-VCH GmbH.)

Significant efforts have been dedicated to designing porous organic cage compounds with geometric complexity and topological diversity. However, the use of these cage molecules as premade building units for constructing infinite cage-based superstructures remains unexplored. Here, we report the use of a panel-decorated phosphine organic cage as a special monomer to achieve supramolecular polymerization, resulting in cage-by-cage noncovalent polymers through the synergy of metal-coordination and intercage π - π dimerization. At a monomer concentration of 122 mM, the average degree of polymerization reaches 17, corresponding to a molecular weight of 26 kDa. The obtained cage-based supramolecular polymers can further hierarchically self-assemble into vesicular morphologies or one-dimensional nanofiber architectures. Selective control over the cosolvents can regulate their structural hierarchy and assembled morphology. This approach paves a new way for the construction of cage-based hierarchical assemblies and materials., (© 2024 IOP Publishing Ltd.)

In this letter, a novel one‐dimensional supramolecular polymer has been successfully constructed from 4‐(4‐(1‐benzyl‐pyridinium)styryl)‐1‐methyl‐pyridinium chloride (BPSMP) guest molecule and a host CB[8] depending on the host‐guest interactions which was characterized by NMR, electronic absorption, ITC, DLS, ESI‐MS and fluorescence spectroscopy. Interestingly, the supramolecular polymers could transform into synergistic covalent and supramolecular polymers when irradiated with visible light, from irreversible polymerization of a preorganized supramolecular polymer through cucurbit[8]uril (CB[8])‐controlled [2+2] photodimerization. [ABSTRACT FROM AUTHOR]

Additive manufacturing has significantly changed polymer science and technology by engineering complex material shapes and compositions. With the advent of dynamic properties in polymeric materials as a fundamental principle to achieve, e.g., self-healing properties, the use of supramolecular chemistry as a tool for molecular ordering has become important. By adjusting molecular nanoscopic (supramolecular) bonds in polymers, rheological properties, immanent for 3D printing, can be adjusted, resulting in shape persistence and improved printing. We here review recent progress in the 3D printing of supramolecular polymers, with a focus on fused deposition modelling (FDM) to overcome some of its limitations still being present up to date and open perspectives for their application.

High molecular polymers have been widely studied and applied in the field of enhanced oil recovery (EOR). At present, the focus of research has been changed to the design of polymer networks with unique properties such as anti-temperature and anti-salinity, good injection and so on. Supramolecular polymers have high viscoelasticity as well as excellent temperature, salt resistance and injection properties. Can supramolecular polymers become another material choice for polymer flooding to enhance oil recovery? The present review aims to systematically introduce supramolecular polymers, including its design strategy, interactions and rheological properties, and address three main concerns: (1) Why choose supramolecular polymers? (2) How do we synthesize and characterize supramolecular polymers in the field of oilfield chemistry? (3) What has been the application progress of supramolecular polymers in improving oil recovery? The introduction of a supramolecular interaction system provides a new idea for polymer flooding and opens up a new research direction to improve oil recovery. Aiming at the “reversible dynamic” supramolecular polymers, the supramolecular polymers are compared with the conventional covalent macromolecular polymer networks, and the challenges and future research directions of supramolecular polymers in EOR are discussed. Finally, the author’s viewpoints and perspectives in this emerging field are discussed.

Cucurbit[n]urils, the pumpkin shaped macrocyclic host molecules possessing a hydrophobic cavity and two identical carbonyl portals, have drawn a lot of attention in recent years due to their high‐affinity yet dynamic molecular recognition properties in water. The reversible and stimuli‐responsive nature of their host‐guest complexes imparts "smart" features leading to materials with intriguing optical, mechanical and morphological properties. In this review, we focus on the design of cucurbituril based luminescent materials in aqueous media as well in solid or film state. The design principles of fluorescent complexes, small assemblies as well as supramolecular polymers along with their stimuli‐responsive properties and applications in diverse areas such as optoelectronic devices, light harvesting, anti‐counterfeiting and information technology, cell imaging, etc are highlighted with selected examples from recent literature. We also discuss examples of room temperature phosphorescent materials derived from purely organic luminogens in the presence of cucurbiturils. [ABSTRACT FROM AUTHOR]

Chirality can have unexpected consequences including on properties other than spectroscopic. We show herein that a racemic mixture of bis‐urea stereoisomers forms thermodynamically stable supramolecular polymers that result in a more viscous solution than for the pure stereoisomer. The origin of this macroscopic property was probed by characterizing the structure and stability of the assemblies. Both racemic and non‐racemic bis‐urea stereoisomers form two competing helical supramolecular polymers in solution: a double and a single helical structure at low and high temperature, respectively. The transition temperature between these assemblies, as probed by spectroscopic and calorimetric analyses, is strongly influenced by the composition (by up to 70 °C). A simple model that accounts for the thermodynamics of this system, indicates that the stereochemical defects (chiral mismatches and helix reversals) affect much more the stability of single helices. Therefore, the heterochiral double helical structure predominates over the single helical structure (whilst the opposite holds for the homochiral structures), which explains the aforementioned higher viscosity of the racemic bis‐urea solution. This rationale constitutes a new basis to tune the macroscopic properties of the increasing number of supramolecular polymers reported to exhibit competing chiral nanostructures. [ABSTRACT FROM AUTHOR]

The iterative association of monomer units through noncovalent interactions often leads to chiral supramolecular polymers. Monomers comprising these materials can be further divided into those with chiral centers and those without. The latter class is often less studied but attractive since it features monomer designs with chirality at the core rather than the periphery of the molecules. In this mini‐review, we summarize the existing strategies to construct supramolecular polymers from chiral molecules with no chiral centers and offer perspectives on fundamental trends and differences between them and their counterparts with chiral centers. © 2020 Society of Industrial Chemistry [ABSTRACT FROM AUTHOR]

A series of supramolecular polyurethanes (SPUs) were designed and synthesised with synergetic multifunctional hydrogen bonding aliphatic amide end-caps. Hydrogen bonding between the urethane, urea, and amide motifs in the polymers afford strong dynamic association between polymer chains in the solid state. Phase separation of the apolar and polar components of the polyurethanes also serves to reinforce their thermal and mechanical properties. The supramolecular polyurethane with bisamide-morpholine end caps associates via multiple hydrogen bonds and exhibits enhanced tensile and thermal properties when compared to the other materials. Variable-temperature infrared spectroscopy (VT-IR) and atomic force microscopy (AFM), were carried out to study the phase morphology of the polymers and revealed a correlation between increased phase separation and the introduction of amide motifs in the end-caps. These SPUs also exhibit excellent healing abilities, requiring temperatures >200 °C to recover their physical properties. [Display omitted] • Self-assembly of polyurethanes via hydrogen bonding and phase separation • Recovery of physical properties post damage at elevated temperatures • Re-adhesion demonstrated on both glass and aluminium over three cycles [ABSTRACT FROM AUTHOR]

Endowing superhydrophobic surfaces (SHS) with self-healing capability has been considered a promising approach to prolonging the lifespan of SHS. However, the reported SHS consisted of self-healing polymers and adhesive nanoparticles are still subject to the contradictions between robustness and complicated repairing conditions. In this work, a room-temperature self-healable, robust superhydrophobic coating was fabricated by combining dual cross-linking supramolecular silicone polymer (BPDI), which contains multiple hydrogen interactions and reversible nitrogen-coordinated boroxines, and SiO 2 nanoparticles via facile spraying methods. Benefiting from the synergetic dual reversible bonds and high mobility of BPDI polymer chains, the supramolecular resin exhibits excellent self-healing ability, recyclability, and high adhesive strength to the substrates. After the incorporation of SiO 2 nanoparticles, the surface of composite coatings revealed lotus-leaf-like morphology with an averaged roughness of 105 nm and superhydrophobicity with a WCA of 158.6°. More importantly, the obtained coatings could repair themselves spontaneously and repeatedly at room temperature via surface reorganization when the composites suffer chemical deterioration such as plasma etching. Furthermore, the coated surface can maintain superhydrophobicity even after being exposed to repeated mechanical or chemical damages, including sandpaper abrasion, solvent immersion, water dripping, and UV aging. The facts are reasonably attributed to the excellent stability of BPDI resins and robust interfacial adhesion with the substrate. Moreover, the prepared superhydrophobic composites with room-temperature self-healing capability and mechanochemical durability have been applied for self-cleaning and antifouling aspects on diverse substrates. • Supramolecular polymers with multiple hydrogen bonds and reversible nitrogen-coordinated boroxines have been prepared. • Superhydrophobic surfaces on diverse substrates were fabricated by spraying the mixture of polymers and SiO 2 nanoparticles. • The composite coatings with highly adhesive resins exhibited the superhydrophobic self-healing ability at room temperature. • Excellent self-cleaning and anti-fouling performances of the spayed coatings were achieved. [ABSTRACT FROM AUTHOR]

Supramolecular chemistry now presents an elaborate „enabling tool" that offers exciting opportunities for novel functional material design. One of the areas to benefit from recent advances in supramolecular chemistry is the field of molecularly imprinted polymers (MIPs), also known as "synthetic antibodies". It uses the memory of template molecules to form tailor-made binding sites in the polymer matrix. This review provides insights from rigorous recognition mode analysis perspectives and highlights evolving approaches in MIPs. First, the principles and recognition mode of molecular imprinting technology are carefully reviewed. The similarities and major differences between MIPs and enzymes are discussed. The internal 3D structure model of MIP is depicted, the origin and consequences of binding site heterogeneity are highlighted, and methods for the optimization of the recognition degree and imprinting efficiency are summarized. The criteria for evaluating imprinting efficacy and the role of chiral recognition in molecular imprinting are discussed. Subsequently, important approaches for the design and synthesis of MIPs a reviewed. Relevant approaches include dye displacement strategy for MIP sensors, multi-functional group recognition, monomolecular imprinting using dendrimers, solvent programmable polymer (SPP) based on restricted rotation, template activated molecular imprinting strategy, molecular imprinting with click chemistry, and evolution of molecular imprinting with computational strategies. Finally, the exciting progress of MIPs for recognition of biomacromolecules such as proteins, bacteria and viruses are discussed. The goal of this review is thus to inspire new applications of MIP materials and to provide a guide for how these applications might become a reality. Rigorous recognition mode analysis of molecularly imprinted polymers—Rational design, challenges, and opportunities. [Display omitted] [ABSTRACT FROM AUTHOR]