ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img

Assembling a Natural Small Molecule into a Supramolecular Network with High Structural Order and Dynamic Functions

  • Qi Zhang
    Qi Zhang
    Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China
    More by Qi Zhang
  • Yuan-Xin Deng
    Yuan-Xin Deng
    Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China
  • Hong-Xi Luo
    Hong-Xi Luo
    Department of Chemical Engineering, University of Virginia, 102 Engineers’ Way, P.O. Box 400741, Charlottesville, Virginia 22904, United States
    More by Hong-Xi Luo
  • Chen-Yu Shi
    Chen-Yu Shi
    Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China
    More by Chen-Yu Shi
  • Geoffrey M. Geise
    Geoffrey M. Geise
    Department of Chemical Engineering, University of Virginia, 102 Engineers’ Way, P.O. Box 400741, Charlottesville, Virginia 22904, United States
  • Ben L. Feringa*
    Ben L. Feringa
    Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China
    Centre for Systems Chemistry, Stratingh Institute for Chemistry and Zernike Institute for Advanced Materials, Faculty of Mathematics and Natural Sciences, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands
    *[email protected]
  • He Tian
    He Tian
    Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China
    More by He Tian
  • , and 
  • Da-Hui Qu*
    Da-Hui Qu
    Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China
    *[email protected]
    More by Da-Hui Qu
Cite this: J. Am. Chem. Soc. 2019, 141, 32, 12804–12814
Publication Date (Web):July 26, 2019
https://doi.org/10.1021/jacs.9b05740

Copyright © 2019 American Chemical Society. This publication is licensed under CC-BY-NC-ND.

  • Open Access

Article Views

21338

Altmetric

-

Citations

LEARN ABOUT THESE METRICS
PDF (8 MB)
Supporting Info (2)»

Abstract

Programming the hierarchical self-assembly of small molecules has been a fundamental topic of great significance in biological systems and artificial supramolecular systems. Precise and highly programmed self-assembly can produce supramolecular architectures with distinct structural features. However, it still remains a challenge how to precisely control the self-assembly pathway in a desirable way by introducing abundant structural information into a limited molecular backbone. Here we disclose a strategy that directs the hierarchical self-assembly of sodium thioctate, a small molecule of biological origin, into a highly ordered supramolecular layered network. By combining the unique dynamic covalent ring-opening-polymerization of sodium thioctate and an evaporation-induced interfacial confinement effect, we precisely direct the dynamic supramolecular self-assembly of this simple small molecule in a scheduled hierarchical pathway, resulting in a layered structure with long-range order at both macroscopic and molecular scales, which is revealed by small-angle and wide-angle X-ray scattering technologies. The resulting supramolecular layers are found to be able to bind water molecules as structural water, which works as an interlayer lubricant to modulate the material properties, such as mechanical performance, self-healing capability, and actuating function. Analogous to many reversibly self-assembled biological systems, the highly dynamic polymeric network can be degraded into monomers and reformed by a water-mediated route, exhibiting full recyclability in a facile, mild, and environmentally friendly way. This approach for assembling commercial small molecules into structurally complex materials paves the way for low-cost functional supramolecular materials based on synthetically simple procedures.

Introduction

ARTICLE SECTIONS
Jump To

Molecular self-assembly has emerged as a topic of great significance in general as it holds great promise toward next generations’ functional materials. (1−5) A variety of approaches followed by chemists triggered the rapid expansion of supramolecular self-assembly as an interdisciplinary area. (6,7) Using a “bottom-up” strategy, complex materials can be prepared by highly programmed self-assembly of small-molecule building blocks, (8−12) which might enable the precise tailoring and manipulation of matter and functional control along various length scales. (13,14) Until recently, supramolecular self-assembly in artificial molecular systems had exhibited a predominant capability to form morphology-controlled multidimensional structures, such as amphiphilic vesicles/micelles, (15) gels, (16,17) linear polymers, (18) and the cross-linked networks. (19) The hierarchical self-assembly of these primary structures can further result in truly unique soft matter. (20−22) The diversity, complexity, and functionality of these materials can be especially striking if the molecular self-assembly of the small building blocks is precisely controlled in a programmed mode, (23−25) also signifying the opportunity to program information via the molecular self-assembly mode into molecular structures as information. (26) In this context, structural information in a precursor molecule would enable the precisely controlled self-assembly of small molecules into large-scale assemblies with desirable organized structures and properties. However, to meet the rising need for advanced materials with sophisticated and even multiple functions, tedious synthetic routes are frequently required to prepare precursor molecules via complex chemical modifications, whereas simple buildings blocks leading to complexity would be highly desirable.
Very recently, we explored a small molecule of biological origin, called as thioctic acid, which is a naturally tailored building block that readily forms an amorphous supramolecular network, taking advantage of its disulfide-containing main chain cross-linked by hydrogen bonds and metal-carboxyl complexes, (27) which can be easily prepared by a solvent-free mild method. Although such an amorphous network exhibits potential applications in flexible and wearable materials, (28−32) the disordered cross-linking of the polymer chains hardly produces structurally ordered polymeric materials, which play a crucial role in many other areas, such as liquid crystals, (33−35) soft actuators, (36−40) ionic transport membranes, (41) and high-strength materials. (10,42) Herein, we focus on how this naturally tailored small molecule can be programmed by strategic molecular engineering to realize its precise self-assembly into long-range-order supramolecular architectures. We hope that exploring such a dynamic supramolecular self-assembly process toward structurally ordered assemblies could provide a new generation of molecular tools for the design and construction of supramolecular systems as well as natural product-based polymer materials. (43)
On the basis of this hypothesis, we demonstrate a rational derivation on the natural structure of thioctic acid by simple deprotonation to form amphiphilic sodium thioctate (ST). This simple small molecule can self-assemble into primary linear polymers at high concentrations by dynamic covalent ring-opening-polymerization (ROP), which undergo further self-organization into a highly ordered supramolecular network with a large-scale layered structure using a facile evaporation process. This is to the best of our knowledge an unprecedented example of directly assembling simple small molecules into supramolecular materials with high structural order, which is attributed to the naturally programmed structural information in this unique small-molecule building block. The dynamic covalent polymeric backbones and structural-water-cross-linked layered network simultaneously render the polymeric materials with good mechanical properties, humidity-actuated ability, and closed-loop recyclability.

Results and Discussion

ARTICLE SECTIONS
Jump To

Design Concept and Aqueous Self-Assembly

Structurally ordered assemblies are generally created by highly synergetic intermolecular interactions. The coexisting multiple species involved in molecular self-organization should be highly hierarchical in binding affinity as well as spatial distribution. (44) The thermal one-pot solvent-free polymerization of thioctic acid was a fast and homogeneous assembly process resulting in amorphous assemblies. (27) Structurally ordered self-assembly mostly involves a slow and thermodynamically controlled process, with relatively low growth rate kinetics to push the dynamic equilibrium toward a thermodynamically stable state. (22) Therefore, two issues should be addressed to realize the ordered self-assembly of thioctic acid: (i) the self-assembly process should not be instantaneous but be programmed with longer time scales, and (ii) multiple molecular interactions with different binding affinities should be introduced to enable a hierarchical self-assembly process with distinct spatial distribution. Notably, the order (or sequence in time) of these hierarchical molecular recognition processes should be also programmed in a precise and desirable pathway.
On the basis of these preconditions, we notice the unique structural features of thioctic acid for potential amphiphilic molecules. The terminal carboxylic group can be deprotonated to form a hydrophilic carboxylate group, while the five-membered disulfide-containing ring is hydrophobic, and the middle C4-methylene chain links the hydrophilic and hydrophobic parts as a typical amphiphilic structure (Figure 1A). This amphiphilic feature could work as structural information for molecular recognition, driving the self-organization of these small-molecule building blocks toward a more thermodynamically stable situation, in which the hydrophobic five-membered rings tend to aggregate to decrease interaction with the surrounding high-energy water molecules. This primary amphiphilic self-assembly further triggers the secondary dynamic covalent ROP reaction by the intermolecular dynamic covalent exchange of disulfide bonds facilitated by the increased intermolecular proximity. Furthermore, the subsequent self-assembly can be enabled using the outer hydrophilic carboxylate groups which recognized each other to form ionic bonds after the removal of solvent, forming an ionic-bond-cross-linked polymeric network (Figure 1B). As a consequence, these features enable the complex hierarchical self-assembly from small molecules to form three-dimensional polymeric networks.

Figure 1

Figure 1. Self-assembly process of sodium thioctate in water. (A and B) Molecular structures (A) and schematic representation (B) of the ST monomers, ST polymers, and their networks. (C) Photographs of the ST crystalline powder, viscous ST polymer solution, and the resulting free-standing flexible solid film. (D) Schematic mechanism of the evaporation-induced interfacial supramolecular self-assembly from disordered polymers in aqueous solution to dry-ordered film network.

Gram-scale ST monomers can easily be obtained by the quantitative deprotonation reaction of thioctic acid with sodium hydroxide in ethanol and subsequent filtration, yielding a light-yellow crystalline powder with high water-solubility (over 400 g/L at 298 K). Dissolving ST powder in water resulted in a homogeneous yellow solution, and the concentrated solution (over 200 g/L) exhibited remarkably increased viscosity (Figure 1C), suggesting polymerization. The formation of ring-opened linear poly(ST) polymer was confirmed by distinctive proton shifts (27) and broadening in the 1H NMR spectrum (Figure S1). Meanwhile, the disulfide-containing five-membered ring can be considered a chromophore because of its characteristic absorption maximum at 330 nm (Figure S2A), which originates from the red-shifted absorption of the disulfide group as a result of five-membered-ring tension. (45) Therefore, the absorbance of this chromophore can be used to detect the dynamic covalent ROP process in aqueous solution. (46) At concentrations lower than 150 g/L, the absorbance versus concentration plot of ST strictly follows Lambert–Beer’s law, while the absorbance of the 200 g/L sample exhibited a remarkable decrease in slope (Figure S2B), confirming the ROP process. It should be noted that the polymers and monomers coexisted in a concentrated state due to the presence of absorption at 330 nm. The coexistence is attributed to the dynamic nature of the dynamic covalent self-assembly process. (47) The viscous polymer solution exhibited excellent stability at room temperature, without phase separation or viscosity decrease after three months of observation (Figure S3). At an extremely high concentration (400 g/L), the high viscosity can even support the formation of a transparent hydrogel network at relatively low temperature (10 °C) (Figure S4), which can be rationalized on the basis of the formation of high-molecular-weight polymers and ionic-bond cross-links. The hydrogel is labile to concentration decrease and temperature increase, which would transform the material into a viscous polymer solution upon heating or dilution by water, revealing the dynamic reversible nature of this supramolecular polymer.

Evaporation-Induced Interfacial Self-Assembly

As demonstrated previously, the key to forming a structurally ordered network includes a long-time growth process and temporal distribution of the hierarchical self-assembly steps programmed in a precise and desirable pathway. The equilibrium states of the hierarchical dynamic self-assembly processes of poly(ST) are strongly dependent on concentration, indicating that a concentration increase can be a key factor to drive the proposed dynamic self-assembly equilibrium. On the basis of this notion, we employ a solvent-evaporation strategy to direct the hierarchical self-assembly process in a thermodynamically controlled manner. The evaporation-directed method has been used in controlling uniform assembled morphology of nanostructures. (48) Here we demonstrate that the evaporation process enables a dynamic covalent ROP templated by interfacial self-assembly (Figure 1D), i.e., the edge of the ellipsoidal droplet bears the fastest evaporation kinetic, thus undergoing nucleation at the edge region when the localized solution is oversaturated. Upon further solvent evaporation, the air/liquid/solid interface moves slowly along the evaporation direction, where the linear polymers assemble and grow at the three-phase interface, eventually producing a structurally ordered layered network. We propose that the interfacial confinement effect could well organize these unique small-molecule building blocks by producing a localized concentration gradient at the interface. Therefore, this whole process from small molecules (ST) to polymeric network poly(ST) can be identified as an evaporation-induced interfacial self-assembly (EIISA) route.
The EIISA process can be performed readily by dispensing the ST aqueous solution on a glass or polyethylene substrate followed by slow evaporation at ambient conditions, resulting in a free-standing dry solid polymeric film, which can be easily separated from the substrate (Figures 1C and S5 and S6). Polarized optical microscopy was employed to detect the self-assembly process with evaporation-induced interface movement in real time (Figures 2a and S7). Initially, the aqueous solution of ST is homogeneous and isotropic, hence exhibiting an invisible birefringence property. With the evaporation of the solution, a bright pattern of cyan color appeared to form an interface, suggesting the formation of structurally ordered assemblies. Then the interface moved along the evaporation direction, leaving the progressing route with expanded cyan patterns. The bright cyan regions changed into yellow patterns with further evaporation, which can be attributed to the shrinking of the assembled layers induced by water release.

Figure 2

Figure 2. (A) Real-time detection of the formation of a crystalline-phase structure, upon water evaporation, by polarized optical microscopy. The colored bright spots indicated the presence of ordered crystallites in the corresponding region. (B) Photographs of a poly(ST) polymer film with natural light showing good transparency. (C) Photographs of a poly(ST) polymer film under polarized light suggesting the extensive presence of ordered crystalline regions. (D) SEM images of poly(ST) polymer film.

The resulting polymer film exhibited good optical transparency (Figure 2B) and showed a remarkable birefringence feature (Figure 2C), indicating long-range-ordered self-assembly in bulk phase. The identical peak signals from the ST monomer powder and polymer film in the Fourier-transform infrared (FT-IR) spectrum (Figure S8) and Raman spectra (Figure S9) indicated similar chemical structures both before and after the EIISA process, confirming the absence of other side reactions. Scanning electron microscope (SEM) images (Figures 2D and S10) showed the compact surface morphology of the resulting films. Wrinkled nanostructures were observed, which might be the result of surface folding induced by solvent evaporation.

Structural Characterization of the Resulting Polymers

The polymeric nature of the resulting poly(ST) film can be confirmed by its optical properties. The diluted aqueous solution of monomer ST (1 g/L) containing a five-membered ring exhibited a characteristic absorption at 330 nm (Figure 3A) and photochemical excitation induced the ring-opening process to produce disulfide radicals, which were rebonded intramolecularly due to the uninitiated primary amphiphilic self-assembly at 1 g/L. The UV–vis reflection spectrum of the resulting poly(ST) film showed a peak at 312 nm, while no distinctive absorption was visible at 330 nm, indicating the absence of ST monomers. Differential scanning calorimetry (DSC) on the ST powder also showed a distinctive dehydration peak at 81.1 °C (Figure 3B), and no dehydration peak was observed at this region in the poly(ST) film, indicating a higher binding energy of bound water in the poly(ST) film compared to the powder. This result also suggests complete polymerization in the poly(ST)film because of the lack of a dehydration peak in the ST monomer thermogram.

Figure 3

Figure 3. (A) UV–vis absorption spectra of ST aqueous solution (1 g/L) and dry poly(ST) film. (B) DSC curves of the ST powder and poly(ST) polymer film. (C) Hydration number (λ) measurements under varying relative humidity. (D) FT-IR spectra of the poly(ST) polymer film before (red line) and after (black line) release of adsorbed D2O.

The water-sensitive ionic bonds in the network create the poly(ST) film’s humidity-responsive capability. The dry robust polymer film can adsorb water molecules from the air, leading to an increase in hydration that scales with the relative humidity (RH) of the air (Figure 3C). To quantitatively evaluate the hydration number (λ, defined as the number of water molecules per carboxylate group) of the humidity-responsive poly(ST) film, humidity-varying thermogravimetry was performed on the ST powder and poly(ST) film (Figure S11–S13). The ST powder exhibited a low λ value from 0.03 (RH = 0%) to 0.65 (RH = 98%) at 25 °C. However, the poly(ST) film bear a much higher λ which increased from 0.12 (RH = 0%) to 1.64 (RH = 98%) at 25 °C, and an increased temperature (40 °C) led to a slight difference of this range from 0.04 (RH = 0%) to 1.98 (RH = 98%). The higher λ number of poly(ST) film is attributed to its ordered layered structure, wherein the hydrophilic carboxylate groups associate to form interlayer water channels by ionic bonding. This enables the abundant spatial sites and carboxylate interlayers as the water diffusion channels. However, for the ST powder samples, the poor structural order resulted in the limited diffusion and hydration in the inner cores. On the contrary, notably slower hydration kinetics of poly(ST) film were observed compared with that of ST powder (Figure S14), which is attributed to the ordered layered structure of periodically alternating hydrophobic/hydrophilic layers. The sandwich-like layers confined the hydrophilic water channels in two-dimension between the hydrophobic polymer mainchain phase, thus slowing the hydration kinetics in the low humidity regions (Figure S15). The observed differences in hydration thermodynamics and kinetics between the ST powders and poly(ST) films further supports the proposed long-range-order layered structure with water channels in the poly(ST) films formed by EIISA method.
The water adsorption mechanism was confirmed by analysis of the FT-IR spectra (Figure S16). A slight IR shift for the carboxylate groups was observed from 1562 to 1552 cm–1 after adsorbing water, which was attributed to the hydration of the carboxylate groups. The disappearance of a shoulder peak at 1432 cm–1 after water adsorption also suggested the hydration of the carboxylate groups while the increased peak around 3400 cm–1 indicated bound water in the network. The release process was further confirmed by D2O because of its characteristic feature signal at around 2500 cm–1 (Figure 3D). The D2O molecules adsorbed in the poly(ST) network were found to be totally released by placing the film into dry air condition at room temperature, indicating that the bound water in the network can be fully exchanged in an ambient atmosphere.
X-ray diffraction and scattering tests (Figure 4) were performed to characterize the structural order of the resulting poly(ST) film. X-ray diffraction (XRD) of the dry poly(ST) film showed sharp and high-intensity diffraction peaks in the small angle regime (less than 20°), indicating a typical, highly ordered structure at the nanoscale (Figure 4A). The peak at 4.38° was attributed to a layer distance of 2.02 nm (calculated by the Bragg equation). The periodic signals also suggested a highly ordered layered structure. Meanwhile, the broad and low peak at around 23° suggested an amorphous hydrophobic disulfide-containing polymer main chain phase. (27) As a reference, ST powder was also measured, which showed a largely amorphous structure with poor structural order, indicating the significance of the EIISA method for the formation of structurally ordered poly(ST) film. Small-angle X-ray scattering (SAXS) showed a sharp scattering signal at 0.297 Å–1 (Figure 4B), indicating the high structural order with 2.11 nm spacing grazing-incidence wide-angle X-ray scattering (GIWAXS) further revealing the highly ordered layered structure of the resulting poly(ST) film (Figure 4C,D). The periodic one-dimensional scattering sharp peaks and two-dimensional high-intensity scattering rings confirmed the highly ordered layered structure in the poly(ST) network. (41) The observed scattering vector q = 0.302 Å–1 can be attributed to the layer distance of 2.08 nm of the resulting poly(ST) film, which was consistent with the XRD and SAXS results, confirming the interlayer distance as 2.1 nm of the layered poly(ST) film.

Figure 4

Figure 4. (A) XRD patterns of the ST monomer powders and the resulting poly(ST) film. (B) Synchrotron radiation SAXS pattern of the poly(ST) film. Inset image shows the distinctive scattering ring of the sample. (C) One-dimensional GIWAXS plot of the poly(ST) film. Scattering intensity is plotted versus qz. (D) Two-dimensional GIWAXS pattern of the poly(ST) film.

Rheology and Mechanical Properties

The storage moduli (G′) was higher than the loss moduli (G″) over the entire range of frequencies (Figure S17A) and also exhibited a single plateau region in the dynamic moduli. It should be noted that the moduli can be commensurate with that of the previously reported covalent-/iron(III)-co-cross-linked network, (27) even in the absence of a covalent cross-linker or iron(III) ions in the poly(ST) film. In a temperature-varied experiment (Figure S17B), moduli and viscosity slightly decreased with rising temperatures, which might be attributed to the thermo-labile disulfide bonds in the polymer main chain.
The dry polymer film exhibited robust mechanical properties with a Young’s tensile modulus of 168.8 MPa (Figure 5A), which was attributed to the ordered layered structure and high-affinity ionic bonds in the dry network. Interestingly, an increased hydrated degree led to a remarkable decrease in the tensile strength but also an increasing flexibility and stretchability (Figure 5A). This observation was attributed to the hydration of high-affinity ionic groups by bound water molecules, which worked as a lubricant-like structural water (49−51) by forming weak but dynamic hydrogen bonds in the interlayers of the network. The hydrated poly(ST) film exhibited a fast relaxation-recovery ability (Figure 5B and Movie S1) and an elasticity in a cyclic experiment (Figure S18). In the highly hydrated state (RH > 95%), the hydrated poly(ST) polymer turned very soft and viscous, showing a lower birefraction degree (Figure S19) and amorphous diffraction peaks (Figure S20), which is attributed to the formation of the hydrogen-bond-cross-linked network.

Figure 5

Figure 5. (A) Tensile stress curves of the poly(ST) film under different RH (5%, 50%, and 80%, respectively). Inset photographs show the stretched poly(ST) film (RH = 80%). (B) Photographs show the rapid relaxation behavior of a stretched poly(ST) film (RH = 80%). (C) Schematic representation of the tension-induced alignment of the elastic poly(ST) film. (D) Optical microscope images of the polymer filaments made by stretching the hydrated poly(ST) films (RH = 80%). Bright field (top) and polarized light field (bottom) show the ordered fibers paralleled with the tension direction. (E) Schematic representation and optical images of the helical filaments which are formed by mechanical tension followed by relaxation.

A notable decrease in optical transparency was observed upon stretching the elastic poly(ST) film (Figure 5A inset), which is the result of tension-induced order of the stretched polymer chain (Figure 5C). The alignment of microfibers along the tension direction can be observed in brightfield and polarized- light-field by optical microscopy (Figure 5D). Interestingly, an instant loosening of the stretched filaments resulted in a rapid formation of helical filaments, in which the aligned order was maintained. This transformation might be the result of an energy dissipation pathway originating from imposed potential energy within the stretched filaments. The helical structure was stable in dry conditions (RH < 50%) for several weeks, while they lost their shape and inner order upon exposure to highly humid conditions due to the decreased structural order by adsorbed water. Hence, the structural order of the layered network is necessary for this relaxation-induced spiraling behavior.

Applications as Dynamic Materials

The resulting structurally ordered layered supramolecular film simultaneously integrates dynamic covalent mainchains and supramolecular interaction in a single network, including noncovalent ionic bonds, hydrogen bonds of bound water, the van der Waals interaction of folded and packed polymer chains, and dynamic covalent disulfide bonds. These distinct features result from the dynamic nature of the polymer main chains with a high-proportion of disulfide groups, which might give this material unique dynamic properties and applications. The self-healing ability of the resulting poly(ST) films was confirmed by scratching experiments (Figure S21A). The film samples with varied degrees of hydration exhibited different self-healing capability, which was activated at the RH regions over 50%, while the dry samples showed no self-healing. In a typical healing experiment, a scratch can be healed almost completely in 12 h. Considering the switchable mechanical properties depending on reversible water adsorption/release, a water-mediated self-healing capability of mechanically robust materials is realized. Self-healing robust materials are very rare because of the limited interface mobility. (52) In our case, the damaged dry robust poly(ST) film can be “lubricated” by adsorbing water to enhance the interface mobility and dynamic properties. Then the damage can be healed, taking advantage of the reversible polymeric main chains and dynamic supramolecular interactions (Figure S21B), followed by releasing the water molecule upon drying to afford repaired and robust films.
Considering the three-dimensional multilayer polymer film, the humidity-induced expansion motion can be expected to be used as a humidity-induced actuator based on the supramolecular network. Placing a flat poly(ST) polymer film above a moisture generator would generate an asymmetric humidity gradient environment, with the film region near the water adsorbing more water molecules than the region away from the water, thus producing an asymmetric volume expansion degree (Figure 6A,B). In a typical experiment, a polymer film can transform from a flat shape into a bent one, while the inverse process can be driven by drying (Figure S22) or triggering the other less-hydrated side of the film (Figure 6C). The humidity-induced layer expansion can be confirmed by XRD patterns (Figure 6D), in which the diffraction angle of the film decreased with the increased RH, indicating the increase of layer distances after adsorbing water molecules. The kinetic curve showed a linear correlation with time and a responding rate of 2.9 deg/s (Figure 6E). Although several polymer actuators have been reported, (53,54) the actuator presented here based on the poly(ST) network, is totally cross-linked by dynamic covalent and supramolecular interactions instead of covalent cross-linkers, with an extremely simple preparation method initiated from natural small molecules.

Figure 6

Figure 6. (A) Schematic representation of the humidity-induced actuation behavior of poly(ST) polymer film. The blue arrows mean the humidity gradient direction. (B) Schematic representation of the expansion mechanism of the interlayers. (C) Photographs show the capability of poly(ST) polymer film acting as a humidity-responsive actuator. (D) XRD patterns of the poly(ST) film under varied RH. (E) Actuating kinetic curve of the bending polymer film to water vapor.

The realization of recyclability in synthetic polymers is a key topic toward environment and energy issues. Though many polymer materials can be degraded or reprocessed, it has been highly challenging to realize fully recyclable polymers which can be transformed into monomer feedstocks in a mild and facile condition. (55−60) Here we propose a polymer-recycling strategy by dynamic covalent ROP. Interestingly, dissolving the poly(ST) polymer film in water resulted in a monomer/oligomer solution (Figures 7A and S23), which was confirmed by 1H NMR spectroscopy (Figure S24). This result revealed that the cross-linked polymer network can be efficiently depolymerized into ring-closed ST monomers and oligomers by the addition of excess water. The high degradation efficiency can be also confirmed by the remarkably decreased moduli (below 5 Pa) and viscosity (below 10 Pas) of a degraded aqueous solution (100 g/L) (Figure S25). Then the recycled monomer/oligomers solution can be used to produce recycled polymer film by a similar EIISA process. Therefore, the closed-loop polymer-recycling process simply requires the mediation by water (Figure 7A) while the depolymerization process can be completed in 20 min (Figure 7B). The recycled polymer film exhibited consistent mechanical properties (Figure 7C), indicating the high recycling efficiency of this water-mediated route. Therefore, this polymer exhibits an unprecedented recyclability that bears no organic solvent, no heat, no high pressure, and no special technique, showing a promising potential toward environmentally friendly and energy-saving polymer materials.

Figure 7

Figure 7. (A) Schematic representation of the water-mediated recycling process of the poly(ST) films. (B) Photographs show the recycling process of the polymer film fragments into a new polymer film. (C) Tensile stress curve of the original and recycled poly(ST) films. The tested samples are dried at room temperature (RH < 10%).

Conclusions

ARTICLE SECTIONS
Jump To

By controlling the dynamic self-assembly of sodium thioctate (ST) in water based on hydrophilic/hydrophobic effects, dynamic covalent ROP, and ionic interactions with evaporation-induced interfacial ordering, we achieved hierarchical self-assembly of a small molecule into a layered supramolecular network with a long-range order. The resulting layered dry network bears alternating layers with hydrophilic ionic stacking and hydrophobic polymer mainchains, with the former being able to bind water molecules to form interlayer water channels. Distinct structural features provide this material with dynamic and adaptive mechanical properties, self-healing capability, and actuation functions. The unique dynamic covalent polymer mainchains can be disassembled into monomers and quantitively reused by a facile room-temperature water-mediated route, providing a conceptually new strategy to design recyclable polymeric materials.
In summary, this supramolecular material based on the self-assembly of deprotonated thioctic acid exhibits simplicity in preparation as well as order and complexity in structure and properties, pushing the versatile supramolecular materials based on thioctic acid from previously disordered elastomers to structurally ordered layers. This work paves the way for what we believe to be one of the fundamental issues in supramolecular chemistry; programming the precisely hierarchical self-assembly of small molecules toward structurally complex architectures, opening new avenues for dynamic polymeric materials in optics, electronics, sensors, coatings, and biomedical systems.

Materials and Methods

ARTICLE SECTIONS
Jump To

Materials Preparation

Sodium thioctate (ST) was prepared as bright yellow solid powder by a one-step reaction of equivalent amounts of thioctic acid and NaOH in ethanol/water solution heated under reflux. The ST powder is highly water-soluble and viscous aqueous solution can be obtained with a high concentration up to 300 g/L. In a typical preparation of poly(ST) film, a small volume of poly(ST) solution (300 g/L) was deposited on the substrate by simply drop-coating (the formed area is about 10 cm2 per 1 mL). The substrate can be glass, plastic dish, or Teflon. Then the polymer solution on the substrate was left in air to allow slow evaporation of the solvent. The evaporation process normally takes 2–6 h depending on the air humidity and the temperature. No remarkable difference was observed in the resulting polymer film obtained in different time within this time regime. The resulting dry polymer can be easily separated from the substrate as a transparent, free-standing, and robust polymer film.

Mechanical Tension Experiments

The stress–strain curves were recorded with an HY-0580 tension machine (HENGYI Company, Shanghai). The tested polymer films were preplaced for at least 2 h at the given RH to reach the adsorption/desorption equilibrium with water. Then the film was quickly fixed onto the tension machine and tested. The whole tension process was completed in 10 min. Considering the low water adsorption/desorption kinetic of the poly(ST) films, the hydration number of the polymer film in mechanical tension experiments can be considered as almost constant. The RH of the testing environment was fluctuated in a limited region (40% ∼ 60%). The film was shaped as a rectangle sample (20 × 10 × 0.5 mm). The initial length was 10 mm. Unless otherwise noted, the tensile stress was measured at a constant speed of 10 mm/min. The data were recorded in real time.

Hydration Number Measurement

The hydration thermodynamics and kinetics of poly(ST) film were measurement by a Relative Humidity Thermogravimetric Analyzer (RH-TGA, TA-Q5000 SA). In a typical experiment, a small piece of dry poly(ST) film (∼7 mg) was loaded into a metal-coated quartz pan, and the pan was transferred into the humidity chamber of the analyzer. The total gas flow rate (water vapor and N2) was chosen as 20 mL/min, and different relative humidity values, namely 0%, 25%, 50%, 75%, and 98%, were achieved by changing the relative flow rates of water vapor saturated N2 and dry N2 gas. The film was first dried at 60 °C at 0% RH for 4 h (8 h for powder) to remove residual moisture, and the film weight was recorded as the dry weight (WD). After the initial drying step, the chamber temperature was reduced to a designated value (i.e., 25 or 40 °C) and the RH value was increased stepwise to 98% (hydration) and then reduced stepwise to 0% (dehydration). The film was allowed to equilibrate at each RH value for 12 h (4 h for powder), and the film weight was recorded at the end of each 12 h equilibration step. The hydrated film weight (WH) at each RH value was taken as the average of the weight recorded during hydration and dehydration ramps. The film hydration number λ [eq(H2O)/eq(−COOH)] was defined as
where the EWST is the equivalent weight of ST and is taken as 228 g/mol.

Supporting Information

ARTICLE SECTIONS
Jump To

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.9b05740.

  • Additional materials and methods, NMR analysis, additional spectrum characterization, humidity-varied thermogravimetry, rheology experiments, and additional sample photographs (PDF)

  • Hydrated poly(ST) film exhibiting a fast relaxation-recovery ability (MP4)

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Author Information

ARTICLE SECTIONS
Jump To

  • Corresponding Authors
    • Ben L. Feringa - Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, ChinaCentre for Systems Chemistry, Stratingh Institute for Chemistry and Zernike Institute for Advanced Materials, Faculty of Mathematics and Natural Sciences, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The NetherlandsOrcidhttp://orcid.org/0000-0003-0588-8435 Email: [email protected]
    • Da-Hui Qu - Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, ChinaOrcidhttp://orcid.org/0000-0002-2039-3564 Email: [email protected]
  • Authors
    • Qi Zhang - Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China
    • Yuan-Xin Deng - Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China
    • Hong-Xi Luo - Department of Chemical Engineering, University of Virginia, 102 Engineers’ Way, P.O. Box 400741, Charlottesville, Virginia 22904, United StatesOrcidhttp://orcid.org/0000-0003-4824-9385
    • Chen-Yu Shi - Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China
    • Geoffrey M. Geise - Department of Chemical Engineering, University of Virginia, 102 Engineers’ Way, P.O. Box 400741, Charlottesville, Virginia 22904, United StatesOrcidhttp://orcid.org/0000-0002-5439-272X
    • He Tian - Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, ChinaOrcidhttp://orcid.org/0000-0003-3547-7485
  • Notes
    The authors declare no competing financial interest.

Acknowledgments

ARTICLE SECTIONS
Jump To

This work was supported by National Natural Science Foundation of China (Grants 21788102, 21790361, 21871084, 21672060, and 21421004), Shanghai Municipal Science and Technology Major Project (Grant 2018SHZDZX03), the Fundamental Research Funds for the Central Universities, the Programme of Introducing Talents of Discipline to Universities (Grant B16017), Program of Shanghai Academic/Technology Research Leader (19XD1421100), and the Shanghai Science and Technology Committee (Grant 17520750100). Geoffrey M. Geise appreciates the support of National Science Foundation under Grant CBET-1752048. Ben L. Feringa acknowledges financial support of The Netherlands Ministry of Education, Culture, and Science (Gravitation program 024.601035). We appreciate Dr. Na Li (BL19U2 beamline of Shanghai Synchrotron Radiation Facility) for her kind help in synchrotron SAXS test and Miss Qi Wei and Prof. Zhijun Ning (ShanghaiTech University) for their kind help in GIWAXS experiments. We thank the Research Center of Analysis and Test of East China University of Science and Technology for help on the material characterization.

References

ARTICLE SECTIONS
Jump To

This article references 60 other publications.

  1. 1
    Lutz, J. F.; Lehn, J. M.; Meijer, E. W.; Matyjaszewski, K. From precision polymers to complex materials and systems. Nat. Rev. Mater. 2016, 1, 16024,  DOI: 10.1038/natrevmats.2016.24
  2. 2
    Kang, J.; Miyajima, D.; Mori, T.; Inoue, Y.; Itoh, Y.; Aida, T. A rational strategy for the realization of chain-growth supramolecular polymerization. Science 2015, 347, 646651,  DOI: 10.1126/science.aaa4249
  3. 3
    Freeman, R.; Han, M.; Álvarez, Z.; Lewis, J. A.; Wester, J. R.; Stephanopoulos, N.; McClendon, M. T.; Lynsky, C.; Godbe, J. M.; Sangji, H.; Luijten, E.; Stupp, S. I. Reversible self-assembly of superstructured networks. Science 2018, 362, 808813,  DOI: 10.1126/science.aat6141
  4. 4
    Van Hameren, R.; Schön, P.; Van Buul, A. M.; Hoogboom, J.; Lazarenko, S. V.; Gerritsen, J. W.; Engelkamp, H.; Christianen, P. C. M.; Heus, H. A.; Maan, J. C.; Rasing, T.; Speller, S.; Rowan, A. E.; Elemans, J. A. A. W.; Nolte, R. J. M. Macroscopic hierarchical surface patterning of porphyrin trimers via self-assembly and dewetting. Science 2006, 314, 14331436,  DOI: 10.1126/science.1133004
  5. 5
    Boekhoven, J.; Hendriksen, W. E.; Koper, G. J. M.; Eelkema, R.; Van Esch, J. H. Transient assembly of active materials fueled by a chemical reaction. Science 2015, 349, 10751079,  DOI: 10.1126/science.aac6103
  6. 6
    Webber, M. J.; Appel, E. A.; Meijer, E. W.; Langer, R. Supramolecular biomaterials. Nat. Mater. 2016, 15, 1326,  DOI: 10.1038/nmat4474
  7. 7
    Yan, X.; Liu, Z.; Zhang, Q.; Lopez, J.; Wang, H.; Wu, H. C.; Niu, S.; Yan, H.; Wang, S.; Lei, T.; Li, J.; Qi, D.; Huang, P.; Huang, J.; Zhang, Y.; Wang, Y.; Li, G.; Tok, J. B. H.; Chen, X.; Bao, Z. Quadruple H-bonding cross-linked supramolecular polymeric materials as substrates for stretchable, antitearing, and self-healable thin film electrodes. J. Am. Chem. Soc. 2018, 140, 52805289,  DOI: 10.1021/jacs.8b01682
  8. 8
    Yamagishi, H.; Sato, H.; Hori, A.; Sato, Y.; Matsuda, R.; Kato, K.; Aida, T. Self-assembly of lattices with high structural complexity from a geometrically simple molecule. Science 2018, 361, 12421246,  DOI: 10.1126/science.aat6394
  9. 9
    Reches, M.; Gazit, E. Casting metal nanowires within discrete self-assembled peptide nanotubes. Science 2003, 300, 625627,  DOI: 10.1126/science.1082387
  10. 10
    Bera, S.; Mondal, S.; Xue, B.; Shimon, L. J. W.; Cao, Y.; Gazit, E. Rigid helical-like assemblies from a self-aggregating tripeptide. Nat. Mater. 2019, 18, 503509,  DOI: 10.1038/s41563-019-0343-2
  11. 11
    Chakraborty, P.; Guterman, T.; Adadi, N.; Yadid, M.; Brosh, T.; Adler-Abramovich, L.; Dvir, T.; Gazit, E. A Self-healing, all-organic, conducting, composite peptide hydrogel as pressure sensor and electrogenic cell soft substrate. ACS Nano 2019, 13, 163175,  DOI: 10.1021/acsnano.8b05067
  12. 12
    Kumar, M.; Ing, N. L.; Narang, V.; Wijerathne, N. K.; Hochbaum, A. I.; Ulijn, R. V. Amino-acid-encoded biocatalytic self-assembly enables the formation of transient conducting nanostructures. Nat. Chem. 2018, 10, 696703,  DOI: 10.1038/s41557-018-0047-2
  13. 13
    Goujon, A.; Moulin, E.; Fuks, G.; Giuseppone, N. [c2]Daisy chain rotaxanes as molecular muscles. CCS Chem. 2019, 1, 8396,  DOI: 10.31635/ccschem.019.20180023
  14. 14
    Gu, Y.; Alt, E. A.; Wang, H.; Li, X.; Willard, A. P.; Johnson, J. A. Photoswitching topology in polymer networks with metal-organic cages as crosslinks. Nature 2018, 560, 6569,  DOI: 10.1038/s41586-018-0339-0
  15. 15
    Hendricks, M. P.; Sato, K.; Palmer, L. C.; Stupp, S. I. Supramolecular assembly of peptide amphiphiles. Acc. Chem. Res. 2017, 50, 24402448,  DOI: 10.1021/acs.accounts.7b00297
  16. 16
    Wang, Q.; Mynar, J. L.; Yoshida, M.; Lee, E.; Lee, M.; Okuro, K.; Kinbara, K.; Aida, T. High-water-content mouldable hydrogels by mixing clay and a dendritic molecular binder. Nature 2010, 463, 339343,  DOI: 10.1038/nature08693
  17. 17
    Sano, K.; Ishida, Y.; Aida, T. Synthesis of anisotropic hydrogels and their applications. Angew. Chem., Int. Ed. 2018, 57, 25322543,  DOI: 10.1002/anie.201708196
  18. 18
    Sijbesma, R. P.; Beijer, F. H.; Brunsveld, L.; Folmer, B. J.; Hirschberg, J. K.; Lange, R. F.; Lowe, J. K. L.; Meijer, E. W. Reversible polymers formed from self-complementary monomers using quadruple hydrogen bonding. Science 1997, 278, 16011604,  DOI: 10.1126/science.278.5343.1601
  19. 19
    Supramolecular Polymer Chemistry; Harada, A., Ed.; Wiley-VCH: Weinheim, 2011.
  20. 20
    Doncom, K. E.; Blackman, L. D.; Wright, D. B.; Gibson, M. I.; O’Reilly, R. K. Dispersity effects in polymer self-assemblies: a matter of hierarchical control. Chem. Soc. Rev. 2017, 46, 41194134,  DOI: 10.1039/C6CS00818F
  21. 21
    Sun, C.; Shen, M.; Chavez, A. D.; Evans, A. M.; Liu, X.; Harutyunyan, B.; Flanders, N. C.; Hersam, M. C.; Bedzyk, M. J.; De La Cruz, M. O.; Dichtel, W. R. High aspect ratio nanotubes assembled from macrocyclic iminium salts. Proc. Natl. Acad. Sci. U. S. A. 2018, 115, 88838888,  DOI: 10.1073/pnas.1809383115
  22. 22
    Wei, P.; Yan, X.; Huang, F. Supramolecular polymers constructed by orthogonal self-assembly based on host–guest and metal–ligand interactions. Chem. Soc. Rev. 2015, 44, 815832,  DOI: 10.1039/C4CS00327F
  23. 23
    Lehn, J. M. Perspectives in chemistry—steps towards complex matter. Angew. Chem., Int. Ed. 2013, 52, 28362850,  DOI: 10.1002/anie.201208397
  24. 24
    Aida, T.; Meijer, E. W.; Stupp, S. I. Functional supramolecular polymers. Science 2012, 335, 813817,  DOI: 10.1126/science.1205962
  25. 25
    Vantomme, G.; Meijer, E. W. The construction of supramolecular systems. Science 2019, 363, 13961397,  DOI: 10.1126/science.aav4677
  26. 26
    Rutten, M. G. T. A.; Vaandrager, F. W.; Elemans, J. A. A. W.; Nolte, R. J. M. Encoding information into polymers. Nat. Rev. Chem. 2018, 2, 365381,  DOI: 10.1038/s41570-018-0051-5
  27. 27
    Zhang, Q.; Shi, C. Y.; Qu, D. H.; Long, Y. T.; Feringa, B. L.; Tian, H. Exploring a naturally tailored small molecule for stretchable, self-healing, and adhesive supramolecular polymers. Sci. Adv. 2018, 4, eaat8192  DOI: 10.1126/sciadv.aat8192
  28. 28
    Wang, S.; Xu, J.; Wang, W.; Wang, G.; Rastak, R.; Molina-Lopez, F.; Chung, J. W.; Niu, S.; Feig, V. R.; Lopez, J.; Lei, T.; Kwon, S. K.; Kim, Y.; Foudeh, A. M.; Ehrlich, A.; Gasperini, A.; Yun, Y.; Murmann, B.; Tok, J. B. H.; Bao, Z. Skin electronics from scalable fabrication of an intrinsically stretchable transistor array. Nature 2018, 555, 8388,  DOI: 10.1038/nature25494
  29. 29
    Kim, Y.; Chortos, A.; Xu, W.; Liu, Y.; Oh, J. Y.; Son, D.; Kang, J.; Foudeh, A. M.; Zhu, C.; Lee, Y.; Niu, S.; Liu, J.; Pfattner, R.; Bao, Z.; Lee, T. W. A bioinspired flexible organic artificial afferent nerve. Science 2018, 360, 9981003,  DOI: 10.1126/science.aao0098
  30. 30
    Son, D.; Kang, J.; Vardoulis, O.; Kim, Y.; Matsuhisa, N.; Oh, J. Y.; To, J. W. F.; Mun, J.; Katsumata, T.; Liu, Y.; McGuire, A. F.; Krason, M.; Molina-Lopez, F.; Ham, J.; Kraft, U.; Lee, Y.; Yun, Y.; Tok, J. B. H.; Bao, Z. An integrated self-healable electronic skin system fabricated via dynamic reconstruction of a nanostructured conducting network. Nat. Nanotechnol. 2018, 13, 10571065,  DOI: 10.1038/s41565-018-0244-6
  31. 31
    Xu, J.; Wang, S.; Wang, G. J. N.; Zhu, C.; Luo, S.; Jin, L.; Rondeau-Gagné, S.; Park, S.; Schroeder, B. C.; Lu, C.; Lu, C.; Oh, J. Y.; Wang, Y.; Kim, Y. H.; Yan, H.; Sinclair, R.; Zhou, D.; Xue, G.; Murmann, B.; Linder, C.; Cai, W.; Tok, J. B. H.; Chung, J. W.; Bao, Z. Highly stretchable polymer semiconductor films through the nanoconfinement effect. Science 2017, 355, 5964,  DOI: 10.1126/science.aah4496
  32. 32
    Nan, K.; Kang, S. D.; Li, K.; Yu, K. J.; Zhu, F.; Wang, J.; Dunn, A. C.; Zhou, C.; Xie, Z.; Agne, M. T.; Wang, H.; Luan, H.; Zhang, Y.; Huang, Y.; Synder, G. J.; Rogers, J. A. Compliant and stretchable thermoelectric coils for energy harvesting in miniature flexible devices. Sci. Adv. 2018, 4, eaau5849  DOI: 10.1126/sciadv.aau5849
  33. 33
    Miyajima, D.; Araoka, F.; Takezoe, H.; Kim, J.; Kato, K.; Takata, M.; Aida, T. Ferroelectric columnar liquid crystal featuring confined polar groups within core–shell architecture. Science 2012, 336, 209213,  DOI: 10.1126/science.1217954
  34. 34
    Xia, Y.; Mathis, T. S.; Zhao, M. Q.; Anasori, B.; Dang, A.; Zhou, Z.; Cho, H.; Gogotsi, Y.; Yang, S. Thickness-independent capacitance of vertically aligned liquid-crystalline MXenes. Nature 2018, 557, 409412,  DOI: 10.1038/s41586-018-0109-z
  35. 35
    Nyström, G.; Arcari, M.; Mezzenga, R. Confinement-induced liquid crystalline transitions in amyloid fibril cholesteric tactoids. Nat. Nanotechnol. 2018, 13, 330336,  DOI: 10.1038/s41565-018-0071-9
  36. 36
    Arazoe, H.; Miyajima, D.; Akaike, K.; Araoka, F.; Sato, E.; Hikima, T.; Kawamoto, M.; Aida, T. An autonomous actuator driven by fluctuations in ambient humidity. Nat. Mater. 2016, 15, 10841089,  DOI: 10.1038/nmat4693
  37. 37
    Gelebart, A. H.; Mulder, D. J.; Varga, M.; Konya, A.; Vantomme, G.; Meijer, E. W.; Selinger, R. L. B.; Broer, D. J. Making waves in a photoactive polymer film. Nature 2017, 546, 632636,  DOI: 10.1038/nature22987
  38. 38
    Lv, J. A.; Liu, Y.; Wei, J.; Chen, E.; Qin, L.; Yu, Y. Photocontrol of fluid slugs in liquid crystal polymer microactuators. Nature 2016, 537, 179184,  DOI: 10.1038/nature19344
  39. 39
    Eelkema, R.; Pollard, M. M.; Vicario, J.; Katsonis, N.; Ramon, B. S.; Bastiaansen, C. W.; Broer, D. J.; Feringa, B. L. Nanomotor rotates microscale objects. Nature 2006, 440, 163,  DOI: 10.1038/440163a
  40. 40
    Ware, T. H.; McConney, M. E.; Wie, J. J.; Tondiglia, V. P.; White, T. J. Voxelated liquid crystal elastomers. Science 2015, 347, 982984,  DOI: 10.1126/science.1261019
  41. 41
    Trigg, E. B.; Gaines, T. W.; Maréchal, M.; Moed, D. E.; Rannou, P.; Wagener, K. B.; Stevens, M. J.; Winey, K. I. Self-assembled highly ordered acid layers in precisely sulfonated polyethylene produce efficient proton transport. Nat. Mater. 2018, 17, 725731,  DOI: 10.1038/s41563-018-0097-2
  42. 42
    Song, J.; Chen, C.; Zhu, S.; Zhu, M.; Dai, J.; Ray, U.; Li, Y.; Kuang, Y.; Li, Y.; Quispe, N.; Yao, Y.; Gong, A.; Leiste, U. H.; Bruck, H. A.; Zhu, J. Y.; Vellore, A.; Li, H.; Minus, M. L.; Jia, Z.; Martini, A.; Li, T.; Hu, L. Processing bulk natural wood into a high-performance structural material. Nature 2018, 554, 224228,  DOI: 10.1038/nature25476
  43. 43
    Kristufek, S. L.; Wacker, K. T.; Tsao, Y.-Y.; Su, L.; Wooley, K. L. Monomer design strategies to create natural product-based polymer materials. Nat. Prod. Rep. 2017, 34, 433459,  DOI: 10.1039/C6NP00112B
  44. 44
    Yu, Z.; Tantakitti, F.; Yu, T.; Palmer, L. C.; Schatz, G. C.; Stupp, S. I. Simultaneous covalent and noncovalent hybrid polymerizations. Science 2016, 351, 497502,  DOI: 10.1126/science.aad4091
  45. 45
    Barltrop, J. A.; Hayes, P. M.; Calvin, M. The chemistry of 1,2-dithiolane (trimethylene disulfide) as a model for the primary quantum conversion act in photosynthesis. J. Am. Chem. Soc. 1954, 76, 43484367,  DOI: 10.1021/ja01646a029
  46. 46
    Fava, A.; Iliceto, A.; Camera, E. Kinetics of the thiol-disulfide exchange. J. Am. Chem. Soc. 1957, 79, 833838,  DOI: 10.1021/ja01561a014
  47. 47
    Zhang, X.; Waymouth, R. M. 1,2-Dithiolane-derived dynamic, covalent materials: cooperative self-assembly and reversible cross-linking. J. Am. Chem. Soc. 2017, 139, 38223833,  DOI: 10.1021/jacs.7b00039
  48. 48
    Singh, G.; Chan, H.; Baskin, A.; Gelman, E.; Repnin, N.; Král, P.; Klajn, R. Self-assembly of magnetite nanocubes into helical superstructures. Science 2014, 345, 11491153,  DOI: 10.1126/science.1254132
  49. 49
    Dong, S.; Leng, J.; Feng, Y.; Liu, M.; Stackhouse, C. J.; Schönhals, A.; Chiappisi, L.; Gao, L.; Chen, W.; Shang, J.; Jin, L.; Qi, Z.; Schalley, C. A. Structural water as an essential comonomer in supramolecular polymerization. Sci. Adv. 2017, 3, eaao0900  DOI: 10.1126/sciadv.aao0900
  50. 50
    Zhang, Q.; Li, T.; Duan, A.; Dong, S.; Zhao, W.; Stang, P. J. Formation of a supramolecular polymeric adhesive via water-participant hydrogen bond formation. J. Am. Chem. Soc. 2019, 141, 80588063,  DOI: 10.1021/jacs.9b02677
  51. 51
    Van Zee, N. J.; Adelizzi, B.; Mabesoone, M. F.; Meng, X.; Aloi, A.; Zha, R. H.; Lutz, M.; Filot, I. A. W.; Palmans, A. R. A.; Meijer, E. W. Potential enthalpic energy of water in oils exploited to control supramolecular structure. Nature 2018, 558, 100103,  DOI: 10.1038/s41586-018-0169-0
  52. 52
    Yanagisawa, Y.; Nan, Y.; Okuro, K.; Aida, T. Mechanically robust, readily repairable polymers via tailored noncovalent cross-linking. Science 2018, 359, 7276,  DOI: 10.1126/science.aam7588
  53. 53
    De Haan, L. T.; Verjans, J. M.; Broer, D. J.; Bastiaansen, C. W.; Schenning, A. P. Humidity-responsive liquid crystalline polymer actuators with an asymmetry in the molecular trigger that bend, fold, and curl. J. Am. Chem. Soc. 2014, 136, 1058510588,  DOI: 10.1021/ja505475x
  54. 54
    Ma, M.; Guo, L.; Anderson, D. G.; Langer, R. Bio-inspired polymer composite actuator and generator driven by water gradients. Science 2013, 339, 186189,  DOI: 10.1126/science.1230262
  55. 55
    Lloyd, E. M.; Lopez Hernandez, H.; Feinberg, A. M.; Yourdkhani, M.; Zen, E. K.; Mejia, E. B.; Sottos, N. R.; Moore, J. S.; White, S. R. Fully recyclable metastable polymers and composites. Chem. Mater. 2019, 31, 398406,  DOI: 10.1021/acs.chemmater.8b03585
  56. 56
    Zou, Z.; Zhu, C.; Li, Y.; Lei, X.; Zhang, W.; Xiao, J. Rehealable, fully recyclable, and malleable electronic skin enabled by dynamic covalent thermoset nanocomposite. Sci. Adv. 2018, 4, eaaq0508  DOI: 10.1126/sciadv.aaq0508
  57. 57
    Christensen, P. R.; Scheuermann, A. M.; Loeffler, K. E.; Helms, B. A. Closed-loop recycling of plastics enabled by dynamic covalent diketoenamine bonds. Nat. Chem. 2019, 11, 442448,  DOI: 10.1038/s41557-019-0249-2
  58. 58
    Miller, K. A.; Morado, E. G.; Samanta, S. R.; Walker, B. A.; Nelson, A. Z.; Sen, S.; Tran, D. T.; Whitaker, D. J.; Ewoldt, R. H.; Braun, P. V.; Zimmerman, S. C. Acid-triggered, acid-generating, and self-amplifying degradable polymers. J. Am. Chem. Soc. 2019, 141, 28382842,  DOI: 10.1021/jacs.8b07705
  59. 59
    Zhu, J. B.; Watson, E. M.; Tang, J.; Chen, E. Y. X. A synthetic polymer system with repeatable chemical recyclability. Science 2018, 360, 398403,  DOI: 10.1126/science.aar5498
  60. 60
    Rahimi, A.; García, J. M. Chemical recycling of waste plastics for new materials production. Nat. Rev. Chem. 2017, 1, 0046,  DOI: 10.1038/s41570-017-0046

Cited By

ARTICLE SECTIONS
Jump To

This article is cited by 184 publications.

  1. Jinwei Cui, Xuesu Su, Bining Jiao, Wei Xiang, Yangyang Fang. Efficiently Synthesized, Multifunctional Recyclable Hydrogel for Accelerated Wound Healing. ACS Applied Polymer Materials 2024, Article ASAP.
  2. Jianhua Lu, Yuanhao Dai, Yahui He, Ting Zhang, Jing Zhang, Xiangmei Chen, Changtao Jiang, Hua Lu. Organ/Cell-Selective Intracellular Delivery of Biologics via N-Acetylated Galactosamine-Functionalized Polydisulfide Conjugates. Journal of the American Chemical Society 2024, 146 (6) , 3974-3983. https://doi.org/10.1021/jacs.3c11914
  3. Tianyi Du, Boming Shen, Jieyu Dai, Miaomiao Zhang, Xingjian Chen, Peiyuan Yu, Yun Liu. Controlled and Regioselective Ring-Opening Polymerization for Poly(disulfide)s by Anion-Binding Catalysis. Journal of the American Chemical Society 2023, 145 (50) , 27788-27799. https://doi.org/10.1021/jacs.3c10708
  4. Kirti Wasnik, Prem Shankar Gupta, Sudip Mukherjee, Alagu Oviya, Ravi Prakash, Divya Pareek, Sukanya Patra, Somedutta Maity, Vipin Rai, Monika Singh, Gurmeet Singh, Desh Deepak Yadav, Santanu Das, Pralay Maiti, Pradip Paik. Poly(N-acryloylglycine-acrylamide) Hydrogel Mimics the Cellular Microenvironment and Promotes Neurite Growth with Protection from Oxidative Stress. ACS Applied Bio Materials 2023, 6 (12) , 5644-5661. https://doi.org/10.1021/acsabm.3c00807
  5. Hee-won Bahng, Cathrin D. Ertl, Jennifer Yuan, Michael O. Wolf. Light-Controlled Switching of Perylene Bisimide Assemblies. The Journal of Physical Chemistry Letters 2023, 14 (46) , 10369-10377. https://doi.org/10.1021/acs.jpclett.3c02468
  6. Hongtian Zhang, Yongke Hu, Zhulan Liu, Ren’ai Li, Yunfeng Cao. A Highly Transparent, Underwater Self-Healing, Self-Adhesive, and Recyclable Supramolecular Eutectogel for Liquid Metal Encapsulation. ACS Materials Letters 2023, 5 (10) , 2621-2628. https://doi.org/10.1021/acsmaterialslett.3c00555
  7. Zhengyu Deng, Elizabeth R. Gillies. Emerging Trends in the Chemistry of End-to-End Depolymerization. JACS Au 2023, 3 (9) , 2436-2450. https://doi.org/10.1021/jacsau.3c00345
  8. Sijia Zheng, Haiyan Xue, Jun Yao, Yang Chen, Michael A. Brook, Muhammad Ebad Noman, Zhihai Cao. Exploring Lipoic Acid-Mediated Dynamic Bottlebrush Elastomers as a New Platform for the Design of High-Performance Thermally Conductive Materials. ACS Applied Materials & Interfaces 2023, 15 (34) , 41043-41054. https://doi.org/10.1021/acsami.3c09826
  9. Yuetao Liu, Susu Zhao, Yujie Jiang, Qian Liu, Zhi Liu, Chengxin Song, Cancai Wang. AgNP Hybrid Organosilicon Antifouling Coating with Spontaneous Self-Healing and Long-Term Antifouling Properties. Industrial & Engineering Chemistry Research 2023, 62 (33) , 12999-13008. https://doi.org/10.1021/acs.iecr.3c01569
  10. Yuchen Guo, Yuhang Liu, Xinyang Zhao, Jun Zhao, Yongming Wang, Xinhai Zhang, Zhewen Guo, Xuzhou Yan. Synergistic Covalent-and-Supramolecular Polymers with an Interwoven Topology. ACS Applied Materials & Interfaces 2023, 15 (21) , 25161-25172. https://doi.org/10.1021/acsami.2c10404
  11. Karan Vivek Dikshit, Aseem Milind Visal, Femke Janssen, Alexander Larsen, Carson J. Bruns. Pressure-Sensitive Supramolecular Adhesives Based on Lipoic Acid and Biofriendly Dynamic Cyclodextrin and Polyrotaxane Cross-Linkers. ACS Applied Materials & Interfaces 2023, 15 (13) , 17256-17267. https://doi.org/10.1021/acsami.3c00927
  12. Caikun Liu, Ruilin Lu, Mengqi Jia, Xiao Xiao, Yun Chen, Pengfei Li, Shiyong Zhang. Biological Glue from Only Lipoic Acid for Scarless Wound Healing by Anti-inflammation and TGF-β Regulation. Chemistry of Materials 2023, 35 (6) , 2588-2599. https://doi.org/10.1021/acs.chemmater.3c00049
  13. Yuanxin Deng, Qi Zhang, Da-Hui Qu. Emerging Hydrogen-Bond Design for High-Performance Dynamic Polymeric Materials. ACS Materials Letters 2023, 5 (2) , 480-490. https://doi.org/10.1021/acsmaterialslett.2c00865
  14. Zhiwu Chen, Yonglin He, Xinglei Tao, Yingchao Ma, Jichen Jia, Yapei Wang. Thermal Nociception of Ionic Skin: TRPV1 Ion Channel-Inspired Heat-Activated Dynamic Ionic Liquid. The Journal of Physical Chemistry Letters 2022, 13 (43) , 10076-10084. https://doi.org/10.1021/acs.jpclett.2c02952
  15. Qianfu Luo, Chenyu Shi, Zhaoxia Wang, Meng Chen, Da-Hui Qu. Introducing the Latest Self-healing Polymer Based on Thioctic Acid into the Undergraduate Chemistry Laboratory. Journal of Chemical Education 2022, 99 (10) , 3488-3496. https://doi.org/10.1021/acs.jchemed.2c00463
  16. Kaiming Zhang, Sheng Chen, Yanglei Chen, Liangying Jia, Can Cheng, Shuli Dong, Jingcheng Hao. Elastomeric Liquid-Free Conductor for Iontronic Devices. Langmuir 2022, 38 (39) , 11994-12004. https://doi.org/10.1021/acs.langmuir.2c01749
  17. Jianhua Lu, Zhun Xu, Hailin Fu, Yao Lin, Huan Wang, Hua Lu. Room-Temperature Grafting from Synthesis of Protein–Polydisulfide Conjugates via Aggregation-Induced Polymerization. Journal of the American Chemical Society 2022, 144 (34) , 15709-15717. https://doi.org/10.1021/jacs.2c05997
  18. Shanshan Liu, Jianpei Xu, Yipu Liu, Yang You, Laozhi Xie, Shiqiang Tong, Yu Chen, Kaifan Liang, Songlei Zhou, Fengan Li, Zhuang Tang, Ni Mei, Huiping Lu, Xiaolin Wang, Xiaoling Gao, Jun Chen. Neutrophil-Biomimetic “Nanobuffer” for Remodeling the Microenvironment in the Infarct Core and Protecting Neurons in the Penumbra via Neutralization of Detrimental Factors to Treat Ischemic Stroke. ACS Applied Materials & Interfaces 2022, 14 (24) , 27743-27761. https://doi.org/10.1021/acsami.2c09020
  19. Xiaoling Kong, Xin Jin, Meng Xiao, Jumin Yang, Yang Zou, Xianhua Xie, Changjun Liu, Xiangyu Wei, Jianhai Yang, Wei Wang. An Extensively Adhesive Patch with Multiple Physical Interactions and Chemical Crosslinking as a Wound Dressing and Strain Sensor. ACS Applied Polymer Materials 2022, 4 (5) , 3926-3941. https://doi.org/10.1021/acsapm.2c00390
  20. Fuxing Zhao, Hao Liu, Hanxin Li, Yixin Cao, Xuyu Hua, Shengzhuo Ge, Yu He, Chongwen Jiang, Dewen He. Cogel Strategy for the Preparation of a “Thorn”-Like Porous Halloysite/Gelatin Composite Aerogel with Excellent Mechanical Properties and Thermal Insulation. ACS Applied Materials & Interfaces 2022, 14 (15) , 17763-17773. https://doi.org/10.1021/acsami.1c23647
  21. Yang Wang, Yu Zhang, Zheng Zhang, Ting Li, Jie Jiang, Xuhui Zhang, Tianxi Liu, Jinliang Qiao, Jing Huang, Weifu Dong. Pistachio-Inspired Bulk Graphene Oxide-Based Materials with Shapeability and Recyclability. ACS Nano 2022, 16 (2) , 3394-3403. https://doi.org/10.1021/acsnano.2c00281
  22. Qi Zhang, Da-Hui Qu, Ben L. Feringa, He Tian. Disulfide-Mediated Reversible Polymerization toward Intrinsically Dynamic Smart Materials. Journal of the American Chemical Society 2022, 144 (5) , 2022-2033. https://doi.org/10.1021/jacs.1c10359
  23. Hongjun Jin, Cheng Ma, Wenkai Wang, Yiteng Cai, Jinwan Qi, Tongyue Wu, Peilong Liao, Hongpeng Li, Qing Zeng, Mengqi Xie, Jianbin Huang, Yun Yan. Using Molecules with Superior Water-Plasticity to Build Solid-Phase Molecular Self-Assembly: Room-Temperature Engineering Mendable and Recyclable Functional Supramolecular Plastics. ACS Materials Letters 2022, 4 (1) , 145-152. https://doi.org/10.1021/acsmaterialslett.1c00724
  24. Changyong Cai, Shuanggen Wu, Zhijian Tan, Fenfang Li, Shengyi Dong. On-Site Supramolecular Adhesion to Wet and Soft Surfaces via Solvent Exchange. ACS Applied Materials & Interfaces 2021, 13 (44) , 53083-53090. https://doi.org/10.1021/acsami.1c15959
  25. Chen-Yu Shi, Qi Zhang, Bang-Sen Wang, Meng Chen, Da-Hui Qu. Intrinsically Photopolymerizable Dynamic Polymers Derived from a Natural Small Molecule. ACS Applied Materials & Interfaces 2021, 13 (37) , 44860-44867. https://doi.org/10.1021/acsami.1c11679
  26. Ruirui Gu, Jean-Marie Lehn. Constitutional Dynamic Selection at Low Reynolds Number in a Triple Dynamic System: Covalent Dynamic Adaptation Driven by Double Supramolecular Self-Assembly. Journal of the American Chemical Society 2021, 143 (35) , 14136-14146. https://doi.org/10.1021/jacs.1c04446
  27. Shuai Huang, Yikang Shen, Hari K. Bisoyi, Yu Tao, Zhongcheng Liu, Meng Wang, Hong Yang, Quan Li. Covalent Adaptable Liquid Crystal Networks Enabled by Reversible Ring-Opening Cascades of Cyclic Disulfides. Journal of the American Chemical Society 2021, 143 (32) , 12543-12551. https://doi.org/10.1021/jacs.1c03661
  28. Zhiwu Chen, Naiwei Gao, Yanji Chu, Yonglin He, Yapei Wang. Ionic Network Based on Dynamic Ionic Liquids for Electronic Tattoo Application. ACS Applied Materials & Interfaces 2021, 13 (28) , 33557-33565. https://doi.org/10.1021/acsami.1c09278
  29. Jian Li, Hongyao Niu, Yingfeng Yu, Yulei Gao, Qiang Wu, Fenfen Wang, Pingchuan Sun. Supramolecular Polydimethylsiloxane Elastomer with Enhanced Mechanical Properties and Self-Healing Ability Engineered by Synergetic Dynamic Bonds. ACS Applied Polymer Materials 2021, 3 (7) , 3373-3382. https://doi.org/10.1021/acsapm.1c00271
  30. Quentin Laurent, Rémi Martinent, Bumhee Lim, Anh-Tuan Pham, Takehiro Kato, Javier López-Andarias, Naomi Sakai, Stefan Matile. Thiol-Mediated Uptake. JACS Au 2021, 1 (6) , 710-728. https://doi.org/10.1021/jacsau.1c00128
  31. Jing Huang, Aleksandra Alicja Wróblewska, Jan Steinkoenig, Stephan Maes, Filip E. Du Prez. Assembling Lipoic Acid and Nanoclay into Nacre-Mimetic Nanocomposites. Macromolecules 2021, 54 (10) , 4658-4668. https://doi.org/10.1021/acs.macromol.1c00281
  32. Mingyeong Shin, Seulgi Kim, Eunji Lee, Jong Hwa Jung, In-Hyeok Park, Shim Sung Lee. Pillar[5]-bis-trithiacrown: Influence of Host–Guest Interactions on the Formation of Coordination Networks. Inorganic Chemistry 2021, 60 (8) , 5804-5811. https://doi.org/10.1021/acs.inorgchem.1c00114
  33. Jakub W. Trzciński, Lucía Morillas-Becerril, Sara Scarpa, Marco Tannorella, Francesco Muraca, Federico Rastrelli, Chiara Castellani, Marny Fedrigo, Annalisa Angelini, Regina Tavano, Emanuele Papini, Fabrizio Mancin. Poly(lipoic acid)-Based Nanoparticles as Self-Organized, Biocompatible, and Corona-Free Nanovectors. Biomacromolecules 2021, 22 (2) , 467-480. https://doi.org/10.1021/acs.biomac.0c01321
  34. Kai Liu, Lin Cheng, Ningbin Zhang, Hui Pan, Xiwen Fan, Guangfeng Li, Zhaoming Zhang, Dong Zhao, Jun Zhao, Xue Yang, Yongming Wang, Ruixue Bai, Yuhang Liu, Zhiyuan Liu, Sheng Wang, Xinglong Gong, Zhenan Bao, Guoying Gu, Wei Yu, Xuzhou Yan. Biomimetic Impact Protective Supramolecular Polymeric Materials Enabled by Quadruple H-Bonding. Journal of the American Chemical Society 2021, 143 (2) , 1162-1170. https://doi.org/10.1021/jacs.0c12119
  35. Jun-Bo Hou, Zhi-Hui Chen, Shao-Xia Zhang, Zi-Jun Nie, Shu-Ting Fan, Hao-Ran Shu, Sheng Zhang, Bang-Jing Li, Ya Cao. A Tough Self-Healing Elastomer with a Slip-Ring Structure. Industrial & Engineering Chemistry Research 2021, 60 (1) , 251-262. https://doi.org/10.1021/acs.iecr.0c04190
  36. Joshua C. Worch, Andrew P. Dove. 100th Anniversary of Macromolecular Science Viewpoint: Toward Catalytic Chemical Recycling of Waste (and Future) Plastics. ACS Macro Letters 2020, 9 (11) , 1494-1506. https://doi.org/10.1021/acsmacrolett.0c00582
  37. Kaiming Zhang, Jiawen Sun, Jingyao Song, Chuanhui Gao, Zhe Wang, Chengxin Song, Yumin Wu, Yuetao Liu. Self-Healing Ti3C2 MXene/PDMS Supramolecular Elastomers Based on Small Biomolecules Modification for Wearable Sensors. ACS Applied Materials & Interfaces 2020, 12 (40) , 45306-45314. https://doi.org/10.1021/acsami.0c13653
  38. Kui Wang, Mi-Ni Wang, Qi-Qi Wang, Chang Liu, Yu-Han Du, Siyang Xing, Bolin Zhu. UV Accelerated Assemblies Constructed Using Calixpyridinium in Aqueous Solution. Langmuir 2020, 36 (37) , 11161-11168. https://doi.org/10.1021/acs.langmuir.0c02356
  39. Chunxiao Chai, Yiyi Guo, Zhaohui Huang, Zhuo Zhang, Shuang Yang, Weiwei Li, Yunpeng Zhao, Jingcheng Hao. Antiswelling and Durable Adhesion Biodegradable Hydrogels for Tissue Repairs and Strain Sensors. Langmuir 2020, 36 (35) , 10448-10459. https://doi.org/10.1021/acs.langmuir.0c01605
  40. Rodrigo Cezar de Campos Ferreira, Alejandro Pérez Paz, Duncan John Mowbray, Jean-Yves Roulet, Richard Landers, Abner de Siervo. Supramolecular Ordering and Reactions of a Chlorophenyl Porphyrin on Ag(111). The Journal of Physical Chemistry C 2020, 124 (26) , 14220-14228. https://doi.org/10.1021/acs.jpcc.0c02953
  41. Chao Dang, Zhongyuan Huang, Yian Chen, Shenghui Zhou, Xiao Feng, Guixian Chen, Fanglin Dai, Haisong Qi. Direct Dissolution of Cellulose in NaOH/Urea/α-Lipoic Acid Aqueous Solution to Fabricate All Biomass-Based Nitrogen, Sulfur Dual-Doped Hierarchical Porous Carbon Aerogels for Supercapacitors. ACS Applied Materials & Interfaces 2020, 12 (19) , 21528-21538. https://doi.org/10.1021/acsami.0c01537
  42. Javier López-Andarias, Jacques Saarbach, Dimitri Moreau, Yangyang Cheng, Emmanuel Derivery, Quentin Laurent, Marcos González-Gaitán, Nicolas Winssinger, Naomi Sakai, Stefan Matile. Cell-Penetrating Streptavidin: A General Tool for Bifunctional Delivery with Spatiotemporal Control, Mediated by Transport Systems Such as Adaptive Benzopolysulfane Networks. Journal of the American Chemical Society 2020, 142 (10) , 4784-4792. https://doi.org/10.1021/jacs.9b13621
  43. Guangchen Sun, Jiajie Pan, Yifan Wu, Yue Liu, Wei Chen, Zhiyun Zhang, Jianhua Su. Supramolecular Assembly-Driven Color-Tuning and White-Light Emission Based on Crown-Ether-Functionalized Dihydrophenazine. ACS Applied Materials & Interfaces 2020, 12 (9) , 10875-10882. https://doi.org/10.1021/acsami.0c00780
  44. Wuhou Fan, Yong Jin, Liangjie Shi, Weining Du, Rong Zhou, Shuanquan Lai, Yichao Shen, Yupeng Li. Achieving Fast Self-Healing and Reprocessing of Supertough Water-Dispersed “Living” Supramolecular Polymers Containing Dynamic Ditelluride Bonds under Visible Light. ACS Applied Materials & Interfaces 2020, 12 (5) , 6383-6395. https://doi.org/10.1021/acsami.9b18985
  45. Lei Wang, Lin Cheng, Guangfeng Li, Kai Liu, Zhaoming Zhang, Peitong Li, Shengyi Dong, Wei Yu, Feihe Huang, Xuzhou Yan. A Self-Cross-Linking Supramolecular Polymer Network Enabled by Crown-Ether-Based Molecular Recognition. Journal of the American Chemical Society 2020, 142 (4) , 2051-2058. https://doi.org/10.1021/jacs.9b12164
  46. Jianhua Lu, Hao Wang, Ziyou Tian, Yingqin Hou, Hua Lu. Cryopolymerization of 1,2-Dithiolanes for the Facile and Reversible Grafting-from Synthesis of Protein–Polydisulfide Conjugates. Journal of the American Chemical Society 2020, 142 (3) , 1217-1221. https://doi.org/10.1021/jacs.9b12937
  47. Guo Ye, Zizheng Song, Tianhao Yu, Qishuo Tan, Yan Zhang, Tinglei Chen, Changcheng He, Lihua Jin, Nan Liu. Dynamic Ag–N Bond Enhanced Stretchable Conductor for Transparent and Self-Healing Electronic Skin. ACS Applied Materials & Interfaces 2020, 12 (1) , 1486-1494. https://doi.org/10.1021/acsami.9b17354
  48. Bo Yi, Peng Liu, Changshun Hou, Chunyan Cao, Jianqiang Zhang, Hongyan Sun, Xi Yao. Dual-Cross-Linked Supramolecular Polysiloxanes for Mechanically Tunable, Damage-Healable and Oil-Repellent Polymeric Coatings. ACS Applied Materials & Interfaces 2019, 11 (50) , 47382-47389. https://doi.org/10.1021/acsami.9b17199
  49. Yun Liu, Yuan Jia, Qiong Wu, Jeffrey S. Moore. Architecture-Controlled Ring-Opening Polymerization for Dynamic Covalent Poly(disulfide)s. Journal of the American Chemical Society 2019, 141 (43) , 17075-17080. https://doi.org/10.1021/jacs.9b08957
  50. Ying Qi, Chenyu Xu, Zhuodan Zhang, Qian Zhang, Ziyang Xu, Xinrui Zhao, Yanhong Zhao, Chunyan Cui, Wenguang Liu. Wet environment-induced adhesion and softening of coenzyme-based polymer elastic patch for treating periodontitis. Bioactive Materials 2024, 35 , 259-273. https://doi.org/10.1016/j.bioactmat.2024.02.002
  51. Hao Guo, Wenjie Zhang, Zhaoli Jia, Penghui Wang, Qing Shao, Haifeng Shen, Jialing Li, Qiang Chen, Bo Chi. A Biodegradable Supramolecular Adhesive with Robust Instant Wet Adhesion for Urgent Hemostasis and Wound Repair. Advanced Functional Materials 2024, https://doi.org/10.1002/adfm.202401529
  52. Ayhan Yurtsever, Kaito Hirata, Ryohei Kojima, Keisuke Miyazawa, Kazuki Miyata, Sanhanut Kesornsit, Hadi Zareie, Linhao Sun, Katsuhiro Maeda, Mehmet Sarikaya, Takeshi Fukuma. Dynamics of Molecular Self‐Assembly of Short Peptides at Liquid–Solid Interfaces – Effect of Charged Amino Acid Point Mutations. Small 2024, 14 https://doi.org/10.1002/smll.202400653
  53. Chenhui Cui, Fang Wang, Xingxing Chen, Ting Xu, Zhen Li, Kexiang Chen, Yinzhou Guo, Yilong Cheng, Zhishen Ge, Yanfeng Zhang. Covalent Adaptable Networks with Dual Dynamic Covalent Bonds for Self‐Repairing Infrared Transmitting Materials. Advanced Functional Materials 2024, 74 https://doi.org/10.1002/adfm.202315469
  54. Yang Lou, Edmund F. Palermo. Dynamic Antimicrobial Poly(disulfide) Coatings Exfoliate Biofilms On Demand Via Triggered Depolymerization. Advanced Healthcare Materials 2024, 78 https://doi.org/10.1002/adhm.202303359
  55. Jianhua Zhang, Yunjuan Su, Jian Wu, Hongdong Wang. Recent advances in ocular lubrication. Friction 2024, 86 https://doi.org/10.1007/s40544-023-0828-5
  56. Yuanxin Deng, Qi Zhang, Ben L. Feringa. Dynamic Chemistry Toolbox for Advanced Sustainable Materials. Advanced Science 2024, 69 https://doi.org/10.1002/advs.202308666
  57. Leilei Wu, Bingjie Fan, Biaobiao Yan, Ying Liu, Yuanyuan Yu, Li Cui, Man Zhou, Qiang Wang, Ping Wang. Construction of durable antibacterial cellulose textiles through grafting dynamic disulfide-containing amino-compound and nanosilver deposition. International Journal of Biological Macromolecules 2024, 259 , 129085. https://doi.org/10.1016/j.ijbiomac.2023.129085
  58. Hang-Tian Zhang, Li-Ke Hou, Guang-Wen Chu, Jie-Xin Wang, Liang-Liang Zhang, Jian-Feng Chen. Cationic ring-opening polymerization of natural thioctic acid to chemically recyclable and self-healable poly(thioctic acid) supramolecular material. Chemical Engineering Journal 2024, 482 , 148816. https://doi.org/10.1016/j.cej.2024.148816
  59. Dengfeng He, Chunyan Liao, Pengfei Li, Xiaoming Liao, Shiyong Zhang. Multifunctional photothermally responsive hydrogel as an effective whole-process management platform to accelerate chronic diabetic wound healing. Acta Biomaterialia 2024, 174 , 153-162. https://doi.org/10.1016/j.actbio.2023.11.043
  60. Dengfeng He, Xingmou Liu, Jiezhi Jia, Bo Peng, Na Xu, Qing Zhang, Shang Wang, Lei Li, Menglong Liu, Yong Huang, Xiaorong Zhang, Yunlong Yu, Gaoxing Luo. Magnetic Field‐Directed Deep Thermal Therapy via Double‐Layered Microneedle Patch for Promoting Tissue Regeneration in Infected Diabetic Skin Wounds. Advanced Functional Materials 2024, 34 (2) https://doi.org/10.1002/adfm.202306357
  61. Xiang Chen, Chenxi Hu, Yang Wang, Ting Li, Jie Jiang, Jing Huang, Shibo Wang, Weifu Dong, Jinliang Qiao. A Self‐Assemble Supramolecular Film with Humidity Visualization Enabled by Clusteroluminescence. Advanced Science 2024, 11 (1) https://doi.org/10.1002/advs.202304946
  62. Ruiqing Li, Sen Yan, Tianwei Xue, Rongxing Qiu, Yin Li, Wenli Hao, Guangkuo Xu, Yanliang Wang, Yanzhen Hong, Yuzhong Su, Hongtao Wang, Shuliang Yang, Li Peng, Jun Li. A MOF/poly(thioctic acid) composite for enhanced gold extraction from water matrices. Nano Research 2024, 17 (1) , 382-389. https://doi.org/10.1007/s12274-023-6077-0
  63. Julian F. Highmoore, Lasith S. Kariyawasam, Scott R. Trenor, Ying Yang. Design of depolymerizable polymers toward a circular economy. Green Chemistry 2024, 540 https://doi.org/10.1039/D3GC04215D
  64. Song Chen, Xinyu Chen, Kaiying Luo, Wenwei Yang, Xueling Yan, Lan Liu. Thermo-growing ion clusters enabled healing strengthening and tough adhesion for highly reliable skin electronics. Materials Horizons 2024, 24 https://doi.org/10.1039/D3MH01975F
  65. Leilei Wu, Xueming Bao, Zirong Li, Yuanyuan Yu, Ying Liu, Bo Xu, Man Zhou, Qiang Wang, Ping Wang. Rapid photothermal antibacterial and antifungal textiles through dynamic disulfide bond-assisted in-situ deposition of SeNPs. Chemical Engineering Journal 2024, 479 , 147772. https://doi.org/10.1016/j.cej.2023.147772
  66. Ying Zhang, Chenxiao Zhou, Lizhi Lin, Fengtao Pei, Mengqi Xiao, Xiaoyan Yang, Guizhou Yuan, Cheng Zhu, Yu Chen, Qi Chen. Gelation of Hole Transport Layer to Improve the Stability of Perovskite Solar Cells. Nano-Micro Letters 2023, 15 (1) https://doi.org/10.1007/s40820-023-01145-y
  67. Xinyue Wang, Qiang Wang, Ping Wang, Man Zhou, Bo Xu, Ying Liu, Yuanyuan Yu. A soft multifunctional film from chitosan modified with disulfide bond cross-links and prepared by a simple method. International Journal of Biological Macromolecules 2023, 253 , 126774. https://doi.org/10.1016/j.ijbiomac.2023.126774
  68. Jing Sun, Haonan He, Kelu Zhao, Wenhao Cheng, Yuanxin Li, Peng Zhang, Sikang Wan, Yawei Liu, Mengyao Wang, Ming Li, Zheng Wei, Bo Li, Yi Zhang, Cong Li, Yao Sun, Jianlei Shen, Jingjing Li, Fan Wang, Chao Ma, Yang Tian, Juanjuan Su, Dong Chen, Chunhai Fan, Hongjie Zhang, Kai Liu. Protein fibers with self-recoverable mechanical properties via dynamic imine chemistry. Nature Communications 2023, 14 (1) https://doi.org/10.1038/s41467-023-41084-1
  69. Chunyan Cui, Li Mei, Danyang Wang, Pengfei Jia, Qihui Zhou, Wenguang Liu. A self-stabilized and water-responsive deliverable coenzyme-based polymer binary elastomer adhesive patch for treating oral ulcer. Nature Communications 2023, 14 (1) https://doi.org/10.1038/s41467-023-43571-x
  70. Chunyan Cui, Yage Sun, Xiongfeng Nie, Xuxuan Yang, Fushuo Wang, Wenguang Liu. A Coenzyme‐Based Deep Eutectic Supramolecular Polymer Bioadhesive. Advanced Functional Materials 2023, 33 (49) https://doi.org/10.1002/adfm.202307543
  71. Boyan Du, Yongbin Wu, Shifu Lu, Ziqi Yang, Siya Huang. Spider‐Silk‐Inspired Heterogeneous Supramolecular Network with Strain‐Stiffening, High Damping Capacity, and Supercontraction. Advanced Functional Materials 2023, 33 (50) https://doi.org/10.1002/adfm.202306071
  72. Li-Wei Liu, Zheng-Hao Ding, Gang-Gang Ren, Guang-Di Wang, Xin Pan, Guo-Hai Wei, Xiang Zhou, Zhi-Bing Wu, Zhi-Chao Jin, Yonggui Robin Chi, Song Yang. Inorganic Nanoparticles–Driven Self–Assembly of natural small molecules in water for constructing multifunctional nanocapsules against plant diseases. Chemical Engineering Journal 2023, 475 , 146041. https://doi.org/10.1016/j.cej.2023.146041
  73. Guohong Yao, Fenfang Li, Shengyi Dong. Solvent-free bulk soft material with low-temperature tolerance: Transparency, flexibility, stretchability, and adhesion. Chemical Engineering Science 2023, 281 , 119164. https://doi.org/10.1016/j.ces.2023.119164
  74. Liqiang Li, Xiaotong Peng, Di Zhu, Jing Zhang, Pu Xiao. Recent Progress in Polymers with Dynamic Covalent Bonds. Macromolecular Chemistry and Physics 2023, 224 (20) https://doi.org/10.1002/macp.202300224
  75. Jianhua Liu, Xiaolin Li, Kangbo Chen, Yaping Li, ShuaiShuai Feng, Peipei Su, Yang Zou, Yi Li, Wei Wang. Super Adhesive Fluorescent Materials for Encrypted Messages, Underwater Leak Repair, and Their Potential Application in Fluorescent Tattoos. Macromolecular Rapid Communications 2023, 44 (19) https://doi.org/10.1002/marc.202300282
  76. Yun‐Shuai Huang, Yang Zhou, Xiaolong Zeng, Dachuan Zhang, Si Wu. Reversible Crosslinking of Commodity Polymers via Photocontrolled Metal–Ligand Coordination for High‐Performance and Recyclable Thermoset Plastics. Advanced Materials 2023, 35 (41) https://doi.org/10.1002/adma.202305517
  77. Katherine Le, Xia Sun, Junjie Chen, Johnson V. John, Amir Servati, Hossein Heidari, Ali Khademhosseini, Frank Ko, Feng Jiang, Peyman Servati. Stretchable, self-healing, biocompatible, and durable ionogel for continuous wearable strain and physiological signal monitoring. Chemical Engineering Journal 2023, 471 , 144675. https://doi.org/10.1016/j.cej.2023.144675
  78. Yi Zhang, Hua Lu. Ring-opening copolymerization of hydroxyproline-derived thiolactones and lipoic acid derivatives. Polymer Chemistry 2023, 14 (33) , 3813-3820. https://doi.org/10.1039/D3PY00467H
  79. Zhaolin Wu, Yuhang Guo, MingZhi Qin, Chaoyou Liao, Xiufen Wang, Liqun Zhang. Study on fabricating transparent, stretchable, and self-healing ionic conductive elastomers from biomass molecules through solvent-free synthesis. Journal of Materials Chemistry A 2023, 11 (30) , 16074-16083. https://doi.org/10.1039/D3TA02053C
  80. Xinxin Yang, Bowen Zhang, Jingjing Li, Minggui Shen, He Liu, Xu Xu, Shibin Shang. Self-healing, self-adhesive, and stretchable conductive hydrogel for multifunctional sensor prepared by catechol modified nanocellulose stabilized poly(α-thioctic acid). Carbohydrate Polymers 2023, 313 , 120813. https://doi.org/10.1016/j.carbpol.2023.120813
  81. Feng Li, Weidong Gu, Shanshan Gong, Wenrui Zhou, Sheldon.Q. Shi, Qiang Gao, Zhen Fang, Jianzhang Li. Design of amphiphilic-function-aiding biopolymer adhesives for strong and durable underwater adhesion via a simple solvent-exchange approach. Chemical Engineering Journal 2023, 469 , 143793. https://doi.org/10.1016/j.cej.2023.143793
  82. Jiahua Wang, Tiemei Lu, Yuehua Li, Junyou Wang, Evan Spruijt. Aqueous coordination polymer complexes: From colloidal assemblies to bulk materials. Advances in Colloid and Interface Science 2023, 318 , 102964. https://doi.org/10.1016/j.cis.2023.102964
  83. Chunxiao Chai, Pengfei Zhang, Lin Ma, Qi Fan, Zhicheng Liu, Xiang Cheng, Yunpeng Zhao, Weiwei Li, Jingcheng Hao. Regenerative antibacterial hydrogels from medicinal molecule for diabetic wound repair. Bioactive Materials 2023, 25 , 541-554. https://doi.org/10.1016/j.bioactmat.2022.07.020
  84. Animesh Ghosh, Konrad Kozlowski, Terry W. J. Steele. Synthesis and Evaluation of Metal Lipoate Adhesives. Polymers 2023, 15 (13) , 2921. https://doi.org/10.3390/polym15132921
  85. Subhankar Kundu, Subhadeep Das, Abhijit Patra. Fluorescence correlation spectroscopy and fluorescence lifetime imaging microscopy for deciphering the morphological evolution of supramolecular self-assembly. Chemical Communications 2023, 59 (52) , 8017-8031. https://doi.org/10.1039/D2CC06607F
  86. Bang-Sen Wang, Da-Hui Qu. The Many Ways for Reversible Polymerization of 1,2-Dithiolanes. Chemistry Letters 2023, 52 (6) , 496-502. https://doi.org/10.1246/cl.230142
  87. Jiahui Liu, Rong Sheng Li, Lei Zhang, Jie Wang, Qi Dong, Zhigang Xu, Yuejun Kang, Peng Xue. Enzyme‐Activatable Polypeptide for Plasma Membrane Disruption and Antitumor Immunity Elicitation. Small 2023, 19 (24) https://doi.org/10.1002/smll.202206912
  88. Runze Xue, Ning Zhou, Shijie Yin, Zhehao Qian, Zhifeng Dai, Yubing Xiong. All-polymer dynamical ionogel-like materials with benzyl-mediated ultra-strong adhesion for flexible sensor application. Chemical Engineering Journal 2023, 465 , 143072. https://doi.org/10.1016/j.cej.2023.143072
  89. Fang Wang, Jiaqiang Du, Hao Qiao, Dongfan Liu, Dong Guo, Jinjin Chen, Yanfeng Zhang, Yilong Cheng, Xijing He. Natural small molecule-induced polymer hydrogels with inherent antioxidative ability and conductivity for neurogenesis and functional recovery after spinal cord injury. Chemical Engineering Journal 2023, 466 , 143071. https://doi.org/10.1016/j.cej.2023.143071
  90. Jiaqiang Du, Fang Wang, Jiaxi Li, Yuxuan Yang, Dong Guo, Yanfeng Zhang, Aimin Yang, Xijing He, Yilong Cheng. Green polymer hydrogels from a natural monomer with inherent antioxidative capability for efficient wound healing and spinal cord injury treatment. Biomaterials Science 2023, 11 (10) , 3683-3694. https://doi.org/10.1039/D3BM00174A
  91. Jiaxiang Gao, Qing Zhang, Bo Wu, Xiaodan Gao, Zhengyuan Liu, Haoyu Yang, Jikang Yuan, Jijun Huang. Mussel‐Inspired, Underwater Self‐Healing Ionoelastomers Based on α‐Lipoic Acid for Iontronics. Small 2023, 19 (21) https://doi.org/10.1002/smll.202207334
  92. Ziqing Hu, Shaoyu Xu, Hanwei Zhang, Xiaofan Ji. Aggregates of fluorescent gels assembled by interfacial dynamic bonds. Aggregate 2023, 4 (2) https://doi.org/10.1002/agt2.283
  93. Xiangliang Zeng, Lu Xu, Xinnian Xia, Xue Bai, Cheng Zhong, Jianfeng Fan, Linlin Ren, Rong Sun, Xiaoliang Zeng. The Synergy of Hydrogen Bond and Entanglement of Elastomer Captures Unprecedented Flaw Insensitivity Rate. Small 2023, 19 (16) https://doi.org/10.1002/smll.202207409
  94. Hao Xu, Yujun Liu, Xu-Ming Xie. Stretchable alkaline quasi-solid-state electrolytes created by super-tough, fatigue-resistant and alkali-resistant multi-bond network hydrogels. Chinese Chemical Letters 2023, 34 (4) , 107470. https://doi.org/10.1016/j.cclet.2022.04.068
  95. Bang‐Sen Wang, Qi Zhang, Zhi‐Qiang Wang, Chen‐Yu Shi, Xue‐Qing Gong, He Tian, Da‐Hui Qu. Acid‐catalyzed Disulfide‐mediated Reversible Polymerization for Recyclable Dynamic Covalent Materials. Angewandte Chemie 2023, 135 (11) https://doi.org/10.1002/ange.202215329
  96. Bang‐Sen Wang, Qi Zhang, Zhi‐Qiang Wang, Chen‐Yu Shi, Xue‐Qing Gong, He Tian, Da‐Hui Qu. Acid‐catalyzed Disulfide‐mediated Reversible Polymerization for Recyclable Dynamic Covalent Materials. Angewandte Chemie International Edition 2023, 62 (11) https://doi.org/10.1002/anie.202215329
  97. Gang Ge, Kalpana Mandal, Reihaneh Haghniaz, Mengchen Li, Xiao Xiao, Larry Carlson, Vadim Jucaud, Mehmet Remzi Dokmeci, Ghim Wei Ho, Ali Khademhosseini. Deep Eutectic Solvents‐Based Ionogels with Ultrafast Gelation and High Adhesion in Harsh Environments. Advanced Functional Materials 2023, 33 (9) https://doi.org/10.1002/adfm.202207388
  98. Hongjun Jin, Weilin Lin, Ziyan Wu, Xinyu Cheng, Xinyuan Chen, Yingjie Fan, Wangchuan Xiao, Jianbin Huang, Qingrong Qian, Qinghua Chen, Yun Yan. Surface Hydrophobization Provides Hygroscopic Supramolecular Plastics Based on Polysaccharides with Damage‐Specific Healability and Room‐Temperature Recyclability. Advanced Materials 2023, 35 (8) https://doi.org/10.1002/adma.202207688
  99. Xin‐Lei Li, Kai Ma, Fei Xu, Tie‐Qi Xu. Advances in the Synthesis of Chemically Recyclable Polymers. Chemistry – An Asian Journal 2023, 18 (3) https://doi.org/10.1002/asia.202201167
  100. Rong Cui, Bing Li, Chunyan Liao, Shiyong Zhang. Copper-mediated chemodynamic therapy with ultra-low copper consumption by doping cupric ion on cross-linked ( R )-(+)-lipoic acid nanoparticles. Regenerative Biomaterials 2023, 10 https://doi.org/10.1093/rb/rbad021
Load all citations
  • Abstract

    Figure 1

    Figure 1. Self-assembly process of sodium thioctate in water. (A and B) Molecular structures (A) and schematic representation (B) of the ST monomers, ST polymers, and their networks. (C) Photographs of the ST crystalline powder, viscous ST polymer solution, and the resulting free-standing flexible solid film. (D) Schematic mechanism of the evaporation-induced interfacial supramolecular self-assembly from disordered polymers in aqueous solution to dry-ordered film network.

    Figure 2

    Figure 2. (A) Real-time detection of the formation of a crystalline-phase structure, upon water evaporation, by polarized optical microscopy. The colored bright spots indicated the presence of ordered crystallites in the corresponding region. (B) Photographs of a poly(ST) polymer film with natural light showing good transparency. (C) Photographs of a poly(ST) polymer film under polarized light suggesting the extensive presence of ordered crystalline regions. (D) SEM images of poly(ST) polymer film.

    Figure 3

    Figure 3. (A) UV–vis absorption spectra of ST aqueous solution (1 g/L) and dry poly(ST) film. (B) DSC curves of the ST powder and poly(ST) polymer film. (C) Hydration number (λ) measurements under varying relative humidity. (D) FT-IR spectra of the poly(ST) polymer film before (red line) and after (black line) release of adsorbed D2O.

    Figure 4

    Figure 4. (A) XRD patterns of the ST monomer powders and the resulting poly(ST) film. (B) Synchrotron radiation SAXS pattern of the poly(ST) film. Inset image shows the distinctive scattering ring of the sample. (C) One-dimensional GIWAXS plot of the poly(ST) film. Scattering intensity is plotted versus qz. (D) Two-dimensional GIWAXS pattern of the poly(ST) film.

    Figure 5

    Figure 5. (A) Tensile stress curves of the poly(ST) film under different RH (5%, 50%, and 80%, respectively). Inset photographs show the stretched poly(ST) film (RH = 80%). (B) Photographs show the rapid relaxation behavior of a stretched poly(ST) film (RH = 80%). (C) Schematic representation of the tension-induced alignment of the elastic poly(ST) film. (D) Optical microscope images of the polymer filaments made by stretching the hydrated poly(ST) films (RH = 80%). Bright field (top) and polarized light field (bottom) show the ordered fibers paralleled with the tension direction. (E) Schematic representation and optical images of the helical filaments which are formed by mechanical tension followed by relaxation.

    Figure 6

    Figure 6. (A) Schematic representation of the humidity-induced actuation behavior of poly(ST) polymer film. The blue arrows mean the humidity gradient direction. (B) Schematic representation of the expansion mechanism of the interlayers. (C) Photographs show the capability of poly(ST) polymer film acting as a humidity-responsive actuator. (D) XRD patterns of the poly(ST) film under varied RH. (E) Actuating kinetic curve of the bending polymer film to water vapor.

    Figure 7

    Figure 7. (A) Schematic representation of the water-mediated recycling process of the poly(ST) films. (B) Photographs show the recycling process of the polymer film fragments into a new polymer film. (C) Tensile stress curve of the original and recycled poly(ST) films. The tested samples are dried at room temperature (RH < 10%).

  • References

    ARTICLE SECTIONS
    Jump To

    This article references 60 other publications.

    1. 1
      Lutz, J. F.; Lehn, J. M.; Meijer, E. W.; Matyjaszewski, K. From precision polymers to complex materials and systems. Nat. Rev. Mater. 2016, 1, 16024,  DOI: 10.1038/natrevmats.2016.24
    2. 2
      Kang, J.; Miyajima, D.; Mori, T.; Inoue, Y.; Itoh, Y.; Aida, T. A rational strategy for the realization of chain-growth supramolecular polymerization. Science 2015, 347, 646651,  DOI: 10.1126/science.aaa4249
    3. 3
      Freeman, R.; Han, M.; Álvarez, Z.; Lewis, J. A.; Wester, J. R.; Stephanopoulos, N.; McClendon, M. T.; Lynsky, C.; Godbe, J. M.; Sangji, H.; Luijten, E.; Stupp, S. I. Reversible self-assembly of superstructured networks. Science 2018, 362, 808813,  DOI: 10.1126/science.aat6141
    4. 4
      Van Hameren, R.; Schön, P.; Van Buul, A. M.; Hoogboom, J.; Lazarenko, S. V.; Gerritsen, J. W.; Engelkamp, H.; Christianen, P. C. M.; Heus, H. A.; Maan, J. C.; Rasing, T.; Speller, S.; Rowan, A. E.; Elemans, J. A. A. W.; Nolte, R. J. M. Macroscopic hierarchical surface patterning of porphyrin trimers via self-assembly and dewetting. Science 2006, 314, 14331436,  DOI: 10.1126/science.1133004
    5. 5
      Boekhoven, J.; Hendriksen, W. E.; Koper, G. J. M.; Eelkema, R.; Van Esch, J. H. Transient assembly of active materials fueled by a chemical reaction. Science 2015, 349, 10751079,  DOI: 10.1126/science.aac6103
    6. 6
      Webber, M. J.; Appel, E. A.; Meijer, E. W.; Langer, R. Supramolecular biomaterials. Nat. Mater. 2016, 15, 1326,  DOI: 10.1038/nmat4474
    7. 7
      Yan, X.; Liu, Z.; Zhang, Q.; Lopez, J.; Wang, H.; Wu, H. C.; Niu, S.; Yan, H.; Wang, S.; Lei, T.; Li, J.; Qi, D.; Huang, P.; Huang, J.; Zhang, Y.; Wang, Y.; Li, G.; Tok, J. B. H.; Chen, X.; Bao, Z. Quadruple H-bonding cross-linked supramolecular polymeric materials as substrates for stretchable, antitearing, and self-healable thin film electrodes. J. Am. Chem. Soc. 2018, 140, 52805289,  DOI: 10.1021/jacs.8b01682
    8. 8
      Yamagishi, H.; Sato, H.; Hori, A.; Sato, Y.; Matsuda, R.; Kato, K.; Aida, T. Self-assembly of lattices with high structural complexity from a geometrically simple molecule. Science 2018, 361, 12421246,  DOI: 10.1126/science.aat6394
    9. 9
      Reches, M.; Gazit, E. Casting metal nanowires within discrete self-assembled peptide nanotubes. Science 2003, 300, 625627,  DOI: 10.1126/science.1082387
    10. 10
      Bera, S.; Mondal, S.; Xue, B.; Shimon, L. J. W.; Cao, Y.; Gazit, E. Rigid helical-like assemblies from a self-aggregating tripeptide. Nat. Mater. 2019, 18, 503509,  DOI: 10.1038/s41563-019-0343-2
    11. 11
      Chakraborty, P.; Guterman, T.; Adadi, N.; Yadid, M.; Brosh, T.; Adler-Abramovich, L.; Dvir, T.; Gazit, E. A Self-healing, all-organic, conducting, composite peptide hydrogel as pressure sensor and electrogenic cell soft substrate. ACS Nano 2019, 13, 163175,  DOI: 10.1021/acsnano.8b05067
    12. 12
      Kumar, M.; Ing, N. L.; Narang, V.; Wijerathne, N. K.; Hochbaum, A. I.; Ulijn, R. V. Amino-acid-encoded biocatalytic self-assembly enables the formation of transient conducting nanostructures. Nat. Chem. 2018, 10, 696703,  DOI: 10.1038/s41557-018-0047-2
    13. 13
      Goujon, A.; Moulin, E.; Fuks, G.; Giuseppone, N. [c2]Daisy chain rotaxanes as molecular muscles. CCS Chem. 2019, 1, 8396,  DOI: 10.31635/ccschem.019.20180023
    14. 14
      Gu, Y.; Alt, E. A.; Wang, H.; Li, X.; Willard, A. P.; Johnson, J. A. Photoswitching topology in polymer networks with metal-organic cages as crosslinks. Nature 2018, 560, 6569,  DOI: 10.1038/s41586-018-0339-0
    15. 15
      Hendricks, M. P.; Sato, K.; Palmer, L. C.; Stupp, S. I. Supramolecular assembly of peptide amphiphiles. Acc. Chem. Res. 2017, 50, 24402448,  DOI: 10.1021/acs.accounts.7b00297
    16. 16
      Wang, Q.; Mynar, J. L.; Yoshida, M.; Lee, E.; Lee, M.; Okuro, K.; Kinbara, K.; Aida, T. High-water-content mouldable hydrogels by mixing clay and a dendritic molecular binder. Nature 2010, 463, 339343,  DOI: 10.1038/nature08693
    17. 17
      Sano, K.; Ishida, Y.; Aida, T. Synthesis of anisotropic hydrogels and their applications. Angew. Chem., Int. Ed. 2018, 57, 25322543,  DOI: 10.1002/anie.201708196
    18. 18
      Sijbesma, R. P.; Beijer, F. H.; Brunsveld, L.; Folmer, B. J.; Hirschberg, J. K.; Lange, R. F.; Lowe, J. K. L.; Meijer, E. W. Reversible polymers formed from self-complementary monomers using quadruple hydrogen bonding. Science 1997, 278, 16011604,  DOI: 10.1126/science.278.5343.1601
    19. 19
      Supramolecular Polymer Chemistry; Harada, A., Ed.; Wiley-VCH: Weinheim, 2011.
    20. 20
      Doncom, K. E.; Blackman, L. D.; Wright, D. B.; Gibson, M. I.; O’Reilly, R. K. Dispersity effects in polymer self-assemblies: a matter of hierarchical control. Chem. Soc. Rev. 2017, 46, 41194134,  DOI: 10.1039/C6CS00818F
    21. 21
      Sun, C.; Shen, M.; Chavez, A. D.; Evans, A. M.; Liu, X.; Harutyunyan, B.; Flanders, N. C.; Hersam, M. C.; Bedzyk, M. J.; De La Cruz, M. O.; Dichtel, W. R. High aspect ratio nanotubes assembled from macrocyclic iminium salts. Proc. Natl. Acad. Sci. U. S. A. 2018, 115, 88838888,  DOI: 10.1073/pnas.1809383115
    22. 22
      Wei, P.; Yan, X.; Huang, F. Supramolecular polymers constructed by orthogonal self-assembly based on host–guest and metal–ligand interactions. Chem. Soc. Rev. 2015, 44, 815832,  DOI: 10.1039/C4CS00327F
    23. 23
      Lehn, J. M. Perspectives in chemistry—steps towards complex matter. Angew. Chem., Int. Ed. 2013, 52, 28362850,  DOI: 10.1002/anie.201208397
    24. 24
      Aida, T.; Meijer, E. W.; Stupp, S. I. Functional supramolecular polymers. Science 2012, 335, 813817,  DOI: 10.1126/science.1205962
    25. 25
      Vantomme, G.; Meijer, E. W. The construction of supramolecular systems. Science 2019, 363, 13961397,  DOI: 10.1126/science.aav4677
    26. 26
      Rutten, M. G. T. A.; Vaandrager, F. W.; Elemans, J. A. A. W.; Nolte, R. J. M. Encoding information into polymers. Nat. Rev. Chem. 2018, 2, 365381,  DOI: 10.1038/s41570-018-0051-5
    27. 27
      Zhang, Q.; Shi, C. Y.; Qu, D. H.; Long, Y. T.; Feringa, B. L.; Tian, H. Exploring a naturally tailored small molecule for stretchable, self-healing, and adhesive supramolecular polymers. Sci. Adv. 2018, 4, eaat8192  DOI: 10.1126/sciadv.aat8192
    28. 28
      Wang, S.; Xu, J.; Wang, W.; Wang, G.; Rastak, R.; Molina-Lopez, F.; Chung, J. W.; Niu, S.; Feig, V. R.; Lopez, J.; Lei, T.; Kwon, S. K.; Kim, Y.; Foudeh, A. M.; Ehrlich, A.; Gasperini, A.; Yun, Y.; Murmann, B.; Tok, J. B. H.; Bao, Z. Skin electronics from scalable fabrication of an intrinsically stretchable transistor array. Nature 2018, 555, 8388,  DOI: 10.1038/nature25494
    29. 29
      Kim, Y.; Chortos, A.; Xu, W.; Liu, Y.; Oh, J. Y.; Son, D.; Kang, J.; Foudeh, A. M.; Zhu, C.; Lee, Y.; Niu, S.; Liu, J.; Pfattner, R.; Bao, Z.; Lee, T. W. A bioinspired flexible organic artificial afferent nerve. Science 2018, 360, 9981003,  DOI: 10.1126/science.aao0098
    30. 30
      Son, D.; Kang, J.; Vardoulis, O.; Kim, Y.; Matsuhisa, N.; Oh, J. Y.; To, J. W. F.; Mun, J.; Katsumata, T.; Liu, Y.; McGuire, A. F.; Krason, M.; Molina-Lopez, F.; Ham, J.; Kraft, U.; Lee, Y.; Yun, Y.; Tok, J. B. H.; Bao, Z. An integrated self-healable electronic skin system fabricated via dynamic reconstruction of a nanostructured conducting network. Nat. Nanotechnol. 2018, 13, 10571065,  DOI: 10.1038/s41565-018-0244-6
    31. 31
      Xu, J.; Wang, S.; Wang, G. J. N.; Zhu, C.; Luo, S.; Jin, L.; Rondeau-Gagné, S.; Park, S.; Schroeder, B. C.; Lu, C.; Lu, C.; Oh, J. Y.; Wang, Y.; Kim, Y. H.; Yan, H.; Sinclair, R.; Zhou, D.; Xue, G.; Murmann, B.; Linder, C.; Cai, W.; Tok, J. B. H.; Chung, J. W.; Bao, Z. Highly stretchable polymer semiconductor films through the nanoconfinement effect. Science 2017, 355, 5964,  DOI: 10.1126/science.aah4496
    32. 32
      Nan, K.; Kang, S. D.; Li, K.; Yu, K. J.; Zhu, F.; Wang, J.; Dunn, A. C.; Zhou, C.; Xie, Z.; Agne, M. T.; Wang, H.; Luan, H.; Zhang, Y.; Huang, Y.; Synder, G. J.; Rogers, J. A. Compliant and stretchable thermoelectric coils for energy harvesting in miniature flexible devices. Sci. Adv. 2018, 4, eaau5849  DOI: 10.1126/sciadv.aau5849
    33. 33
      Miyajima, D.; Araoka, F.; Takezoe, H.; Kim, J.; Kato, K.; Takata, M.; Aida, T. Ferroelectric columnar liquid crystal featuring confined polar groups within core–shell architecture. Science 2012, 336, 209213,  DOI: 10.1126/science.1217954
    34. 34
      Xia, Y.; Mathis, T. S.; Zhao, M. Q.; Anasori, B.; Dang, A.; Zhou, Z.; Cho, H.; Gogotsi, Y.; Yang, S. Thickness-independent capacitance of vertically aligned liquid-crystalline MXenes. Nature 2018, 557, 409412,  DOI: 10.1038/s41586-018-0109-z
    35. 35
      Nyström, G.; Arcari, M.; Mezzenga, R. Confinement-induced liquid crystalline transitions in amyloid fibril cholesteric tactoids. Nat. Nanotechnol. 2018, 13, 330336,  DOI: 10.1038/s41565-018-0071-9
    36. 36
      Arazoe, H.; Miyajima, D.; Akaike, K.; Araoka, F.; Sato, E.; Hikima, T.; Kawamoto, M.; Aida, T. An autonomous actuator driven by fluctuations in ambient humidity. Nat. Mater. 2016, 15, 10841089,  DOI: 10.1038/nmat4693
    37. 37
      Gelebart, A. H.; Mulder, D. J.; Varga, M.; Konya, A.; Vantomme, G.; Meijer, E. W.; Selinger, R. L. B.; Broer, D. J. Making waves in a photoactive polymer film. Nature 2017, 546, 632636,  DOI: 10.1038/nature22987
    38. 38
      Lv, J. A.; Liu, Y.; Wei, J.; Chen, E.; Qin, L.; Yu, Y. Photocontrol of fluid slugs in liquid crystal polymer microactuators. Nature 2016, 537, 179184,  DOI: 10.1038/nature19344
    39. 39
      Eelkema, R.; Pollard, M. M.; Vicario, J.; Katsonis, N.; Ramon, B. S.; Bastiaansen, C. W.; Broer, D. J.; Feringa, B. L. Nanomotor rotates microscale objects. Nature 2006, 440, 163,  DOI: 10.1038/440163a
    40. 40
      Ware, T. H.; McConney, M. E.; Wie, J. J.; Tondiglia, V. P.; White, T. J. Voxelated liquid crystal elastomers. Science 2015, 347, 982984,  DOI: 10.1126/science.1261019
    41. 41
      Trigg, E. B.; Gaines, T. W.; Maréchal, M.; Moed, D. E.; Rannou, P.; Wagener, K. B.; Stevens, M. J.; Winey, K. I. Self-assembled highly ordered acid layers in precisely sulfonated polyethylene produce efficient proton transport. Nat. Mater. 2018, 17, 725731,  DOI: 10.1038/s41563-018-0097-2
    42. 42
      Song, J.; Chen, C.; Zhu, S.; Zhu, M.; Dai, J.; Ray, U.; Li, Y.; Kuang, Y.; Li, Y.; Quispe, N.; Yao, Y.; Gong, A.; Leiste, U. H.; Bruck, H. A.; Zhu, J. Y.; Vellore, A.; Li, H.; Minus, M. L.; Jia, Z.; Martini, A.; Li, T.; Hu, L. Processing bulk natural wood into a high-performance structural material. Nature 2018, 554, 224228,  DOI: 10.1038/nature25476
    43. 43
      Kristufek, S. L.; Wacker, K. T.; Tsao, Y.-Y.; Su, L.; Wooley, K. L. Monomer design strategies to create natural product-based polymer materials. Nat. Prod. Rep. 2017, 34, 433459,  DOI: 10.1039/C6NP00112B
    44. 44
      Yu, Z.; Tantakitti, F.; Yu, T.; Palmer, L. C.; Schatz, G. C.; Stupp, S. I. Simultaneous covalent and noncovalent hybrid polymerizations. Science 2016, 351, 497502,  DOI: 10.1126/science.aad4091
    45. 45
      Barltrop, J. A.; Hayes, P. M.; Calvin, M. The chemistry of 1,2-dithiolane (trimethylene disulfide) as a model for the primary quantum conversion act in photosynthesis. J. Am. Chem. Soc. 1954, 76, 43484367,  DOI: 10.1021/ja01646a029
    46. 46
      Fava, A.; Iliceto, A.; Camera, E. Kinetics of the thiol-disulfide exchange. J. Am. Chem. Soc. 1957, 79, 833838,  DOI: 10.1021/ja01561a014
    47. 47
      Zhang, X.; Waymouth, R. M. 1,2-Dithiolane-derived dynamic, covalent materials: cooperative self-assembly and reversible cross-linking. J. Am. Chem. Soc. 2017, 139, 38223833,  DOI: 10.1021/jacs.7b00039
    48. 48
      Singh, G.; Chan, H.; Baskin, A.; Gelman, E.; Repnin, N.; Král, P.; Klajn, R. Self-assembly of magnetite nanocubes into helical superstructures. Science 2014, 345, 11491153,  DOI: 10.1126/science.1254132
    49. 49
      Dong, S.; Leng, J.; Feng, Y.; Liu, M.; Stackhouse, C. J.; Schönhals, A.; Chiappisi, L.; Gao, L.; Chen, W.; Shang, J.; Jin, L.; Qi, Z.; Schalley, C. A. Structural water as an essential comonomer in supramolecular polymerization. Sci. Adv. 2017, 3, eaao0900  DOI: 10.1126/sciadv.aao0900
    50. 50
      Zhang, Q.; Li, T.; Duan, A.; Dong, S.; Zhao, W.; Stang, P. J. Formation of a supramolecular polymeric adhesive via water-participant hydrogen bond formation. J. Am. Chem. Soc. 2019, 141, 80588063,  DOI: 10.1021/jacs.9b02677
    51. 51
      Van Zee, N. J.; Adelizzi, B.; Mabesoone, M. F.; Meng, X.; Aloi, A.; Zha, R. H.; Lutz, M.; Filot, I. A. W.; Palmans, A. R. A.; Meijer, E. W. Potential enthalpic energy of water in oils exploited to control supramolecular structure. Nature 2018, 558, 100103,  DOI: 10.1038/s41586-018-0169-0
    52. 52
      Yanagisawa, Y.; Nan, Y.; Okuro, K.; Aida, T. Mechanically robust, readily repairable polymers via tailored noncovalent cross-linking. Science 2018, 359, 7276,  DOI: 10.1126/science.aam7588
    53. 53
      De Haan, L. T.; Verjans, J. M.; Broer, D. J.; Bastiaansen, C. W.; Schenning, A. P. Humidity-responsive liquid crystalline polymer actuators with an asymmetry in the molecular trigger that bend, fold, and curl. J. Am. Chem. Soc. 2014, 136, 1058510588,  DOI: 10.1021/ja505475x
    54. 54
      Ma, M.; Guo, L.; Anderson, D. G.; Langer, R. Bio-inspired polymer composite actuator and generator driven by water gradients. Science 2013, 339, 186189,  DOI: 10.1126/science.1230262
    55. 55
      Lloyd, E. M.; Lopez Hernandez, H.; Feinberg, A. M.; Yourdkhani, M.; Zen, E. K.; Mejia, E. B.; Sottos, N. R.; Moore, J. S.; White, S. R. Fully recyclable metastable polymers and composites. Chem. Mater. 2019, 31, 398406,  DOI: 10.1021/acs.chemmater.8b03585
    56. 56
      Zou, Z.; Zhu, C.; Li, Y.; Lei, X.; Zhang, W.; Xiao, J. Rehealable, fully recyclable, and malleable electronic skin enabled by dynamic covalent thermoset nanocomposite. Sci. Adv. 2018, 4, eaaq0508  DOI: 10.1126/sciadv.aaq0508
    57. 57
      Christensen, P. R.; Scheuermann, A. M.; Loeffler, K. E.; Helms, B. A. Closed-loop recycling of plastics enabled by dynamic covalent diketoenamine bonds. Nat. Chem. 2019, 11, 442448,  DOI: 10.1038/s41557-019-0249-2
    58. 58
      Miller, K. A.; Morado, E. G.; Samanta, S. R.; Walker, B. A.; Nelson, A. Z.; Sen, S.; Tran, D. T.; Whitaker, D. J.; Ewoldt, R. H.; Braun, P. V.; Zimmerman, S. C. Acid-triggered, acid-generating, and self-amplifying degradable polymers. J. Am. Chem. Soc. 2019, 141, 28382842,  DOI: 10.1021/jacs.8b07705
    59. 59
      Zhu, J. B.; Watson, E. M.; Tang, J.; Chen, E. Y. X. A synthetic polymer system with repeatable chemical recyclability. Science 2018, 360, 398403,  DOI: 10.1126/science.aar5498
    60. 60
      Rahimi, A.; García, J. M. Chemical recycling of waste plastics for new materials production. Nat. Rev. Chem. 2017, 1, 0046,  DOI: 10.1038/s41570-017-0046
  • Supporting Information

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.9b05740.

    • Additional materials and methods, NMR analysis, additional spectrum characterization, humidity-varied thermogravimetry, rheology experiments, and additional sample photographs (PDF)

    • Hydrated poly(ST) film exhibiting a fast relaxation-recovery ability (MP4)


    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

STEP 1:
Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

MENDELEY PAIRING EXPIRED
Your Mendeley pairing has expired. Please reconnect