最新刊期
卷 53 ， 期 10 ， 2022
- 摘要：Owing to the dynamic nature and the rich library of supramolecular interactions, supramolecular shape memory polymers have shown unique benefits beyond traditional thermoset shape memory polymers including multi-stimuli response, self-healing, recyclability, and solid-state plasticity. Thanks to extensive research over the last two decades, the above characteristics have become well-established. Despite that, new material design opportunities beyond those continue to emerge in the recent five years. In particular, supramolecular shape memory polymer has been reported to possess unusually high output energy density via strain-induced formation of ordered supramolecular structures, which are beneficial for use as artificial muscles. In addition, the hydrophobic domain in a hydrogel has been demonstrated to be effective in fixing the anisotropy of the poly(N-isopropylacrylamide) chains, giving rise to two-way reversible shape memory behavior in hydrogels. Intriguingly, the change in glassy transition temperature due to photo-isomerization of azobenzene moieties leads to athermal shape memory polymers for which no heating/cooling is required for the entire shape memory cycle. Rational design of a shape memory network with self-complementary hydrogen bonding interactions endows the material with superior toughness and multi-recyclability. Collectively, these recent progresses have expanded the scope of shape memory polymers, which are summarized in the first half of this article. The above developments typically take advantage of the on-off switch offered by supramolecular interactions, but their dynamic reorganization process has been by and large neglected. Several reports in the last three years have shown that this latter characteristic is uniquely useful in designing autonomous shape memory polymers for which no external stimulation is needed to trigger the shape recovery. These supramolecular autonomous shape memory polymers are discussed in the second half of this article. This class of materials utilize the time- and temperature-dependent exchange kinetics of supramolecular interactions to manipulate the entropic energy stored via spatio-temporal programming, as a way to control the shape-shifting. This autonomous shape-shifting mode differs drastically from traditional stimuli-responsive shape memory polymers and its trigger-free nature can open up new device applications in which access to external stimulation is difficult. We believe that the principle of spatio-temporal programming via supramolecular interactions can be potentially expanded to other molecular mechanisms, which will provide a new perspective for smart material design in the future.关键词：Supramolecular interaction;Shape memory polymer;Spatio-temporal programming;Autonomous shapeshifting
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发布时间：2024-10-08 - 摘要：With the complementary and synergistic effects on anticancer function, the combined utilization of photothermal therapy and immunotherapy is one of the priority methods for eliminating solid tumor and metastatic tumor. However, the limitations of photothermal immunoagents currently in use bring drawbacks to their clinical application prospects. The development and optimization of this combined therapy have become a research hotspot in the field of cancer treatment. More and more attention has been paid to functional assemblies based on oligopeptide molecular design. Such assemblies can not only design the assembly structure through amino acid encoding, but also achieve excellent anti-tumor therapeutic performance through the introduction of bioactive peptides. In this feature article, we summarize the recent researches on oligopeptide-based assemblies for tumor photothermal immunotherapy in terms of the different roles of peptide molecules in the construction of assembly system. We first discuss the roles of oligopeptides participating in the assembly regulation of photothermal immune system, and then elaborate the mechanisms of oligopeptides in optimizing system stability, enhancing photothermal conversion efficiency, and inducing immune response in the assembly process. In addition, we also summarize the roles of different functional peptides in photothermal immunotherapy of cancer, and discuss the application prospect of oligopeptide assembly in cancer therapy.关键词：Peptide;Chromophore;Supramolecular self-assembly;Functional assemblies;Photothermal immunotherapy
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发布时间：2024-10-08
Feature Article
- 摘要：DNA molecule is the main genetic material in an organism, which forms a stable double helix structure through base-pairing interactions. Besides, DNA molecule also plays an important role in the fabrication of various nanostructures due to the precise molecular recognition. DNA origami technique possesses great advantages in the fabrication of complex, arbitrary structures with high yield and stability. The excellent ability of DNA origami in building complex shapes with programmability and addressability makes DNA origami a powerful tool to construct various nanostructures that are difficult to achieve with other fabrication techniques. In this review, we mainly introduced the recent progress of metal nanostructures fabricated by DNA origami supramolecular systems and their optical properties. First, we introduced the basic principles of the design and construction of DNA origami. Subsequently, we summarized the recent progress in the fabrication of metal nanostructures based on DNA origami supramolecular self-assemblies and also introduced the optical applications in chirality, surface-enhanced Raman scattering and surface-enhanced fluorescence. Finally, the challenges and the perspectives of this field were also discussed.关键词：Supramolecular systems;DNA origami;Chirality;Surface-enhanced Raman Scattering;Surface-enhanced fluorescence
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发布时间：2024-10-08 - 摘要：Self-assembly of amphiphiles has attracted more and more attention in the fields of biomedicine and materials science during the last decade. For preparing functional nanostructures with specific size and morphology, researchers have developed a variety of robust construction methods, including film hydration, co-solvent, dialysis, microfluidic technologies as well as well frame-guided assembly method, etc. Since the traditional methods have already been well-summarized in detail in many references, therefore, only the construction mechanism and features of these strategies will be addressed here. As a new and effective construction strategy, frame-induced assembly has achieved a series of important achievements in fabrication of three dimensional nanovesicles and two dimensional nanomembranes with precise control on their morphology and size. Based on this novel method, various scaffolds and leading hydrophobic groups have been proven adaptable to form customized nanostructures. In this review, the important research progress of frame-induced assembly strategy in recent ten years will be summarized and evaluated, and the challenges and application prospects of this strategy in the future will be also forecasted.关键词：Amphiphiles;Self-assembly;Construction methods;Frame-guided assembly
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发布时间：2024-10-08 - 摘要：Protein polymers play an important role in biological composition and life activities. Formed through multiple supramolecular interactions, assembly structures of natural supramolecular protein polymers that were preserved in natural selection could satisfy the various advanced life events. To better explore the mysteries of life, in recent years, the construction of protein supramolecular polymers with various and diverse functionalities in a "bottom-up" approach has become one of the hotspots of interest. Flexible construction strategies could be considered as one of the decisive factors for the successful construction of protein supramolecular polymers. In this paper, we introduce some of the most classical constructing strategies of protein supramolecular polymers based on metal coordination, host-guest interactions, multiple hydrogen bond interactions, hydrophobic interactions, π-π interactions and receptor recognition interactions, and their respective characteristics were analyzed and discussed. Due to their good biocompatibility and well-defined structure at the nanoscale, protein polymers act as advanced materials in the biological related fields. Based on the unique structural and functional advantages of protein supramolecular polymers, their applications in biocatalysis, medical diagnosis and treatment, biomimetic light harvesting systems, biosensing and other functional materials were introduced in this paper. The significance of the construction of protein supramolecules and its application potential were also clarified. Finally, the challenges of the preparation and application of protein supramolecular polymers as well as its tendency of future development are prospected.关键词：Protein self-assembly;Supramolecular interfaces;Protein-protein interactions;Nano materials;Biofunctionalization
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发布时间：2024-10-08 - 摘要：The study of chiral polymers has important guiding significance for understanding life processes and preparing smart materials. As a typical photo-responsive chromophore, the introduction of azobenzene groups into chiral polymer systems can endow polymers with optical chirality switch characteristics. Compared with the traditional covalent polymerization by chiral monomers, the use of supramolecular strategy means is a more convenient, efficient and intelligent way to induce polymer chirality. Generally speaking, inducing polymer chirality by supramolecular means can often avoid the use of expensive chiral reagents to save costs, and it can also endow polymer systems with more excellent chirality properties. In recent years, chiral polymers in biomimetic materials, asymmetric catalytic materials and chiral optical devices have shown great application prospects, and promote the interest of scholars in this field. Based on the above background, this paper is classified by the construction methods of azobenzene-based chiral polymers such as chiral monomers, chiral end groups, chiral solvents, chiral gel factors, circularly polarized light and chiral host macrocycles. Then, the effects of different construction strategies on the supramolecular chirality switches are mainly introduced, and the advantages and characteristics of different construction strategies are also summarized. Finally, at the end of this paper, we point out the key scientific issues and challenges in future research of supramolecular chirality switching based on azobenzene polymers.关键词：Chiral polymers;Supramolecular chirality;Chiroptical switches;Azobenzene;Photoresponsive
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发布时间：2024-10-08
Review
- 摘要：A new antitumor treatment based on conjugated polymer/chloroplast biological hybrid material was proposed in this study, in which the conjugated polymer PBF (poly(boron-dipyrromethene-co-fluorene)) with a positive side chain charge could be electrostatically combined with negatively charged chloroplast. The successful combination of conjugated polymer PBF and chloroplast was demonstrated by the UV-Vis absorption spectra, the zeta potentials, and isothermal titration microcalorimetry (ITC) in sequence. In addition, the confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM) were utilized to visualize the structure of the PBF/chloroplast biological hybrid. The CLSM results demonstrated that the conjugated polymer PBF was closely surrounded by the chloroplast. The SEM image showed the PBF/chloroplast biological hybrid material was much rougher than that of the pristine chloroplast on account of the coating behavior of conjugated polymer PBF. As an abiotic component, the conjugated polymer PBF possessed excellent light-harvesting and light conversion capability, which not only improved the utilization efficiency of sunlight in chloroplasts but also accelerated the electron transfer rate of the light reaction center in chloroplasts. The estimation was studied by the NADPH level of the live chloroplast. Under white light illumination, the NADPH in PBF/chloroplast was significantly increased compared to that of the pristine chloroplast. This increase in NADPH indicates that the photoinduced electron transfer by conjugated polymer PBF could improve the efficiency of NADPH-related intracellular reactions. The acceleration of the photosynthetic rate was also investigated through detecting the reduction rate of 2,6-dichlorophenolindophenol (DCPIP), an artificial electron acceptor, which would capture the transported electrons of the chloroplast during the light reaction. Moreover, it further mediated the directional enhancement of reactive oxygen species (ROS) in photosynthesis to realize the efficient clearance of tumor cells. Overall, this work provided another new biological strategy based on conjugated polymer/chloroplast hybrid material for the development of treatments for malignant tumors.关键词：Conjugated polymer;chloroplast hybrid;photosynthesis;reactive oxygen enhancement;Cancer therapy
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发布时间：2024-10-08 - 摘要：As a biological polymeric material, deoxyribonucleic acid (DNA) possesses unique sequence programmability, structural predictability and functional designability. Recently, DNA hydrogel has been widely used in bioimaging, drug delivery, the separation of biological particle and the intervention of cell behavior. However, the materials with DNA as the sole module face the challenges of structural singleness and functional limitations. To explore more synthesis methods and functions of DNA hydrogel, researchers have introduced hybrid functional modules to develop new molecular assembly strategies. As natural polyphenols, tea polyphenols (TP) have been proven to have good antioxidant, antibacterial, antiviral and anti-tumor activities, which make TP potential for various biological applications. Previous studies have shown that stable hydrogen bonds can be formed between the phosphate groups of DNA and the phenolic hydroxyl groups of polyphenols. Herein, a TP-DNA hydrogel based on ultralong DNA chains was synthesized by double rolling circle amplification strategy and the assembly of TP with DNA. The mass ratio of TP to DNA in TP-DNA hybrid hydrogels was optimized. The results of scanning electron microscopy and rheological test showed that TP-DNA hydrogel possessed porous structure and shear thinning property. On the other hand, the experiments of nuclease resistance, biocompatibility, antibacterial activity and wound healing evaluation were performed to explore the effect of TP on the properties of DNA hydrogels. The results showed that TP not only delayed the degradation rate of DNA hydrogel under nuclease, but also endowed the hydrogel with good antibacterial activity. In a rat wound healing model, the TP-DNA hydrogel was proven to significantly promote wound healing.关键词：DNA hydrogel;Tea polyphenols;Antibacterial;Antidegradation
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发布时间：2024-10-08 - 摘要：Stimulus-responsive hydrogels based on host-guest interactions have attractive tremendous attentions in recent years, and have been applied successfully in a variety of research areas. Currently, a lot of macrocyclic hosts—such as cyclodextrin, crown ether, calixarenes, cucurbiturils, and pillararenes, etc.—have been widely investigated in the preparation of stimulus-responsive supramolecular hydrogels. The major approach to introduce stimulus-responsive properties into these supramolecular hydrogels is exploiting specially designed guests which can response to external stimuli. However, most of functional guests—such as organic dyes—are fail to manifest stimulus-responsive properties, which is a big limitation for the development of functional host-guest supramolecular hydrogels. Introducing stimulus-responsive hosts with excellent guest-binding abilities as the building blocks of supramolecular hydrogels may be an efficient way to address this problem. Herein, hyaluronic acid (HA) was modified with N-ethylamino-4-azetidinyl-1,8-naphthalene anhydride (EANA) dyes and used as the polymeric backbone of the hydrogel, and a hypoxia-responsive, deep-cavity azocalix[4]arene (CSAC4A) was exploited as the noncovalent cross-linking agent. By utilizing the strong 1:2 recognition interactions between CSAC4A and the EANA moieties on the HA backbones, a new supramolecular hydrogel with hypoxia-responsiveness was prepared, and its morphology, mechanical properties, and hypoxia-responsive behavior were fully characterized. It has been showed that, the pore sizes of HA-CA are mainly distributed in the range of 40-70 μm, which indicates HA-CA is a typical microporous supramolecular hydrogel. Besides, the storage modulus (G') of HA-CA is stable at around 100 Pa, under the evaluation conditions of 0.5% strain, 1 Hz. When HA-CA was put under a hypoxia environment, the azo bonds of CSAC4A were reduced and cleaved, leading to the release of the encapsulated EANA dyes along with the recovery of their fluorescent emission. At the same time, due to the destruction of the physical cross-linking points, the cross-linked structure of the supramolecular hydrogel was destroyed, and its mechanical strength was significantly reduced. Therefore, HA-CA represents a novel type of hypoxia-responsive supramolecular hydrogel which might be potentially useful for biomedical applications.关键词：Supramolecular hydrogel;Host-guest interaction;Hypoxia response;Macrocyclic host;Azocalix[4]arene
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发布时间：2024-10-08 - 摘要：Rotaxane system that is based on benzo-21-crown-7 (B21C7) and dialkylammonium salts (DAAs) is one of the important molecular machines. Understanding the mechanism of force-induced unbinding and rebinding of such rotaxane system will facilitate the development of rotaxane-based force-responsive materials. In this paper, we have investigated the mechanochemistry and unbinding-rebinding process of a tandem polyrotaxane with B21C7/DAAs repeat units. The binding mode and binding strength have been also revealed. Through the atomic force microscopy (AFM)-based single molecule force spectroscopy (SMFS) method, we are able to get the unbinding information of each rotaxane unit on the whole tandem chain and quantify the strength of the host-guest complexation. A force plateau containing sawtooth peaks was observed, which corresponds to the sequential unbinding of the B21C7/DAAs unit, and the peak force was found in the range of 84-142 pN depending on the force loading rate. Consecutive stretching-relaxation experiments reveal that after detaching from the binding point and sliding along the axle, crown ether moieties can travel back to their original binding sites once the chain is relaxed. The loading rate dependence tells us that the unbinding force increases linearly with the increase of the force loading rate, whereas the rebinding force decreases linearly with the increase of the force loading rate. Furthermore, we can get the kinetic parameters governing the dynamic motion of the polyrotaxane with a dissociation rate constant of 0.26 s-1 and an association rate constant of 1.3×104 s-1. With these kinetic parameters, the potential energy landscape for the unbinding/rebinding of rotaxane was drawn with an equilibrium free energy of -34.6 kJ/mol. These results deepen the understanding of B21C7/DAAs system, and are helpful for the rational design of functional materials with rotaxane molecular machine building blocks. The established method can also be applied in other rotaxane systems.关键词：Polyrotaxanes;Supramolecular materials;Single molecule force spectroscopy;mechanochemistry
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发布时间：2024-10-08
Research Article
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