Supramolecular Materials最新文献

Protein functionality hinges on precise three-dimensional structures, while molecular chaperones orchestrate folding, proteome maintenance, and proteostasis. Recent attention has focused on BRICHOS domain from pro-proteins of pulmonary surfactant protein C (proSP-C), Bri2 and Bri3 as autonomous molecular chaperones, crucial for cellular quality control. Bri2, an integral protein, emerges with expressions ranging from the central nervous system to cancer and lung diseases and exhibits proficiency in combating amyloid aggregation, a hallmark of neurodegenerative disorders like Alzheimer's. The capability of Bri2-BRICHOS to shield aggregation-prone regions, unveiling its role as an intramolecular guardian. In this review, we explore the structure and function of BRI2 and its relation to neurodegenerative diseases, as well as the structural complexities, functional landscapes, and implications of BRICHOS domains in diverse neurodegenerative disorders. Furthermore, it sheds light on Bri2-BRICHOS as a possible candidate for therapeutic approaches in protein aggregation disorders.

Endowing a robust pressure-sensitive adhesive (PSA) with sensable properties is of great significance for in-situ stress detection and information encryption in the fields of electronics, energy storage, flexible sensing, etc. However, it remains great challenge due to the difficulty in balancing interfacial wetting and cohesive strength. Herein, a microphase-separated strategy is proposed to construct an ionogel with a lower modulus of 1.96MPa, a strength of 728kPa as well as a remarkable toughness of 2258.9kJ/m³, which can be used as a sturdy PSA bonded to various substrates (metals, polar plastics, non-polar plastics) under gentle pressure. The comparable modulus and cohesive strength give it an excellent adhesion strength of 1340kPa, which far exceeds most of reported high-performance PSAs. Furthermore, due to the orientation of a large number of ionic groups, the adhesion strength increases by 31.3% once a voltage of 20V is applied. Finally, the sensitive force-resistance response of such PSA that can be used for encrypted messaging was demonstrated.

Liquid-liquid phase separation (LLPS) is a captivating phenomenon in which a uniform mixture spontaneously divides into two liquid phases with differing component concentrations. It is prevalent in soft matter, is observed in systems involving polymers, organic molecules, and proteins, and is influenced by environmental factors and component properties. Recent recognition of LLPS within living organisms reveals its role in creating cellular compartments to orchestrate complex biochemical reactions, requiring distinct boundaries and unhindered molecular movement. Nonmembrane compartments, stemming from cytoplasmic LLPS, such as nucleoli, hold promise for synthetic cell engineering and cellular function insights. Under certain conditions, LLPS is linked to diseases such as sickle-cell disease, cancer, and neurodegenerative diseases. This review offers a concise overview of LLPS in soft matter, emphasizing its relevance in soft material engineering. We delve into fundamental mechanisms, focusing on biological systems, and explore the implications of LLPS, spanning organelles, substance exchange, molecular diffusion, and disease associations. LLPS enables soft material engineering, with applications in biomedicine and bioengineering, shaping future possibilities in bioengineering, from foundational cellular constructs to intricate artificial tissue development.

Keeping in view recent advancements in designing biomaterials from bioactive polysaccharides, the present work deals with the design of protein (gelatin)-polysaccharide (tragacanth gum) based bioactive copolymeric network by supramolecular interactions and covalent linkage for sustained drug delivery (DD) applications. The network copolymeric structure was characterized by field emission-scanning electron micrographs (FE-SEM), electron dispersion X-ray analysis (EDAX), Fourier transform infrared spectroscopy (FTIR), ¹³C-nuclear magnetic resonance (NMR), and X-ray diffraction (XRD). FESEM and XRD analyses revealed the heterogeneous morphology of copolymers with an amorphous nature. ¹³C NMR and FTIR spectra demonstrated the incorporation of poly(acrylamide) (AAm) into network structure by copolymerization reaction. Diffusion of anticancer drug 5-flurouracil (5-FU) occurred in a sustained manner with the Fickian mechanism and was best fitted in first order kinetic model. Polymer-blood interactions revealed the non-hemolytic character of hydrogels. An antioxidant assay evaluated their antioxidant property (26.61 ± 0.85 % of free radical scavenging). Copolymers exhibited mucoadhesiveness during polymer-mucous membrane interactions and required 113.33 ± 5.68 mN detachment forces. Furthermore, the combination of polysaccharide-gelatin has enhanced supramolecular interactions and improved physiological and biomedical properties of network hydrogels. Overall, these properties revealed the suitability of copolymeric hydrogels for drug delivery applications.

Techniques to acquire chiral information from molecules are essential for deciphering important biological processes and improving the performance of industrial chiral materials. Herein, we report novel supramolecular gelators that enable widely accessible chiral supramolecular organogels for simple naked-eye enantiodifferentiation of specific enantiomers (left- or right-handedness) for wide-range substances. The supramolecular gelators featuring multiple hydrogen-bonding sites and large π-π conjugated groups are produced by complexing commercially available chiral tartaric acids and achiral 1-naphthylmethylamine. The highly polar and insoluble acid-amine complexes drive the aggregation of the supramolecular gelators, which further form chiral nanofibers due to chirality transfer from tartaric acid to the supramolecular nanofibers through multiple hydrogen-bonding between the hydroxyl groups of chiral tartaric acids and π-π stacking between 1-naphthylmethylamine molecules. At high concentrations, physical crosslinking of the chiral nanofibers creates a chiral gel structure that facilitates interactions between its chirally and non-covalently associated components and enantiomers, making the gel system particularly sensitive to specific types of enantiomers. Consequently, sensitive naked-eye detection of specific enantiomers of diverse substances is achieved via observing “gel-to-micelle” transitions, which occurs when the enantiomers generate complexes that disrupt chirality transfer in the co-assembly and destroy the hierarchical structures.

The self-healing capability of a material refers to its ability to autonomously heal fractures or defects and restore its original structures and functionalities. Self-healing hydrogels, with enhanced lifespan and mechanical performances compared to traditional fragile hydrogels, can serve as ideal synthetic analogues of living tissues, holding great promise in a wide range of biomedical, electrical and environmental applications. Reversible interactions play crucial roles in the construction of self-healing hydrogel networks. A deep understanding of these bonds is critical for the rational design of hydrogels with desirable properties. In this short review, we first introduce the experimental tools for the direct measurements of reversible intermolecular interactions, followed by discussing the self-healing hydrogels via diverse noncovalent interactions (i.e., hydrogen bonding, ionic interaction, metal-ligand coordination, hydrophobic association and π-interactions) and dynamic covalent bonds (i.e., imines, boronic esters, hydrazones and disulfide bond). Challenges and our opinions on future development of self-healing hydrogels are also provided.

Ion channels play a vital role in regulating the flow of ions across cell membranes to maintain physiological functions. Mimicking this biological process and fabricating artificial nano-/micro-channels with similar functions are expected to solve challenges involving ion transport in fields such as energy, environment, and human health. As a flexible and controllable preparation technology, supramolecular self-assembly is a powerful tool for designing biomimetic channels for specific purposes. Although various artificial channels have been reported, ever-increasing research interest in their application potential call for a bridge between design principles and engineering applications. In this Perspective, we summarized the recent advances in this new field and analyzed the working mechanism based on the grounded theory of supramolecular chemistry and nanofluidic systems. To promote the progress of this field, the opportunities and key challenges in this field for future research and applications are highlighted.

We present a brief overview of current investigations on the dynamics of supramolecular assemblies, with the focus on applying broadband dielectric spectroscopy (BDS) combined with different techniques. The dielectric methods have significant advantages in probing the dynamical signature and scaling of supra-structures. We summarize various mechanisms describing supramolecular dynamics, which could produce a relaxation governed by supramolecular association slower than the glass-transition-related structural relaxation. Next, we also discuss the relaxation dynamics in phase-separated supramolecular assemblies and supramolecular assembly under nanoconfinement, for controlling bonus macroscopic performances. This perspective emphasizes the idea that the relaxational response of supramolecular assemblies is generic to some extent. It does not necessarily depend on the chemistry of associations, but could reflect supra-materials’ behaviors determined by their molecular architectures.

Self-healing elastomers provide extended longevity of functional materials, due to their unique adaptability and durability. However, a major scientific challenge remains in developing materials with a rapid healing process combined with decent mechanical properties, that can be prepared by a relatively simple synthesis approach. Herein, we report a versatile design approach on self-healing elastomers by incorporating two different hydrogen bonding containing monomers, i.e., 2-[[(butylamino)carbonyl]oxy]ethyl acrylate (BCOE) and 2-ureido-4[1H]pyrimidinone (UPy) functionalized ethyl methacrylate. Poly(BCOE-r-UPy)s are synthesized by reversible addition−fragmentation chain-transfer (RAFT) polymerization, and controlling the ratio of two monomers enables well-tunable mechanical properties with tensile strength ranging from 0.04 to 6.3 MPa and tensile strain up to 3,000 %. The characteristic dissociation energy is calculated from a temperature dependence of terminal relaxation followed by subtracting the segmental relaxation. The rapid autonomous self-healing is achieved when the molar composition of Poly(BCOE-r-UPy) is tailored to BCOE/UPy = 99/1. The self-healing process is monitored in situ by a helium-ion microscope, and its macroscopic study using tensile tests indicates that Poly(BCOE-r-UPy1) with 1 % molar ratio of UPy recovers 70 % of its original toughness at ambient temperature within 10 mins. 3D printing of Poly(BCOE-r-UPy) affords a self-healable 3D structure, demonstrating the adaptability of Poly(BCOE-r-UPy) for on-demand fabrication. The simplicity of synthesis, well-tunable mechanical properties, unique self-healability, and 3D printing capability of Poly(BCOE-r-UPy)s indicate their potential for a range of applications.

Hydrogels containing dynamically crosslinked networks through covalent bonds have garnered substantial attention in both academia and technology sectors. This interest stems from their impressive mechanical stability and their unique spatiotemporal dynamic characteristics. Among the various type of dynamic covalent bonds used for preparation hydrogel, the 5-methylene pyrrolones (5MP) and thiol reaction stands out as one of the most prevalent. Given its reliability, efficiency and selectivity, thiol-5MP reaction has long been recognized as some of the most efficient Micheal additions. In this work, by utilizing thiol-5MP Michael addition with improved stability and specificity, a new type of dynamic hydrogel is easily prepared. Notably, the mechanical attributes of the resultant thiol-5MP hydrogels can be finely tuned by modulating the pH during their preparation process. Furthermore, hydrogels formulated under neutral (pH 7.5) or alkaline (pH 8.5) conditions display enhanced stress-relaxation response and superior self-healing capabilities compared to those generated under acidic conditions (pH 6.5). As revealed by single-molecule force spectroscopy assays, the pH-tunable mechanical properties are attributed to the pH-dependent dynamics of thiol-5MP bonds. This work showcases an innovative avenue for crafting dynamic hydrogels featuring pH-adjustable bulk characteristics, highlighting the versatility of thiol-5MP bonds as fundamental building blocks for the design of functional hydrogel materials.