Supramolecular Materials最新文献

Metal ions play a pivotal role in regulating and determining the functions of proteins and peptides in nature. This study aims to investigate the regulatory role of metal ions in peptide assembly and explore the influence of sequence variations and metal ions on the structure and function of resulting peptide nanoarchitectures. Dipeptide sequences with distinct charged properties (positive and negative) and functional groups (-COOH, -NH₂, and phenolic hydroxyl) were meticulously selected and co-assembled with various metal ions (Au³⁺, Ag⁺, and Pt⁴⁺). The findings highlight the crucial functional role of the phenolic hydroxyl group of tyrosine in metal ion reduction, while positively charged groups promote metal ion accumulation through electrostatic forces, facilitating co-assembly. The formation of ordered structures in Au@Fmoc-YK and Au@Fmoc-YR nanoarchitectures further validates the significant interaction among metal ions, tyrosine-OH, and positively charged NH₂. Notably, these nanoarchitectures possess the unique attribute of being prepared under physiological conditions, specifically at 37 °C, without the need for organic solvents or chemical modifications of peptides. This approach offers a straightforward means of constructing diverse functional nanoarchitectures based on peptides and metal ions. Moreover, Au@Fmoc-YR exhibits good performance as a nanoenzyme for detecting glucose in complex bodily fluids and plasma GSH in tumor patients, showcasing its promising potential for medical applications.

Chiral recognition plays a crucial role in the normal functioning of biological systems. The recognition of proteins in chiral environments underpins many fundamental life processes. Taking advantage of the distinct interactions between different proteins and chiral environments, this study presents the design of homochiral metal–organic framework (MOF)/nanochannels based membrane separator, enabling highly selective and high-throughput protein separation. The chiral separation membrane was fabricated by employing TiO₂ nanochannel membrane (TM) as the supporting membrane and Ti ion source. Using terephthalic acid (BDC) and d/l-phenylalanine (DP/LP) as ligands, a layered TiMOF (MIL-125(Ti) used in this study) incorporating chiral selector molecules (named as DP/M and LP/M) were synthesized in situ within the TiO₂ nanochannels. The bovine serum albumin (BSA) adsorption capacity of DP/M decorated TM was demonstrated to be 2.8 times higher than that of LP/M decorated TM, and was found to be related to the content of the chiral selector DP in the separation membrane. Furthermore, different recognition abilities by the chiral channels were observed for proteins with different isoelectric points. Based on a comprehensive exploration of the variations in the interaction forces between protein and chiral selector molecules, a nanoscale chromatography column-like separation model was proposed. The chiral separation membranes designed in this study provide a new platform for understanding the interactions between chiral compounds and proteins, and open up new avenues for fabricating chiral bio-interface materials, elucidating the role of chiral recognition in biological systems, and developing novel biomaterials and devices.

Peptidomimetics have garnered increased attention due to their unique structural properties and self-assembly, as well as their promising applications in material sciences and peptidomimetic drug design. N-acetylated-N-aminoethyl amino acid oligomers (AApeptides), a novel class of helical foldamer, have been effectively utilized to imitate protein helices and regulate protein-protein interactions. While the structures of a series of AApeptides have been determined experimentally, the chemical diversity of AApeptides is impeding the advancement of peptide inhibitor development and high-level architecture design through purely experimental methods. Consequently, there's an urgent need for effective computational tools to facilitate the structural design of more complex systems using AApeptides. While a general AMBER force field (GAFF) can be applied to simulate AApeptides, it is crucial to evaluate the accuracy of such a force field and consider alternatives to enhance accuracy. In this study, we employed molecular dynamics simulations (MD) to assess the stability of a helical AApeptide. Our findings indicate that GAFF alone is insufficient to stabilize the helical structure of our AApeptide. We suggest the use of restraints derived from experimentally determined structures to guide the simulation and maintain this helical structure. Although any set of restraint definitions used in this study can simulate helical packing, a minimum of three points per AApeptide building block restraint is necessary to accurately reproduce the hydrogen bonding pattern.

Owing to excellent biocompatibility, tunable modulus to match biological tissues, full of water environment, and wide range of constituents, injectable hydrogels have always been preferred as superior performers of regenerative medicine. In principle, the inclusion of macroporous structures in hydrogels facilitates the diffusion of oxygen and nutrients for cell survival and the removal of the metabolic waste, thus strengthening the integration between materials and host tissues. So far, it is still a challenge to construct macroporous structure in hydrogels in situ with preservation of mechanical strength after injecting hydrogel precursors into the biological tissues. In this study, we propose an innovative in situ gas-forming strategy for preparing a kind of bioactive injectable macroporous hydrogel with the assistance of Mg microparticles (MgMPs). Hydrogen gas as a product of MgMPs reacting with water acts as porous template during the gelation process. So the porosity is closely related to the amount of MgMPs, which is a crucial factor for improving cell viability and proliferation throughout the macroporous hydrogel. Referring to the in vivo wound care experiments, regenerated epidermis and extensive blood vessels are found in the macroporous hydrogel, indicating enhanced tissue regeneration. This in situ gas-templating strategy for preparing injectable macroporous hydrogels holds promise as a technique for providing improved biological scaffolds.

Bioelectric phenomena play important roles in living organisms and are essential for regulating cellular and tissue behavior. Electroactive assemblies can facilitate tissue repair and/or regulate neural activity by simulating the tissue microenvironment, while providing electrical signals and biocompatible component niches. Self-powered nanogenerators including TENG and PENG are essential part in electroactive assemblies. Assemblies incorporating TENG or PENG can present the advantages of controllable morphology, portability, low cost, and flexibility, making them a new and promising research content in the biomedical field. Herein, we describe in detail the basic physical rules underlining electric field generations in assemblies, and discuss constructing rules and research progress of self-powered assemblies in tissue engineering. Their applications in the fields of bone tissue repair and regeneration, nerve modulation and injury repair, skin wound healing, and antibacterial are sequentially discussed. Finally, current challenges and possible solutions of self-powered artificial assemblies are discussed, expecting to promote the research efforts and advance the self-powered assemblies from laboratory to clinical applications.

A new supramolecular approach toward the reductive degradation of organic dyes by hybridizing hydrophilic hydrazide-pillar[5]arene (HP5A) as surface-modifiers with silver nanoparticles (AgNPs) has been demonstrated. The fabricated supramolecular hybrid nanomaterial (denoted as HP5A-AgNPs) with ideal mono-dispersity, improved stability, and smaller size, show high catalytic activity in boosting organic dyes degradation, as delivered by a broad spectrum of organic dyes, including rhodamine B, rhodamine 6G, methylene blue, and methyl orange. This work expands the application scope of macrocycles-derived organic-inorganic nanohybrids into catalytic degradation and environmental protection areas.

Nanostructured block copolymer (BCP) particles are attractive due to their ordered internal structures, unique shape and surface patterns; however, their structural integrity can be easily lost because of weak intermolecular interactions, which limits their practical applications. In this study, we present a simple and reliable method to fabricate nanostructured particles of polystyrene-block-poly(4-vinylpyridine) with tunable and robust nanostructures by employing hydrogen-bonding and cross-linking strategies. The key feature of poly(4-vinylpyridine) is the presence of reactive pyridyl moieties, which allow precise regulation of internal nanostructures via hydrogen bonds and locking of the structural integrity via quaternarization by feeding hydrogen bond donors and cross-linkers, respectively. The solvent resistance is well proven by immersing the particles in either selective solvents of the continuous phase or good solvent of the BCP. Furthermore, mesoporous BCP particles derived from the cross-linked particles are obtained simply by a swelling/deswelling treatment. This study provides a way to improve the structural robustness of BCP particles and could be a key step that advances the functionalization and subsequent applications of such nanostructured BCP colloidal particles.

Drug resistance is one of the major causes of cancer treatment failures. In recent years, to combat the issue of drug resistance, a large volume of strategies has been established along the development of biomedical nanomaterials. Compared with traditional nanocarrier-based drug delivery strategies, in situ supramolecular self-assembly has emerged as a promising strategy to overcome drug resistance. This review first introduced the concept of in situ supramolecular self-assembly. The second part illustrated the mechanisms of constructing in situ supramolecular self-assembly as a multi-step process. The third part elucidated the role of in situ supramolecular self-assembly to reverse drug resistance, which included three categories: active self-assembly materials, drug-carrier self-assembly materials and drug-coupled self-assembly materials. At last, we summarized the current development of in situ supramolecular self-assembly for the reversal of drug resistance and the remaining concerns to be addressed.

Adhesive bonding to diverse substances is vital to a great number of the established, cutting-edge and emerging applications. We have witnessed, in the last few years, the transformative progress in achieving robust adhesive bonding and tunable debonding behavior, which mostly employing the supramolecular forces. Among the diverse supramolecular forces, the contribution of hydrogen-bonds (H-bonds) to adhesives, on the modality of directionality, selectivity and sensitivity, can function as nano-scaled bonding agents for improved interfacial interactions, thus paved novel perspectives to the design and creation of glue materials with outstanding performance. On account of the dynamic and reversible feature, a characteristic principally determined for H-bonding (macro)molecules could be employed as adhesive platform for affording outstanding attaching, connecting and on demand disconnecting, arising from the combination of adhesion/cohesion process via H-bonding interactions and the responsive characteristics. Thus, H-bonded adhesives with abundant diverse molecular configuration furnish a rich toolbox that can fulfill universal yet specific needs with unique advantages, demonstrating great opportunities for fundamental researches and practical applications. Herein we outline and summarize the design and creation of H-bonded adhesives, responsive attaching/detaching, and applications in advanced materials. We propose the guidance for further designing H-bonded adhesives, in concert with biomedical science, physics, mechanical and electric, informatics or robotics of promising future.

Perylene diimides (PDIs) with high fluorescence quantum yield and well π-conjugated plane have been widely studied to construct supramolecular aggregates via noncovalent interactions and to further develop supramolecular fluorescent sensors triggered by analytes. This review summarizes recent progress in the design strategies and sensing applications of the PDI supramolecular aggregates. Besides the inherent π-π stacking of the PDI plane, the additional driving forces to promote the construction of PDI supramolecular aggregates are classified into four parts including hydrogen bonding interactions, electrostatic interactions, metal-coordination interactions and host-guest interactions. Then, the PDI supramolecular aggregates can be used to detect metal ions, biomolecules and organic molecules. Finally, the potential future developments of the PDI supramolecular aggregates in sensing applications are discussed.