Stretchable and autonomously self-healable elastomers with wide-ranging tunable mechanical properties have attracted increasing attention in various industries. To date, it continues to be a huge challenge to synthesize selfhealing elastomers integrating extreme stretchability, relatively high mechanical modulus, and autonomous and rapid selfhealing capability. Herein, we propose a novel covalent/ supramolecular hybrid construction strategy, in which the covalent cross-links are responsible for providing high modulus and elasticity, while supramolecular cross-links realize extreme stretchability and rapid self-healing under room temperature depending on the ultrafast exchange kinetics of metal−ligand motifs and multicoordination modes. The representative polyurea hybrid elastomer, CSH-PPG-Zn-0.25, can be stretched more than 180× its original length with the highest Young's modulus (1.78 ± 0.08 MPa) among reported ultrastretchable materials. CSH-PPG-Zn-0.25 can fully restore mechanical properties of completely cut samples within 3 h. Note that the healing process can take place under a low temperature of −20 °C and unaffected by surface aging and atmospheric moisture. Merely tailoring the molar ratio of metal/ligand actualizes wide-ranging tunability of mechanical and dynamic properties, such as Young's modulus (from 1.71 ± 0.08 MPa to 5.56 ± 0.22 MPa), maximum tensile strength (from 0.32 ± 0.03 MPa to 4.42 ± 0.23 MPa), strain at break (from >18000% to 630 ± 27%), and storage modulus, ascribed to the increase of cross-linking density and formation of stiff ionic clusters. On the basis of the different material characteristics, two typical elastomers are employed, respectively, as flexible and self-healable conductor and self-healable automotive paint. Benefiting from the fantastic antiaging and low-temperature healing features of CSH-PPG-Zn-0.25, the prepared Ag-NWs/ CSH-PPG-Zn-0.25 conductor can even regain its conductive function below zero. CSH-PPG-Zn-0.50 material, meeting the strict mechanical requirements of automotive paints, is able to thoroughly eliminate the surface scratches and recover anticorrosion function in the local damaged region under the atmospheric environment.
The self-complexation of mono-benzimidazole functionalized β-cyclodextrins was investigated. The unique molecular structure employed as supramolecular nanovalves were installed on the external surface of mesoporous silica to assemble mechanized silica nanoparticles, which showed pH-triggered release property.
Developing artificial systems to
mimic the emergence of chirality
is of vital importance in better understanding the mysterious origin
of natural homochirality and guiding the design of advanced chiroptical
materials. Herein, we present a DNA-inspired control over the emergence
of supramolecular nanoscale chirality in multiple hydrogen-bonded
self-assemblies. N-Terminated aromatic amino acids
bearing serine and aromatic domains could self-assemble into lamellar
microsheets without nanoscale chirality, ascribed to their pronounced
molecular stacking preference on two-dimensional orientations. Significantly,
when achiral bipyridine-, melamine-, and imidazole-based molecular
binders that could potentially form hydrogen-bonded complexes with
these aromatic amino acids were introduced, the induced chiral nanostructures
from the resulting coassemblies were observed. Melamine and its derivatives
presented an excellent capability to generate ordered supramolecular
structures and induce the nanoscale chirality. Assisted by the key
duplex hydrogen bonds between the melamine core and serine segments,
chiral nanotubes and ribbons were obtained. This study reveals that
multiple hydrogen bonds are the prerequisite for inducing the emergence
of chiral nanostructures from integrated coassemblies.
Abstract:Benefiting from the development of nanotechnology, drug delivery systems (DDSs) with stimuli-responsive controlled release function show great potential in clinical anti-tumor applications. By using a DDS, the harsh side effects of traditional anti-cancer drug treatments and damage to normal tissues and organs can be avoided to the greatest extent. An ideal DDS must firstly meet bio-safety standards and secondarily the efficiency-related demands of a large drug payload and controlled release function. This review highlights recent research progress on DDSs with stimuli-responsive characteristics. The first section briefly reviews the nanoscale scaffolds of DDSs, including mesoporous nanoparticles, polymers, metal-organic frameworks (MOFs), quantum dots (QDs) and carbon nanotubes (CNTs). The second section presents the main types of stimuli-responsive mechanisms and classifies these into two categories: intrinsic (pH, redox state, biomolecules) and extrinsic (temperature, light irradiation, magnetic field and ultrasound) ones. Clinical applications of DDS, future challenges and perspectives are also mentioned.
Corrosion potential stimulus-responsive smart nanocontainers (CP-SNCs) are designed and synthesized based on the installation of the supramolecular assemblies (bipyridinium ⊂ water-soluble pillar[5]arenes) onto the exterior surface of magnetic nanovehicles (FeO@mSiO), linked by disulfide linkers. The supramolecular assemblies with high binding affinity as gatekeepers effectively block the encapsulated organic corrosion inhibitor, 8-hydroxyquinoline (8-HQ), within the mesopores of FeO@mSiO. When the corrosion potential of the magnesium alloy (-1.5 V vs SHE) is exerted, 8-HQ is released instantly because of the cleavage of disulfide linkers and the removal of the supramolecular assemblies. CP-SNCs were incorporated into the hybrid organic-inorganic sol-gel coating to construct a corrosion potential stimulus-feedback anticorrosion coating (CP-SFAC) that was then deposited on the magnesium alloy, AZ31B. With the aid of a magnetic field, CP-SNCs were gathered in the proximity of the surface of AZ31B. CP-SFAC showed a satisfactory anticorrosion performance, more importantly, through the evaluation of microzone electrochemical techniques. CP-SFAC presented the rapid self-healing functionality when the localized corrosion occurred. Shortening the distance between CP-SNCs and the surface of AZ31B enhances the availability of the incorporated CP-SNCs and makes most of the CP-SNCs to timely respond to the corrosion potential stimulus and facilitates the formation of a compact molecular protective film before the corrosion products pile up. The characteristics of fast response time and quick self-healing rate meet the requirements of the magnesium alloy for self-healing in local regions.
Advanced rechargeable lithium-based batteries have a profound effect on our global society and polymer materials are one of the key components of these batteries. The key roles of polymers applied in battery technology are presented in terms of binders, package coatings, separators, and electrolytes. However, the loathsomely structural changes during repeated charge/discharge processes result in the mechanical fracture problems of polymers inside batteries, which significantly reduce the cycling lifetimes. The use of intrinsic self-healing polymers as substitutes is one of the most favored strategies for reviving lithium-based batteries since self-healing polymers spontaneously eliminate the mechanical cracks or damages and result in greatly enhanced electrochemical performances. In this review, we first introduce the advances and working mechanism of intrinsic self-healing polymers. Then, we discuss the opportunities and challenges in the development of advanced lithium-based batteries with Si, Li-metal, S electrodes, and polymer electrolytes, respectively, and summarize the up-to-date key progress in intrinsic self-healing polymers for solving the above-mentioned challenges. Finally, we propose some designing principles of desired intrinsic self-healing polymers from the perspectives of basic structures, ionic conductivities, mechanical properties, chemical interactions, and the self-healing capabilities.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.