Mechanically interlocked networks (MINs) have emerged as an encouraging platform for the development of mechanically robust yet adaptive materials. However, the difficulty in reversibly breaking the mechanical bonds poses a real challenge to MINs as customizable and sustainable materials. Herein, we couple the vitrimer chemistry with mechanically interlocked structures to generate a new class of MINsreferred to as mechanically interlocked vitrimers (MIVs)to address the challenge. Specifically, we have prepared the acetoacetatedecorated [2]rotaxane that undergoes catalyst-free condensation reaction with two commercially available multiamine monomers to furnish MIVs. Compared with the control whose wheels are nonslidable under applied force, our MIVs with slidable mechanically interlocked motifs showcase enhanced mechanical performance including Young's modulus (18.5 ± 0.9 vs 1.0 ± 0.1 MPa), toughness (3.7 ± 0.1 vs 0.9 ± 0.1 MJ/m 3 ), and damping capacity (98% vs 72%). The structural basis behind unique property profiles is demonstrated to be the force-induced host−guest dissociation and consequential intramolecular sliding of the wheels along the axles. The peculiar behaviors represent a consecutive energy dissipation mechanism, which provides a complement to other pathways that mainly depend on the breaking of sacrificial bonds. Moreover, by virtue of the vitrimer chemistry of vinylogous urethanes, we impart reprocessability and chemical recyclability to the MINs, thereby empowering the reconfiguration of the networks without breaking of the mechanical bonds. Finally, it is disclosed that the intramolecular motions of [2]rotaxanes could accelerate the dynamic exchange of the vinylogous urethane bonds via loosening the network, suggestive of a synergistic effect between the dual dynamic entities.
A thin filament stimulated by Ca2+ to combine with myosin is the structural basis to achieve filament sliding and muscle contraction. Though a large variety of artificial materials has been developed by mimicking muscle, the on-demand combination of the actin filament and myosin has never been precisely reproduced in polymeric systems. Herein, we show that both the combination process and the combined structure of actin filament and myosin have been mimicked to construct synergistic covalent and supramolecular polymers (CSPs). Specifically, photoirradiation as a stimulus induces the independently formed covalent polymers (CPs) and supramolecular polymers (SPs) to interact with each other through activated quadruple H-bonding. The resultant CSPs possess a unique network structure which not only facilitates the synergistic effect of CPs and SPs to afford stiff, strong, yet tough materials but also provides efficient pathways to dissipate energy with the damping capacity of the representative material being higher than 95%. Furthermore, muscle functions, for example, by becoming stiff during contraction and self-growth by training, are imitated well in our system via in situ phototriggered formation of CSP in the solid state. We hope that the fundamental understanding gained from this work will promote the development of synergistic CSP systems with emergent functions and applications by mimicking the principle of muscle movements.
In this work, a new strategy for developing light-triggered Pickering emulsions as smart soft vehicles for on-demand release is proposed. Initially, UV-induced tailored wettability allows anchoring of TiO2 nanoparticles at the interface to prepare stable water in oil emulsions. Such emulsions show the efficacy of microencapsulation and controlled release by demulsification due to the hydrophilic conversion of the TiO2 nanoparticles using a noninvasive light irradiation trigger. A molecule of interest is selected as a model cargo to quantitatively evaluate the as-prepared Pickering emulsions for their encapsulation and release behaviors. Moreover, light-responsive emulsion destabilization mechanism is studied as a function of particle concentration, light wavelength, and light intensity, respectively, determined by drop diameter evolution and droplet coalescence kinetics plots. For consideration of application in life sciences, Pickering emulsions sensitive to visible light are also established based on nitrogen doping of TiO2 nanoparticle emulsifiers.
Emulsion droplets can serve as ideal compartments for reactions. In fact, in many cases, the chemical reactions are supposed to be triggered at a desired position and time without change of the system environment. Here, we present a type of light and magnetic dual-responsive Pickering emulsion microreactor by coadsorption of light-sensitive titania (TiO) and super paramagnetic iron oxide (FeO) nanoparticles at the oil-water interface of emulsion droplets. The droplets encapsulating different reactants in advance can be driven close to each other by an external magnetic field, and then the chemical reaction is triggered by UV illumination due to the contact of the isolated reactants as a result of droplet coalescence. An insight into the incorporation of hydrophobic TiO and hydrophilic FeO nanoparticles simultaneously at the emulsion interface is achieved. On the basis of that, an account is given of the coalescence mechanism of the Pickering emulsion microreactors. Our work not only provides a novel Pickering emulsion microreactor platform for triggering chemical reactions in a nonintrusive and well-controlled way but also opens a promising avenue to construct multifunctional Pickering emulsions by assembly of versatile building block nanoparticles at the interface of emulsion droplets.
Nature has been inspiring scientists to fabricate impact protective materials for applications in various aspects. However, it is still challenging to integrate flexible, stiffness-changeable, and protective properties into a single polymer, although these merits are of great interest in many burgeoning areas. Herein, we report an impact-protective supramolecular polymeric material (SPM) with unique impact-hardening and reversible stiffness-switching characteristics by mimicking sea cucumber dermis. The emergence of softness−stiffness switchability and subsequent protective properties relies on the dynamic aggregation of the nanoscale hard segments in soft transient polymeric networks modulated by quadruple H-bonding. As such, we demonstrate that our SPM could efficiently reduce the impact force and increase the buffer time of the impact. Importantly, we elucidate the underlying mechanism behind the impact hardening and energy dissipation in our SPM. Based on these findings, we fabricate impact-and puncture-resistant demos to show the potential of our SPM for protective applications.
A robust Pickering emulsion stabilized by lipase-immobilized alginate gel microparticles with a coating of silanized titania nanoparticles is developed for biphasic biocatalysis.
Mortise‐and‐tenon joints have been widely used for thousands of years in wooden architectures in virtue of their artistic and functional performance. However, imitation of similar structural and mechanical design philosophy to construct mechanically adaptive materials at the molecular level is a challenge. Herein, we report a mortise‐and‐tenon joint inspired mechanically interlocked network (MIN), in which the [2]rotaxane crosslink not only mimics the joint in structure, but also reproduces its function in modifying mechanical properties of the MIN. Benefiting from the hierarchical energy dissipative ability along with the controllable intramolecular movement of the mechanically interlocked crosslink, the resultant MIN simultaneously exhibits notable mechanical adaptivity and structural stability in a single system, as manifested by decent stiffness, strength, toughness, and deformation recovery capacity.
In this work, switchable Pickering emulsions that utilize UV/dark manipulation employ a type of smart TiO2 nanoparticle as emulsifiers. The emulsifiers can be awakened when needed via UV-induced degradation of grafted silanes on TiO2 nanoparticles. By tuning the surface wettability of TiO2 nanoparticles in situ via UV/dark actuation, emulsions stabilized by the nanoparticles can be reversibly switched between the water-in-oil (W/O) type and oil-in-water (O/W) type for several cycles. Due to the convertible wettability, the smart nanoparticle emulsifiers can be settled in either the oil phase or the water phase as desired during phase separation, making it convenient for recycling. The present work provides a facile and noninvasive method to freely manipulate the formation, breakage, and switching of the emulsion; this method has promising potential as a powerful technique for use in energy-efficient and environmentally friendly industries.
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