Living organisms are capable of dynamically changing their structures for adaptive functions through sophisticated reaction-diffusion processes. Here we show how active supramolecular hydrogels with programmable lifetimes and macroscopic structures can be created by relying on a simple reaction-diffusion strategy. Two hydrogel precursors (poly(acrylic acid) PAA/CaCl₂ and Na₂CO₃) diffuse from different locations and generate amorphous calcium carbonate (ACC) nanoparticles at the diffusional fronts, leading to the formation of hydrogel structures driven by electrostatic interactions between PAA and ACC nanoparticles. Interestingly, the formed hydrogels are capable of autonomously disintegrating over time because of a delayed influx of electrostatic-interaction inhibitors (NaCl). The hydrogel growth process is well explained by a reaction-diffusion model which offers a theoretical means to program the dynamic growth of structured hydrogels. Furthermore, we demonstrate a conceptual access to dynamic information storage in soft materials using the developed reaction-diffusion strategy. This work may serve as a starting point for the development of life-like materials with adaptive structures and functionalities.

Transient materials that function out-of-equilibrium have been of great interest due to their unique properties that are rarely observed in thermodynamically stable occasions. However, the current advances are still limited to supramolecular objects, and the applications using this transient nature remain largely unexplored. Herein we report on chemical fuel powered transient polymer hydrogels for controlled formation and free release of pharmaceutical crystals. The transient polymer hydrogels with highly tunable stiffness and lifetime were created by chemical fuel powered crosslinking, which can be well regenerated without obvious deteriorations by simply refueling. On the basis of these properties, especially the transient nature, these hydrogels can serve as novel reusable platforms to control the pharmaceutical crystallization, more importantly, freely release the obtained crystals, which is inaccessible by conventional static gels. This work is expected to serve as an example to accelerate the development of more advanced out-of-equilibrium materials and exploitations of their high-tech applications.

Here, transient supramolecular hydrogels that are formed through simple aging-induced seeded self-assembly of molecular gelators are reported. In the involved molecular self-assembly system, multicomponent gelators are formed from a mixture of precursor molecules and, typically, can spontaneously self-assemble into thermodynamically more stable hydrogels through a multilevel self-sorting process. In the present work, it is surprisingly found that one of the precursor molecules is capable of self-assembling into nano-sized aggregates upon a gentle aging treatment. Importantly, these tiny aggregates can serve as seeds to force the self-assembly of gelators along a kinetically controlled pathway, leading to transient hydrogels that eventually spontaneously convert into thermodynamically more stable hydrogels over time. Such an aging-induced seeded self-assembly process is not only a new route toward synthetic out-of-equilibrium supramolecular systems, but also suggests the necessity of reporting the age of self-assembling building block solutions in other self-assembly systems.

Supramolecular structures with strain-stiffening properties are ubiquitous in nature but remain rare in the lab. Herein, we report on strain-stiffening supramolecular hydrogels that are entirely produced through the self-assembly of synthetic molecular gelators. The involved gelators self-assemble into semi-flexible fibers, which thereby crosslink into hydrogels. Interestingly, these hydrogels are capable of stiffening in response to applied stress, resembling biological intermediate filaments system. Furthermore, strain-stiffening hydrogel networks embedded with liposomes are constructed through orthogonal self-assembly of gelators and phospholipids, mimicking biological tissues in both architecture and mechanical properties. This work furthers the development of biomimetic soft materials with mechanical responsiveness and presents potentially enticing applications in diverse fields, such as tissue engineering, artificial life, and strain sensors.

The present work demonstrates how drug-loaded mesoporous silica nanoparticles (MSNPs) can be prepared by a sequential flash nanoprecipitation (FNP) technique. A sequential FNP technique is developed relying on a combination of two multi-inlet vortex mixers (MIVM), by which a continuous process that involves the formation of micelle-based templates followed by an in situ formation of MSNPs is achieved. Moreover, a widely used biological nematicide, abamectin (Abm), is added during the formation of micelles, ultimately leading to Abm-loaded MSNPs with high encapsulation efficiency. The obtained Abm-loaded MSNPs show excellent stability and inhibition activity against the livability of Meloidogyne incognita. Importantly, the parameters of the resulting MSNPs, such as silica shell thickness and inner cavity size of MSNPs, can be easily controlled by tuning the compositions of the reactant streams. We believe that such a simple approach towards direct preparation of drug-loaded MSNPs would find promising up-scale applications in various fields, such as drug delivery, bioimaging, and formulation technology.

Aromatic micropollutants found in wastewater pose threats to human health, and it is necessary to remove them from wastewater. Cyclodextrin hydrogel is one of the most promising environmentally friendly materials for removing aromatic micropollutants from wastewater by means of adsorption. In this study, we have synthesized a cyclodextrin hydrogel designed to simultaneously adsorb a cationic dye (methylene blue, MB) and an endocrine-disrupting compound, EDC (bisphenol A, BPA) and provide insights into the design of adsorbents for multicomponent wastewater purification. Polymeric dextran-poly(acrylic acid)-β-cyclodextrin (Dex-PAA-CD) was prepared by the copolymerization of glycidyl methacrylate (GMA), methacrylate-substituted dextran (Dex-MA), acrylic acid, and vinyl-derivatized β-cyclodextrin (β-CD-MA). The adsorption of MB and BPA by the Dex-PAA-CD hydrogel presented short equilibrium time. The adsorption of MB and BPA was independent of each other, and their adsorption mechanisms were proved to be electronic interaction and cyclodextrin host-guest interaction, respectively. The maximum adsorption capacities of MB and BPA onto Dex-PAA-CD are determined to be 5.60 and 0.144 mmol/g by the Sips isotherm. The Dex-PAA-CD hydrogel retains a high adsorption capacity even after five adsorption/desorption cycles and demonstrates the feasibility of designing reusable adsorbents to remove multiple pollutants from wastewater.

The present work shows how transient supramolecular hydrogels can be formed by catalytically controlled molecular self-assembly. Catalysis formation of molecular gelators leads the self-assembly along a kinetically favored pathway, resulting in transient hydrogels. This work demonstrates an effective approach towards pathway-dependent supramolecular materials.

Hierarchical compartmentalization through the bottom-up approach is ubiquitous in living cells but remains a formidable task in synthetic systems. Here we report on hierarchically compartmentalized supramolecular gels that are spontaneously formed by multilevel self-sorting. Two types of molecular gelators are formed in situ from nonassembling building blocks and self-assemble into distinct gel fibers through a kinetic self-sorting process; interestingly, these distinct fibers further self-sort into separated microdomains, leading to microscale compartmentalized gel networks. Such spontaneously multilevel self-sorting systems provide a "bottom-up" approach toward hierarchically structured functional materials and may play a role in intracellular organization.

Here we report on how metastable supramolecular gels can be formed through seeded self-assembly of multicomponent gelators. Hydrazone-based gelators decorated with non-ionic and anionic groups are formed in situ from hydrazide and aldehyde building blocks, and lead through multiple self-sorting processes to the formation of heterogeneous gels approaching thermodynamic equilibrium. Interestingly, the addition of seeds composing of oligomers of gelators bypasses the self-sorting processes and accelerates the self-assembly along a kinetically favored pathway, resulting in homogeneous gels of which the network morphologies and gel stiffness are markedly different from the thermodynamically more stable gel products. Importantly, over time, these metastable homogeneous gel networks are capable of converting into the thermodynamically more stable state. This seeding-driven formation of out-of-equilibrium supramolecular structures is expected to serve as a simple approach towards functional materials with pathway-dependent properties.

A biocompatible Dex-MA/PAA hydrogel was prepared through copolymerization of glycidyl methacrylate substituted dextran (Dex-MA) with acrylic acid (AA), which was applied as the adsorbent to remove cationic dyes from aqueous solutions. Dex-MA/PAA hydrogel presented a fast adsorption rate and the removal efficiency of Methylene Blue (MB) and Crystal Violet (CV) reached 93.9% and 86.4%, respectively within one minute at an initial concentration of 50 mg L^-1. The adsorption equilibrium data fitted the Sips isotherm model well with high adsorption capacities of 1994 mg g^-1 for MB and 2390 mg g^-1 for CV. Besides, dye adsorption occurred efficiently over the pH range 3-10 and the temperature range 20-60 °C. Moreover, the removal efficiencies for MB and CV were still >95% even after five adsorption/desorption cycles which indicates the robust nature of the Dex-MA/PAA hydrogel and its potential as an eco-friendly adsorbent for water treatment.

Herein, the micropatterning of supramolecular gels with oriented growth direction and controllable spatial dimensions by directing the self-assembly of small molecular gelators is reported. This process is associated with an acid-catalyzed formation of gelators from two soluble precursor molecules. To control the localized formation and self-assembly of gelators, micropatterned poly(acrylic acid) (PAA) brushes are employed to create a local and controllable acidic environment. The results show that the gel formation can be well confined in the catalytic surface plane with dimensions ranging from micro- to centimeter. Furthermore, the gels show a preferential growth along the normal direction of the catalytic surface, and the thickness of the resultant gel patterns can be easily controlled by tuning the grafting density of PAA brushes. This work shows an effective “bottom-up” strategy toward control over the spatial organization of materials and is expected to find promising applications in, e.g., microelectronics, tissue engineering, and biomedicine.

The work presented here shows that the growth of supramolecular hydrogel fibers can be spatially directed at the nanoscale by catalytic negatively charged nanoparticles (NCNPs). The NCNPs with surfaces grafted with negatively charged polymer chains create a local proton gradient that facilitates an acid-catalyzed formation of hydrogelators in the vicinity of NCNPs, ultimately leading to the selective formation of gel fibers around NCNPs. The presence of NCNPs has a dominant effect on the properties of the resulting gels, including gelation time, mechanical properties, and network morphology. Interestingly, local fiber formation can selectively entrap and precipitate out NCNPs from a mixture of different nanoparticles. These findings show a new possibility to use directed molecular self-assembly to selectively trap target nano-objects, which may find applications in therapy, such as virus infection prevention, or engineering applications, like water treatment and nanoparticle separation.

Hollow silica nanoparticles were prepared through generating a silica layer in spherical polyelectrolyte nanogels (SPN), which consisted of a solid core of polystyrene (PS) and a shell of crosslinked poly(acrylic acid) (PAA), followed by removing the PS core via solvent dissolution. Small angle X-ray scattering (SAXS) in combination with TEM were employed to observe SPN, silica-polymer composite, and hollow silica nanoparticles. It was confirmed that SAXS is a powerful method to monitor the generation of silica layer in SPN. The density and thickness of generated silica layer in SPN were found to be tunable by controlling the crosslinking density of the templates. The porous structure and pH sensitivity of silica layer allowed the obtained hollow silica to be ideal carriers for controlled drug delivery.

Chitosan has been used to cross-link poly(acrylic acid) to give three pH-sensitive hydrogels designed to control the release of the drugs amoxicillin and meloxicam. The extent of cross-linking and solution pH was found to dominate the swelling behavior of these hydrogels as shown by scanning electron microscopy and swelling time dependencies. The rates of release of amoxicillin and meloxicam from the loaded hydrogels increased with increase in pH consistent with the extent of hydrogen bonding between hydrogel components and between the hydrogel and the drugs being important determinants of release rate. Both the Korsemeyer-Peppas and Weibull models fitted release data consistent with drug release occurred through a combination of drug diffusion and hydrogel relaxation processes. These hydrogels appear to provide an ideal basis for controlled drug delivery systems.