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Hydrogels of biopolymers such as agar and gelatin are widely used in many applications, and in many cases, the gels are loaded with nanoparticles. The polymer chains in these gels are cross-linked by physical bonds into three-dimensional networks, with the mesh size of these networks typically being 10-100 nm. One class of "soft" nanoparticles are liposomes, which have an aqueous core surrounded by a lipid bilayer. Solutes encapsulated in the liposomal core can be delivered externally over time. In this paper, we create liposomes with diameters ∼150 nm from an unsaturated phospholipid (lecithin) and embed them in agar gels (the aqueous phase also contains 0-50% of glycerol, which is an active ingredient in cosmetic products). Upon placing this gel in quiescent water, we find that the liposomes release out of the gel into the water over a period of 1-3 days, even though the gel remains intact.

Nanoemulsions are widely used in applications such as in food products, pharmaceutical ingredients and cosmetics. Moreover, nanoemulsions have been a model colloidal system due to their ease of synthesis and the flexibility in formulations that allows one to engineer the inter-droplet potentials and thus to rationally tune the material microstructures and rheological properties. In this article, we study a nanoemulsion system in which the inter-droplet interactions are modulated by temperature and pH. We develop a nanoemulsion suspension in which the droplets are stabilized by weak acid surfactants whose charged state can be independently controlled by temperature and pH, leading to a responsive electrostatic repulsion. Moreover, the additional poly(ethylene glycol) segment (PEG) on the surfactant gives rise to a temperature responsive attraction between droplets via PEG-PEG association and ion-dipole interaction. The interplay of these three interactions gives rise to non-monotonic trends in material properties and structures as a function of temperature. The underlying mechanism resulting in these trends is obtained by carefully characterizing the nanoemulsion droplets and studying the molecular interactions. Such mechanistic understanding also provides guidance to modulate the inter-droplet potential using pH and ionic strength. Moreover, the molecular understanding of the weak acid surfactant also sheds light on the destabilization of the nanoemulsion droplets triggered by a switch in pH. The control of the competition of attractive and repulsive interactions using external stimuli opens up the possibility to design complex nanoemulsion-based soft materials with controllable structures and rheological properties.

Many biological materials, such as the squid beak and the spinal disc, have a combination of stiff and soft parts with very different mechanical properties, for example, the elastic modulus (stiffness) of the stiffest part of the squid beak is about 100 times that of the softest part. Researchers have attempted to mimic such structures using hydrogels but have not succeeded in synthesizing bulk gels with such large variations in moduli. Here, we present a general approach that can be used to form hydrogels with two or more zones having appreciably different mechanical characters. For this purpose, we use a technique developed in our lab for creating hybrid hydrogels with distinct zones. For the soft zone of the gel, we form a polymer network using a conventional acrylic monomer [ N, N'-dimethylacrylamide (DMAA)] and with laponite (LAP) nanoparticles as the cross-linkers. For the stiff zone, we combine DMAA, LAP, and a methacrylated silica precursor ([3-(methacryloyloxy)-propyl]trimethoxy-silane). When this mixture is polymerized, nanoscale silica particles (∼300 nm in diameter) are formed, and these serve as additional cross-links between the polymer chains, making this network very stiff. The unique character of each zone is preserved in the hybrid gel, and different zones are covalently linked to each other, thereby ensuring robust interfaces. Rheological measurements show that the elastic modulus of the stiff zone can be more than 100 times that of the soft zone. This ratio of moduli is the highest reported to date in a single, continuous gel and is comparable to the ratio in the squid beak. We present different variations of our soft-stiff hybrid gels, including multizone cylinders and core-shell discs. Such soft-stiff gels could have utility in bioengineering, such as in interfacing stiff medical implants with soft tissues.

External triggers such as pH or temperature can induce hydrogels to swell or shrink rapidly. Recently, these triggers have also been used to alter the three-dimensional (3-D) shapes of gels: for example, a flat gel sheet can be induced to fold into a tube. Self-folding gels are reminiscent of natural structures such as the Venus flytrap, which folds its leaves to entrap its prey. They are also of interest for applications in sensing or microrobotics. However, to advance the utility of self-folding gels, the range of triggers needs to be expanded beyond the conventional ones. Toward this end, we have designed a class of gels that change shape in response to very low concentrations of specific biomolecules. The gels are hybrids of three different constituents: (A) polyethylene glycol diacrylate (PEGDA); (B) gelatin methacrylate-co-polyethylene glycol dimethacrylate (GelMA-co-PEGDMA); and (C) N-isopropylacrylamide (NIPA). The thin-film hybrid is constructed as a bilayer or sandwich of two layers, with an A/B layer (alternating strips of A and B) sandwiched above a layer of gel C. Initially, when this hybrid gel is placed in water, the C layer is much more swollen than the A/B layer. Despite the swelling mismatch, the sheet remains flat because the A/B layer is very stiff. When collagenase enzyme is added to the water, it cleaves the gelatin chains in B, thus reducing the stiffness of the A/B layer. As a result, the swollen C layer is able to fold over the A/B layer, causing the sheet to transform into a specific shape. The typical transition is from flat sheet to closed hollow tube, and the time scale for this transition decreases with increasing enzyme concentration. Shape transitions are induced by enzyme levels as low as 0.75 U/mL. Interestingly, a shape transition is also induced by adding the lysate of murine fibroblast cells, which contains enzymes from the matrix metalloproteinase (MMP) family at levels around 0.1 U/mL (MMPs are similar to collagenase in their ability to cleave gelatin). We further show that transitions from flat sheets to other shapes such as helices and pancakes can be engineered by altering the design pattern of the gel. Additionally, we have made a rudimentary analog of the Venus flytrap, with two flat gels ("leaves") flanking a central folding gel ("hinge"). When enzyme is added, the hinge bends and brings the leaves together, trapping objects in the middle.

A highly porous 2D nanomaterial, holey graphene oxide (hGO), is synthesized directly from holey graphene powder and employed to create an aqueous 3D printable ink without the use of additives or binders. Stable dispersions of hydrophilic hGO sheets in water (≈100 mg mL-1 ) can be readily achieved. The shear-thinning behavior of the aqueous hGO ink enables extrusion-based printing of fine filaments into complex 3D architectures, such as stacked mesh structures, on arbitrary substrates. The freestanding 3D printed hGO meshes exhibit trimodal porosity: nanoscale (4-25 nm through-holes on hGO sheets), microscale (tens of micrometer-sized pores introduced by lyophilization), and macroscale (

Diverse structures in nature, such as the spinal disc and the onion have many concentric layers, and are created starting from the core and proceeding outwards. Here, we demonstrate an inside-out technique for creating multilayered polymer capsules. First, an initiator-loaded gel core is placed in a solution of monomer 1. The initiator diffuses outward and induces polymerization, leading to a shell of polymer 1. Thereafter, the core-shell structure is loaded with fresh initiator and placed in monomer 2, which causes a concentric shell of polymer 2 to form around the first shell. This process can be repeated to form multiple layers, each of a distinct polymer, and of controlled layer thickness. We show that these multilayered capsules can exhibit remarkable mechanical resilience as well as stimuli-responsive properties. The release of solutes from these capsules can be tailored to follow specific profiles depending on the chemistry and order of adjacent layers., Multiple concentric layers are present in a variety of structures present in nature, including the onion. Here, the authors show an inside-out strategy to synthesize multilayered polymer capsules, with different layers having specific composition and thereby specific responses to stimuli such as pH and temperature.