The ability to print soft materials into predefined architectures with programmable nanostructures and mechanical properties is a necessary requirement for creating synthetic biomaterials that mimic living tissues. However, the low viscosity of common materials and lack of required mechanical properties in the final product present an obstacle to the use of traditional additive manufacturing approaches. Here, a new liquid-in-liquid 3D printing approach is used to successfully fabricate constructs with internal nanostructures using in situ self-assembly during the extrusion of an aqueous solution containing surfactant and photocurable polymer into a stabilizing polar oil bath. Subsequent photopolymerization preserves the nanostructures created due to surfactant self-assembly at the immiscible liquid-liquid interface, which is confirmed by small-angle X-ray scattering. Mechanical properties of the photopolymerized prints are shown to be tunable based on constituent components of the aqueous solution. The reported 3D printing approach expands the range of low-viscosity materials that can be used in 3D printing, and enables robust constructs production with internal nanostructures and spatially defined features. The reported approach has broad applications in regenerative medicine by providing a platform to print self-assembling biomaterials into complex tissue mimics where internal supramolecular structures and their functionality control biological processes, similar to natural extracellular matrices.

Surfactant molecules have been extensively used as emulsifying agents to stabilize immiscible fluids. Droplet stability has been shown to be increased when ordered nanoscale phases form at the interface of the two fluids due to surfactant association. Here, we report on using mixtures of a cationic surfactant and long chained alkenes with polar head groups [e.g., cetylpyridinium chloride (CPCl) and oleic acid] to create an ordered nanoscale lamellar morphology at aqueous-oil interfaces. The self-assembled nanostructure at the liquid-liquid interface was characterized using small-angle x-ray scattering, and the mechanical properties were measured using interfacial rheology. We hypothesize that the resulting lamellar morphology at the liquid-liquid interface is driven by the change in critical packing parameter when the CPCl molecules are diluted by the presence of the long chain alkenes with polar head groups, which leads to a spherical micelleto-lamellar phase transition. The work presented here has larger implications for using nanostructured interfacial material to separate different fluids in flowing conditions for biosystems and in 3D printing technology.

Polymerization-induced structural transitions have gained attention recently due to the ease of creating and modifying nanostructured materials with controlled morphologies and length scales. Here, we show that order–order and disorder–order nanostructural transitions are possible using in situ polymer grafting from the diblock polymer, poly­(styrene)-block-poly­(butadiene). In our approach, we are able to control the resulting nanostructure (lamellar, hexagonally packed cylinders, and disordered spheres) by changing the initial block polymer/monomer ratio. The nanostructural transition occurs by a grafting from mechanism in which poly­(styrene) chains are initiated from the poly­(butadiene) block via the creation of an allylic radical, which increases the overall molecular weight and the poly­(styrene) volume fraction. The work presented here highlights how the chemical process of converting standard linear diblock copolymers to grafted block polymers drives interesting and controllable polymerization-induced morphology transitions.

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Due to their distinctive molecular architecture, ABA triblock copolymers will undergo specific self-assembly processes into various nanostructures upon introduction into a B-block selective solvent. Although much of the focus in ABA triblock copolymer self-assembly has been on equilibrium nanostructures, little attention has been paid to the guiding principles of nanostructure formation during non-equilibrium processing conditions. Here we report a universal and quantitative method for fabricating and controlling ABA triblock copolymer hierarchical structures using solvent-non-solvent rapid-injection processing. Plasmonic nanocomposite hydrogels containing gold nanoparticles and hierarchically-ordered hydrogels exhibiting structural color can be assembled within one minute using this rapid-injection technique. Surprisingly, the rapid-injection hydrogels display superior mechanical properties compared with those of conventional ABA hydrogels. This work will allow for translation into technologically relevant areas such as drug delivery, tissue engineering, regenerative medicine, and soft robotics, in which structure and mechanical property precision are essential.