Producing synthetic soft worm and rod structures with multiple chemical functionalities on the surface would provide potential utility in drug delivery, nanoreactors, tissue engineering, diagnostics, rheology modifiers, enzyme mimics, and many other applications. Here, we have synthesized multifunctional worms and rods directly in water using a one-step reversible addition-fragmentation chain transfer (RAFT)-mediated dispersion polymerization at high weight fractions of polymer (>10 wt %). The chain-end functionalities included alkyne, pyridyl disulfide, dopamine, β-thiolactone, and biotin groups. These groups could further be converted or coupled with biomolecules or polymers. We further demonstrated a nanorod colorimetric system with good control over the attachment of fluorescent probes.
Currently, there are no straightforward methods to 3D print materials with nanoscale control over morphological and functional properties. Here, a novel approach for the fabrication of materials with controlled nanoscale morphologies using a rapid and commercially available Digital Light Processing 3D printing technique is demonstrated. This process exploits reversible deactivation radical polymerization to control the in‐situ‐polymerization‐induced microphase separation of 3D printing resins, which provides materials with complex architectures controllable from the macro‐ to nanoscale, resulting in the preparation of materials with enhanced mechanical properties. This method does not require specialized equipment or process conditions and thus represents an important development in the production of advanced materials via additive manufacturing.
Although 3D printing allows the macroscopic structure of objects to be easily controlled, controlling the nanostructure of 3D printed materials has rarely been reported. Herein, we report an efficient and versatile process for fabricating 3D printed materials with controlled nanoscale structural features. This approach uses resins containing macromolecular chain transfer agents (macroCTAs) which microphase separate during the photoinduced 3D printing process to form nanostructured materials. By varying the chain length of the macroCTA, we demonstrate a high level of control over the microphase separation behavior, resulting in materials with controllable nanoscale sizes and morphologies. Importantly, the bulk mechanical properties of 3D printed objects are correlated with their morphologies; transitioning from discrete globular to interpenetrating domains results in a marked improvement in mechanical performance, which is ascribed to the increased interfacial interaction between soft and hard domains. Overall, the findings of this work enable the simplified production of materials with tightly controllable nanostructures for broad potential applications.
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