Permanent and reversibly programmable shapes in liquid crystal elastomer microparticles capable of shape switching.

Reversibly programmable liquid crystal elastomer microparticles (LCEMPs), formed as a covalent adaptable network (CAN), with an average diameter of 7 µm ± 2 µm, were synthesized via a thiol-Michael dispersion polymerization. The particles were programmed to a prolate shape via a photoinitiated addition-fragmentation chain-transfer (AFT) exchange reaction by activating the AFT after undergoing compression. Due to the thermotropic nature of the AFT-LCEMPs, shape switching was driven by heating the particles above their nematic-isotropic phase transition temperature (TNI). The programmed particles subsequently displayed cyclable two-way shape switching from prolate to spherical when at low or high temperatures, respectively. Furthermore, the shape programming is reversible, and a second programming step was done to erase the prolate shape by initiating AFT at high temperature while the particles were in their spherical shape. Upon cooling, the particles remained spherical until additional programming steps were taken. Particles were also programmed to maintain a permanent oblate shape. Additionally, the particle surface was programmed with a diffraction grating, demonstrating programmable complex surface topography via AFT activation.

Enabling Applications of Covalent Adaptable Networks.

The ability to behave in a fluidlike manner fundamentally separates thermoset and thermoplastic polymers. Bridging this divide, covalent adaptable networks (CANs) structurally resemble thermosets with permanent covalent crosslinks but are able to flow in a manner that resembles thermoplastic behavior only when a dynamic chemical reaction is active. As a consequence, the rheological behavior of CANs becomes intrinsically tied to the dynamic reaction kinetics and the stimuli that are used to trigger those, including temperature, light, and chemical stimuli, providing unprecedented control over viscoelastic properties. CANs represent a highly capable material that serves as a powerful tool to improve mechanical properties and processing in a wide variety of polymer applications, including composites, hydrogels, and shape-memory polymers. This review aims to highlight the enabling material properties of CANs and the applied fields where the CAN concept has been embraced.

A readily programmable, fully reversible shape-switching material.

Liquid crystalline (LC) elastomers (LCEs) enable large-scale reversible shape changes in polymeric materials; however, they require intensive, irreversible programming approaches in order to facilitate controllable actuation. We have implemented photoinduced dynamic covalent chemistry (DCC) that chemically anneals the LCE toward an applied equilibrium only when and where the light-activated DCC is on. By using light as the stimulus that enables programming, the dynamic bond exchange is orthogonal to LC phase behavior, enabling the LCE to be annealed in any LC phase or in the isotropic phase with various manifestations of this capability explored here. In a photopolymerizable LCE network, we report the synthesis, characterization, and exploitation of readily shape-programmable DCC-functional LCEs to create predictable, complex, and fully reversible shape changes, thus enabling the literal square peg to fit into a round hole.

A multi-stimuli responsive, self-assembling, boronic acid dipeptide.

Modification of the dipeptide of phenylalanine, FF, with a boronic acid (BA) functionality imparts unique aqueous self-assembly behavior that responds to multiple stimuli. Changes in pH and ionic strength are used to trigger hydrogelation via the formation of nanoribbon networks. Furthermore, we show for the first time that the binding of polyols to the BA functionality can modulate a peptide between its assembled and disassembled states.

Surfactant-induced assembly of enzymatically-stable peptide hydrogels.

The secondary structure of peptides in the presence of interacting additives is an important topic of study, having implications in the application of peptide science to a broad range of modern technologies. Surfactants constitute a class of biologically relevant compounds that are known to influence both peptide conformation and aggregation or assembly. We have characterized the secondary structure of a linear nonapeptide composed of a hydrophobic alanine/phenylalanine core flanked by hydrophilic acid/amine units. We show that the anionic surfactant sodium dodecyl sulfate (SDS) induces the formation of ß-sheets and macroscopic gelation in this otherwise unstructured peptide. Through comparison to related additives, we propose that SDS-induced secondary structure formation is the result of amphiphilicity created by electrostatic binding of SDS to the peptide. In addition, we demonstrate a novel utility of surfactants in manipulating and stabilizing peptide nanostructures. SDS is used to simultaneously induce secondary structure in a peptide and to inhibit the activity of a model enzyme, resulting in a peptide hydrogel that is impervious to enzymatic degradation. These results complement our understanding of the behavior of peptides in the presence of interacting secondary molecules and provide new potential pathways for programmable organization of peptides by the addition of such components.