Peptide amphiphiles are a class of molecules that combine the structural features of amphiphilic surfactants with the functions of bioactive peptides and are known to assemble into a variety of nanostructures. A specific type of peptide amphiphiles are known to self-assemble into onedimensional (1D) nanostructures under physiological conditions, predominantly nanofibers with a cylindrical geometry. The resultant nanostructures could be highly bioactive and are of great interest in many biomedical applications, including tissue engineering, regenerative medicine and drug delivery. In this context, we highlight our strategies for using molecular self-assembly as a toolbox to produce peptide amphiphile nanostructures and materials and efforts to translate this technology into applications as therapeutics. We also review our recent progress in using these materials for treating spinal cord injury, inducing angiogenesis, and for hard tissue regeneration and replacement.
different core block chemistry. The key point for choosing the different chemistries of the two hydrophobic blocks is that the two blocks experience a high degree of mutual immiscibility. In the current experiment, polystyrene (PS) and poly(2,3,4,5,6-pentafluorostyrene) (PPFS) were employed as the different, third hydrophobic blocks in the two triblock copolymers (PAA 94-b-PMA 103-b-PS 117 and PAA 93-b-PMA 99-b-PPFS 100) (29). Equal molar amounts of the two triblock copolymers with different respective third blocks were dissolved in pure THF. EDDA was then added to reach a final 1:1 molar ratio of amine groups to acid groups. The diamines underwent complexation with the PAA blocks, thereby forming aggregates with PAA-diamine cores. Notably, these aggregates contained each of the triblock copolymers with both PS and PPFS hydrophobic blocks because of the simple trapping of unlike hydrophobic blocks in the same aggregate by PAA-diamine complexation. Next, introduction of water into the THF solution to a final ratio of THF:water = 1:2 provided for the formation of cylindrical micelles. However, the existence of the original mixed triblock copolymer aggregates, as a result of PAA and diamine complexation, forced the local co-assembly of unlike third hydrophobic blocks into the same micelle core. In addition, the lack of chain exchange in solution that disallows global chain migration and maintains nonequilibrated micelle structures, combined with the fact that the PAA chains in the corona of the newly formed micelles were still complexed with diamines and were not freely mobile within the micelle, guarantee the stability of the mixed-core micelle. The im-miscibility of the two different hydrophobic blocks, PS and PPFS, eventually resulted in internal phase separation on the nanoscale, producing multicompartment micelles. The images shown in Fig. 4, A to D were taken after 4 days of aging a solution of mixed hydrophobic core cylinders. Internal phase separation is clearly indicated by the strong undulations along the cylinder surfaces and the TEM contrast variation along the cylinders. The larger, darker, and more spherical regions within the cylinders are hypothesized to be regions that are concentrated in PAA 94-b-PMA 103-b-PPFS 100 triblock copolymer. First, there is a higher interfacial energy between PPFS and PMA, relative to PS and PMA, causing more chain stretching within PPFS-rich core domains so as to limit PPFS interactions with surrounding PMA blocks. Second, the greater electron density of the PPFS block provides a greater ability to scatter electrons and produce darker images in the TEM. The thinner region of the undulating cylinder would then be occupied primarily by PAA 93-b-PMA 99-b-PS 117 (Fig. 4G). This internal cylinder phase separation only occurred at relatively higher amounts of water in the mixed solvent solutions. Cryo-TEM showed uniform cylinders without undulation on the surface at only 40% water/THF solution after 4 days (Fig. 4E). However, multicompartment cylinders could be observed as th...
A stable phase of toroidal, or ringlike, supramolecular assemblies was formed by combining dilute solution characteristics critical for both bundling of like-charged biopolymers and block copolymer micelle formation. The key to toroid versus classic cylinder micelle formation is the interaction of the negatively charged hydrophilic block of an amphiphilic triblock copolymer with a positively charged divalent organic counterion. This produces a self-attraction of cylindrical micelles that leads to toroid formation, a mechanism akin to the toroidal bundling of semiflexible charged biopolymers such as DNA. The toroids can be kinetically trapped or chemically cross-linked. Insight into the mechanism of toroid formation can be gained by observation of intermediate structures kinetically trapped during film casting.
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