A Hollow Foldecture with Truncated Trigonal Bipyramid Shape from the Self‐Assembly of an 11‐Helical Foldamer

Abstract

The creation of self-assembling microscale architectures that possess new and useful physical properties remains a significant challenge. Herein we report that an 11-helical foldamer self-assembles in a controlled manner to form a series of 3D foldectures with unusual three-fold symmetrical shapes that are distinct from those generated from 12-helical foldamers. The foldamer packing motif was revealed by powder X-ray diffraction technique, and provides an important link between the molecular-level symmetry and the microscale morphologies. The utility of foldectures with hollow interiors as robust and well-defined supramolecular hosts was demonstrated for inorganic, organic, and even protein guests. This work will pave the way for the design of functional foldectures with greater 3D shape diversity and for the development of biocompatible delivery vehicles and containment vessels.

Modulating Hydrogen Bonded Self-assembled Patterns and Morphological Features by a Change in Side Chain of Third Amino Acid of Synthetic γ- Amino Acid Based Tripeptides

“…However, peptide scaffolds are represented as elegant motifs to construct self‐assembled functional materials. [38–63] Hybrid peptides constructed by conventional and un‐conventional amino acids tend to form well‐organized supramolecular structures and which are used as functional materials . Over the past few years, we have explored various applications of low molecular weight linear peptides, which show remarkable self‐assembled nano‐structures under certain physical conditions …”

Self‐Assembly of a β‐Peptide Foldamer: The Role of the Surfactant in Three‐Dimensional Shape Selection

“…We have previously reported that the structural diversity of foldectures encompasses highly exotic 3D morphologies, such as molar teeth and hollow bipyramids . To the best of our knowledge, these are exceptionally unique examples of anisotropic 3D shapes that have not been observed in previous studies of other self‐assembled organic materials.…”

The Diverse World of Foldamers: Endless Possibilities of Self-Assembly

“…Mixed α-β Foldamers Beyond the foldectures based on 12-helices of β-foldamers already reported in Section 2.3, Lee's group also extensively studied the aqueous self-assembly in solid shapes of surfactant-containing solutions of 1:1 alternating α-β foldamers showing the repetition of the Aib-trans-ACPC sequence, as shown in Figure 24a [261][262][263][264][265]. In all of these studies, the exact packing mode could be ascertained by an intelligent use of high-resolution powder X-ray diffraction (PXRD), whereas the morphologies of self-assembled nanostructures were observed by SEM and additional information could be obtained by applying various physico-chemical analyses, such as differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and FT-IR.…”

“…Adding an Aib residue at the C-terminus, thus using the heptamer Boc-(Aib-ACPC) 3 -Aib-OBn, depicted by R 2 = Aib-OBn in Figure 24a, and exploiting again the differential solvation in water or aqueous P123 solutions at increasing concentrations (8, 24, 40, and 48 g L −1 ) to drive the directional growth, it was possible to synthesize amazing self-assembled shapes with the same molecular packing motif [262]. In particular, the tripod (F 0 ) morphology was obtained from distilled water, while the morphologies from F 1 to F 4 , which were all based on a trigonal bipyramid, formed in 8 g L −1 (caudate trigonal bipyramid), 24 g L −1 (trigonal bipyramid), 40 g L −1 (truncated trigonal bipyramid), and 48 g L −1 (truncated trigonal bipyramid with caved face) solutions of P123, respectively, as shown in Figure 24c.…”