The Internal Structure of Helical Pores Self‐Assembled from Dendritic Dipeptides is Stereochemically Programmed and Allosterically Regulated

Abstract

Keeping nature under control: The internal structure of helical porous protein mimics self‐assembled from hybrid dendritic dipeptides is programmed by the stereochemistry of the dipeptide and regulated allosterically. This is the first example of a synthetic helical porous supramolecular structure that is stable both in solution and in the solid state, and that is created by a sequence of events related to those encountered in nature.

Principles of self-assembly of helical pores from dendritic dipeptides

“…15, which is published as supporting information on the PNAS web site). The compounds with n ϭ 10-16 exhibit D pore at the lower limit of our current calculation method (15)(16)(17).…”

“…In addition to the 2D liquid crystalline (⌽ h , ⌽ r-c , and ⌽ r-s ) and 3D crystalline (⌽ h,k ) lattices, all alcohols and the dendritic dipeptides with n ϭ 6, 8, and 10 self-assemble into structures with long-range io (⌽ h io , ⌽ r-c io , and ⌽ r-s io ) (17). Porous supramolecular columns are identified by an increased amplitude of their (11), (20), and (21) diffraction peaks, and the pore diameter (D pore ) is calculated by simulating their x-ray diffractogram (15)(16)(17). Fig.…”

“…In the case of both dendritic alcohols and dendritic dipeptides the highest intensities are observed at the lowest values of n. As n increases a continuous decrease of the intensities is observed. The column diameter (D col ) and D pore were calculated (Table 1) (15)(16)(17), and their dependence on temperature is shown in Fig. 4.…”

“…Recently our laboratory (15) reported the self-assembly of amphiphilic dendritic dipeptides into helical porous structures that are stable in both solution and bulk (15). Preliminary reports have demonstrated that the internal structure and the stability of the porous columns self-assembled from dendritic dipeptides are programmed by the structure and stereochemistry of the dipeptide (15,16), the protective groups of the dipeptide (17), and the structure of the dendron (18) attached to the dipeptide. Here we are reporting a comparative study of the self-assembly and structural and retrostructural analysis of the supramolecular porous structures generated from libraries of (4-3,4-3,5)nG2-CH 2 -Boc-L-Tyr-L-Ala-OMe dendritic dipeptides and their achiral (4-3,4-3,5)nG2-CH 2 OH precursors with n ϭ 1-16.…”

Self‐Assembly of Amphiphilic Janus Dendrimers into Mechanically Robust Supramolecular Hydrogels for Sustained Drug Release

“…[4,5] Dendritic gels rely on well-defined, sequentially branched polymers (dendrimers) to form nanoscale networks. Dendrimers with various architectures and topologies offer a high number of functional surface groups which can be tailored to enhance binding affinity or material structure properties, [6][7][8][9][10][11][12] mediate the formation of hierarchically ordered assemblies and other complex systems, [13,14] transfer and amplify chirality, [15,16] facilitate the formation of crystalline complexes, [8] serve as powerful structuredirecting tectons [17] and as "supramolecular glue". [18,19] Dendritic gels rely on well-defined, sequentially branched polymers (dendrimers) to form nanoscale networks.…”