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Principles of self-assembly of helical pores from dendritic dipeptides

2006; National Academy of Sciences; Volume: 103; Issue: 8 Linguagem: Inglês

10.1073/pnas.0509676103

1091-6490

Virgil Percec, Andrés E. Dulcey, Mihai Peterca, Monica Ilies, Sami Nummelin, Monika J. Sienkowska, Paul A. Heiney,

Metal-Organic Frameworks: Synthesis and Applications

The self-assembly of the dendritic dipeptides (4-3,4-3,5)nG2-CH 2 -Boc- l -Tyr- l -Ala-OMe and their achiral dendritic alcohol (4-3,4-3,5)nG2-CH 2 OH precursors, both with n = 1–16, where n represents the number of methylenic units in the alkyl groups of the dendron, are reported. All chiral dendritic dipeptides and achiral dendritic alcohols self-assemble into helical porous columns that are stable in both solution and solid state. The pore diameter (D pore ) of the columns self-assembled from dendritic dipeptides is ≈10 Å larger than that of structures assembled from dendritic alcohols. The increase of the D pore at the transition from dendritic alcohol to dendritic dipeptide is accompanied by a decreased solid angle of the building block. This trend is in agreement with previous pore size-solid angle dependences observed with different protective groups of the dipeptide and primary structures of the dendron. However, within the series of dendritic alcohols and dendritic dipeptides with various n , the D pore increases when the solid angle increases. The results of these investigations together with those of previous studies on the role of dipeptide stereochemistry and protective groups on this self-assembly process provide the molecular principles required to program the construction of supramolecular helical pores with diameter controlled at the Å level from a single dendritic dipeptide architecture. These principles are expected to be valid for libraries of dendritic dipeptides based on dendrons and dipeptides with various primary structures.