Percec Virgil, Dulcey Andrés E, Peterca Mihai, Adelman Peter, Samant Ritika, Balagurusamy Venkatachalapathy S K, Heiney Paul A
Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA.
J Am Chem Soc. 2007 May 9;129(18):5992-6002. doi: 10.1021/ja071088k. Epub 2007 Apr 13.
The synthesis of dendritic dipeptides (4-3,4-3,5)12G2-CH2-Boc-L-Tyr-X-OMe where X = Gly, L-Val, L-Leu, L-Ile, L-Phe, and L-Pro is reported. Their self-assembly in bulk and in solution and the structural and retrostructural analysis of their periodic assemblies were compared to those of the previously reported and currently reinvestigated dendritic dipeptides with X = L-Ala. All dendritic dipeptides containing as X nonpolar alpha-amino acids self-assemble into helical porous columns. The substituent of X programs the structure of the helical pore and the resulting periodic array, in spite of the fact that its molar mass represents only between 0.05 and 4.77% from the molar mass of the dendritic dipeptide. In addition to the various 2-D columnar lattices, the dendritic dipeptides based on L-Ala, L-Leu, and L-Phe self-organize into 3-D hexagonal columnar crystals while those based on L-Val and L-Ile into an unknown columnar crystal. The principles via which the aliphatic and aromatic substituents of X program the structure of the helical pores indicate synthetic pathways to helical pores with bioinspired functions based on artificial nonpolar alpha-amino acids.
报道了树枝状二肽(4 - 3,4 - 3,5)12G2 - CH2 - Boc - L - Tyr - X - OMe的合成，其中X = Gly、L - Val、L - Leu、L - Ile、L - Phe和L - Pro。将它们在本体和溶液中的自组装以及其周期性组装的结构和逆向结构分析与先前报道并重新研究的X = L - Ala的树枝状二肽进行了比较。所有含非极性α - 氨基酸作为X的树枝状二肽都自组装成螺旋状多孔柱。尽管X的摩尔质量仅占树枝状二肽摩尔质量的0.05%至4.77%，但其取代基决定了螺旋孔的结构以及由此产生的周期性阵列。除了各种二维柱状晶格外，基于L - Ala、L - Leu和L - Phe的树枝状二肽自组装成三维六方柱状晶体，而基于L - Val和L - Ile的树枝状二肽则自组装成未知的柱状晶体。X的脂肪族和芳香族取代基决定螺旋孔结构的原理为基于人工非极性α - 氨基酸的具有仿生功能的螺旋孔提供了合成途径。
