Hierarchical Self-Assembly of Aminopyrazole Peptides into Nanorosettes in Water
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- 作者：Petra Rzepecki ; Katrin Hochdö ; rffer ; Torsten Schaller ; Jan Zienau ; Klaus Harms ; Christian Ochsenfeld ; Xiulan Xie ; Thomas Schrader
- 刊名：Journal of the American Chemical Society
- 出版年：2008
- 出版时间：January 16, 2008
- 年：2008
- 卷：130
- 期：2
- 页码：586 - 591
- 全文大小：311K
- 年卷期：v.130,no.2(January 16, 2008)
- ISSN：1520-5126
文摘
Self-association of aminopyrazole peptide hybrid 1 leads to stacked nanorosettes. Thisremarkable, well-ordered structure obeys the laws of nucleic acid self-assembly. In a strictly hierarchicalprocess, formation of aminopyrazole "base" triplets via a hydrogen bond network is accompanied by
-stacking with a second rosette and final dimerization of two double rosettes to a four-layer superstructure,stabilized by a six-fold half-crown alkylammonium lock. The final complex is soluble in organic as well asin aqueous solution. It was characterized in the solid state by X-ray crystallography, in water by NMRspectroscopy, and in silico by quantum chemical shift calculation. All these methods provide strong evidencefor the same hexameric complex geometry. Its structural features bear striking silimarity to nucleic acidarchitectures and their peptidic counterparts, especially alanyl-PNA. The whole self-assembly process ishighly solvent- and temperature-dependent and occurs with a high degree of cooperativity-no intermediatesare observed. Formation and dissociation of the nanorosette, however, are kinetically slow. The limitationto a hexameric aggregate can be explained by six sterically demanding valine residues, whose replacementby alanines may result in formation of infinite fibers.
-stacking with a second rosette and final dimerization of two double rosettes to a four-layer superstructure,stabilized by a six-fold half-crown alkylammonium lock. The final complex is soluble in organic as well asin aqueous solution. It was characterized in the solid state by X-ray crystallography, in water by NMRspectroscopy, and in silico by quantum chemical shift calculation. All these methods provide strong evidencefor the same hexameric complex geometry. Its structural features bear striking silimarity to nucleic acidarchitectures and their peptidic counterparts, especially alanyl-PNA. The whole self-assembly process ishighly solvent- and temperature-dependent and occurs with a high degree of cooperativity-no intermediatesare observed. Formation and dissociation of the nanorosette, however, are kinetically slow. The limitationto a hexameric aggregate can be explained by six sterically demanding valine residues, whose replacementby alanines may result in formation of infinite fibers.