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<p>Metal-directed assemblies of helical peptides are emerging chiral biomimetic materials, yet dynamic helical peptides remain underexplored. Here we report the coordination-driven assembly of dynamic 12/10-helical β-pentapeptides into distinct metal–peptide frameworks (MPFs) with silver ions. Ligand <b>1</b>, consisting of <i>cis</i>-2-aminocycloheptanecarboxylic acid with alternating chirality, exhibits solvent-dependent screw-sense preference: (<i>P</i>)-helix in protic and (<i>M</i>)-helix in aprotic solvents. The two helical conformers are not enantiomers and assemble into two distinct MPFs (<b>Ag-1M</b> and <b>Ag-1P</b>), while a racemic ligand mixture (<b>1</b> and <Emphasis Type="BoldItalic">ent</Emphasis><b>-1</b>) yields a third MPF (<b>Ag-</b><Emphasis Type="BoldItalic">rac</Emphasis><b>-1PM</b>). A series of modified ligands (<b>2-5</b>), incorporating various central residues, form MPFs analogous to <b>Ag-1M</b> or <b>Ag-1P</b>, with pore environments modulated by side chains. Particularly, an MPF incorporating polar N-acetyl azepane moieties (<b>Ag-5M</b>) selectively recognizes a chiral guest through post-crystallization. These results highlight dynamic helical β-peptides as versatile building blocks for diverse chiral MPFs, with tunable pore environments through rational peptide design.</p>

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Assembly of dynamic helical β-peptides with switchable handedness into multiple types of metal-peptide frameworks

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年10月27日

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  • Ingyu Han,
  • Ha-Jin Lee,
  • Ilia A. Guzei,
  • Soo Hyuk Choi

摘要

Metal-directed assemblies of helical peptides are emerging chiral biomimetic materials, yet dynamic helical peptides remain underexplored. Here we report the coordination-driven assembly of dynamic 12/10-helical β-pentapeptides into distinct metal–peptide frameworks (MPFs) with silver ions. Ligand 1, consisting of cis-2-aminocycloheptanecarboxylic acid with alternating chirality, exhibits solvent-dependent screw-sense preference: (P)-helix in protic and (M)-helix in aprotic solvents. The two helical conformers are not enantiomers and assemble into two distinct MPFs (Ag-1M and Ag-1P), while a racemic ligand mixture (1 and ent-1) yields a third MPF (Ag-rac-1PM). A series of modified ligands (2-5), incorporating various central residues, form MPFs analogous to Ag-1M or Ag-1P, with pore environments modulated by side chains. Particularly, an MPF incorporating polar N-acetyl azepane moieties (Ag-5M) selectively recognizes a chiral guest through post-crystallization. These results highlight dynamic helical β-peptides as versatile building blocks for diverse chiral MPFs, with tunable pore environments through rational peptide design.