4.8 Article

A Chiral Ligand Assembly That Confers One-Electron O2 Reduction Activity for a Cu2+-Selective Metallohydrogel

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 57, Issue 13, Pages 3504-3508

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201801290

Keywords

chiral ligands; cytochrome c; EPR; metallohydrogels; superoxide

Funding

  1. National Key Basic Research Program of China [2013CB921800]
  2. Hunan Provincial Science and Technology Plan Project [2017TP1001]
  3. Hunan Provincial Education Foundation [15A158, 15C1168]
  4. National Natural Science Foundation of China [21473257, 11227901, 31370812, 21773311, 81788104]
  5. double first class construct program of USC

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The design of functional metallohydrogels is attractive but challenging. A rational approach is introduced for designing functional metallohydrogels using chiral ligands, a phenylalanine derivative with a pyridyl group (l/d-PF). Intriguingly, the as-prepared metallohydrogel exhibits excellent O-2 binding and activating properties. Insights into the O-2 binding pathway reveals the presence of a novel [(l+d)-PF-Cu3+-O-2(-)] species, which can efficiently reduce ferric cytochromec with the reactive O-2(-) by receiving an electron from reductant ascorbic acid. This study provides helpful instructions for developing new artificial systems with specific functions through the effective combination of chiral ligands with metal ions.

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