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<p>Visible light photocatalysis, which exploits the reactivity of molecules at their excited state, has triggered a paradigm shift in organic synthesis by enabling some very unique chemical transformations. Yet, achieving precise control of the enantioselectivity in such processes remains a major challenge. A promising strategy involves linking a synthetic transition metal photocatalyst within the chiral architecture of a biomolecule to create a highly selective artificial metallo-photoenzyme. However, such an artificial metalloenzyme that integrates the merits of biocatalysis and photocatalysis to promote abiological reactions with high enantioselectivity is still unknown. Here, we report an artificial metallo-photoDNAzyme resulting from the covalent anchoring of a visible light-absorbing iridium-based photocatalyst within a double-stranded (ds)DNA helix, exhibiting efficient triplet-triplet energy transfer and high levels of enantioselectivity in [2 + 2] intramolecular cycloadditions.</p>

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A metal-DNA biohybrid as enantioselective artificial photoDNAzyme

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年5月13日

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  • Zachary Pastorel,
  • Juliette Zanzi,
  • Mathieu Noël,
  • Alessio Bartocci,
  • Stellios Arseniyadis,
  • Elise Dumont,
  • Yves Canac,
  • Olivier Baslé,
  • Michael Smietana

摘要

Visible light photocatalysis, which exploits the reactivity of molecules at their excited state, has triggered a paradigm shift in organic synthesis by enabling some very unique chemical transformations. Yet, achieving precise control of the enantioselectivity in such processes remains a major challenge. A promising strategy involves linking a synthetic transition metal photocatalyst within the chiral architecture of a biomolecule to create a highly selective artificial metallo-photoenzyme. However, such an artificial metalloenzyme that integrates the merits of biocatalysis and photocatalysis to promote abiological reactions with high enantioselectivity is still unknown. Here, we report an artificial metallo-photoDNAzyme resulting from the covalent anchoring of a visible light-absorbing iridium-based photocatalyst within a double-stranded (ds)DNA helix, exhibiting efficient triplet-triplet energy transfer and high levels of enantioselectivity in [2 + 2] intramolecular cycloadditions.