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<p>A plausible hypothesis for the origin of biological homochirality invokes chiral symmetry breaking, transfer, and amplification driven by autocatalysis. Here we experimentally demonstrate that crystallization-driven template autocatalysis (CDTA) induces mirror symmetry breaking and amplification in helices. CDTA enables the reductive cyclotetramerization of hydrogen-bonded naphthalonitrile precursors into crystalline fibers of naphthalocyanine derivatives. In achiral or racemic systems, a kinetically controlled right-handed helical bias emerges during secondary nucleation and develops into <i>P</i>-helical dominance as the fibers elongate, achieving mirror symmetry breaking. CDTA also transfers the single handedness of chiral seeds formed from enantiopure analogs to achiral naphthalocyanines through template-assisted replication, resulting in chiral amplification. A key mechanistic step involves the preorganization of naphthalonitrile molecules in a counterclockwise direction at the termini of <i>P</i>-helical fibers via <i>J</i>-type <i>π</i>–<i>π</i> stacking and hydrogen-bonding interactions for autocatalytic transformation. Thus, once mirror symmetry is broken, the resulting chiral imbalance is amplified in a self-replicating manner.</p>

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Crystallization-driven template autocatalysis induces mirror symmetry breaking and amplification

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年2月27日

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  • Huimin Wu,
  • Qingxuan Chen,
  • Duan Gao,
  • Zhen Chen

摘要

A plausible hypothesis for the origin of biological homochirality invokes chiral symmetry breaking, transfer, and amplification driven by autocatalysis. Here we experimentally demonstrate that crystallization-driven template autocatalysis (CDTA) induces mirror symmetry breaking and amplification in helices. CDTA enables the reductive cyclotetramerization of hydrogen-bonded naphthalonitrile precursors into crystalline fibers of naphthalocyanine derivatives. In achiral or racemic systems, a kinetically controlled right-handed helical bias emerges during secondary nucleation and develops into P-helical dominance as the fibers elongate, achieving mirror symmetry breaking. CDTA also transfers the single handedness of chiral seeds formed from enantiopure analogs to achiral naphthalocyanines through template-assisted replication, resulting in chiral amplification. A key mechanistic step involves the preorganization of naphthalonitrile molecules in a counterclockwise direction at the termini of P-helical fibers via J-type π–π stacking and hydrogen-bonding interactions for autocatalytic transformation. Thus, once mirror symmetry is broken, the resulting chiral imbalance is amplified in a self-replicating manner.