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<p>Colors in biominerals often arise from the occlusion of low-molecular-weight organic pigments within calcium carbonate (CaCO<sub>3</sub>) mineral phases during biomineralization processes; however, the physicochemical origin of these colors has been overlooked. Here, inspired by the growth of colored sea urchin spines that occurs through amorphous CaCO<sub>3</sub> (ACC) precursors, we show an in-vitro halochromic modulation of ACC crystallization. In this mechanism, the deprotonation of a natural red pigment naphthazarin (NZ) is driven by pH variations during mineral formation and subsequently stabilized within CaCO<sub>3</sub>- hybrid pigments. The latter show lavender-blue to violet-blue hues upon crystallization. Deprotonated&#xa0;NZ has a minimal impact on ACC formation and crystallization, which&#xa0;occurs through local dissolution and reprecipitation mechanisms; however, it limits the formation of vaterite, and calcite distorted nanodomains. Deprotonated NZ nano-inclusions&#xa0;that interact with calcite through water&#xa0;are thus formed. Overall, this study brings insights into the processes behind the coloration of biomineralized organisms.</p>

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Halochromic modulation of amorphous calcium carbonate crystallization driven by pH-responsive bioinspired pigments

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年8月3日

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  • Vaskar Sardhalia,
  • Claudio Dos Reis Ferreira,
  • Guillaume P. Laurent,
  • Mohamed Selmane,
  • Anne Vallée,
  • Mathieu Frégnaux,
  • Xiaoyan Li,
  • Marta de Frutos,
  • Andrew Fitch,
  • Clemens N. Z. Schmitt,
  • Shahrouz Amini,
  • Zhaoyong Zou,
  • Iryna Polishchuk,
  • Boaz Pokroy,
  • Peter Fratzl,
  • Thierry Azaïs,
  • Nadine Nassif,
  • Marie Albéric

摘要

Colors in biominerals often arise from the occlusion of low-molecular-weight organic pigments within calcium carbonate (CaCO3) mineral phases during biomineralization processes; however, the physicochemical origin of these colors has been overlooked. Here, inspired by the growth of colored sea urchin spines that occurs through amorphous CaCO3 (ACC) precursors, we show an in-vitro halochromic modulation of ACC crystallization. In this mechanism, the deprotonation of a natural red pigment naphthazarin (NZ) is driven by pH variations during mineral formation and subsequently stabilized within CaCO3- hybrid pigments. The latter show lavender-blue to violet-blue hues upon crystallization. Deprotonated NZ has a minimal impact on ACC formation and crystallization, which occurs through local dissolution and reprecipitation mechanisms; however, it limits the formation of vaterite, and calcite distorted nanodomains. Deprotonated NZ nano-inclusions that interact with calcite through water are thus formed. Overall, this study brings insights into the processes behind the coloration of biomineralized organisms.