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<p> A positively charged perylene diimide (PDI) with strong π-π interaction was employed alongside aminoferrocene (Fc-NH<sub>2</sub>) as potential-resolved probes to construct a ratiometric biosensor. MnO₂/Au nanorods first served as nanocarriers to load both probes. The proposed sensing mechanism relies on alkaline phosphatase (ALP)-triggered generation of ascorbic acid (AA), which reduces MnO₂ nanorods to Mn²⁺, leading to the release of Fc-NH<sub>2</sub> from the electrode surface while concurrently enhancing the exposure of trimethylaminoethyl perylene diimide (TMPDI) strongly absorbed on GCE through π-π conjugation interaction and electrostatic attractive interaction. With increasing AA concentration, the absolute value of reduction peak current at 0.56&#xa0;V significantly decreased, while the absolute value of reduction peak current at -0.37&#xa0;V gradually increased. The ratiometric signal (<i>I</i><sub>TMPDI</sub>/<i>I</i><sub>Fc−NH2</sub>) exhibits an excellent linear relationship with ALP activity over a wide linear range from 0.01 to 400 U/L with a lower detection limit of 8.5 × 10⁻³ U/L and satisfactory recoveries in the application to human serum samples.</p> Graphical Abstract <p></p>

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Perylene diimide and ferrocene functionalized MnO2 nanorods for ratiometric detection of alkaline phosphatase

  • 期刊论文

  • 发表日期：

    2026年8月1日

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  • Shumin Zhao,
  • Chengyao Li,
  • Xiaoqing Han,
  • Chuan Li,
  • Lei Shang,
  • Rongna Ma,
  • Liping Jia,
  • Xiaojian Li,
  • Guangming Nie,
  • Wei Zhang

摘要

A positively charged perylene diimide (PDI) with strong π-π interaction was employed alongside aminoferrocene (Fc-NH2) as potential-resolved probes to construct a ratiometric biosensor. MnO₂/Au nanorods first served as nanocarriers to load both probes. The proposed sensing mechanism relies on alkaline phosphatase (ALP)-triggered generation of ascorbic acid (AA), which reduces MnO₂ nanorods to Mn²⁺, leading to the release of Fc-NH2 from the electrode surface while concurrently enhancing the exposure of trimethylaminoethyl perylene diimide (TMPDI) strongly absorbed on GCE through π-π conjugation interaction and electrostatic attractive interaction. With increasing AA concentration, the absolute value of reduction peak current at 0.56 V significantly decreased, while the absolute value of reduction peak current at -0.37 V gradually increased. The ratiometric signal (ITMPDI/IFc−NH2) exhibits an excellent linear relationship with ALP activity over a wide linear range from 0.01 to 400 U/L with a lower detection limit of 8.5 × 10⁻³ U/L and satisfactory recoveries in the application to human serum samples.

Graphical Abstract