Rare Self-Luminous Mixed-Valence Eu-MOF with a Self-Enhanced Characteristic as a Near-Infrared Fluorescent ECL Probe for Nondestructive Immunodetection

Steady and efficient sensitized emission of Eu²⁺ to Eu³⁺ can be achieved through a rare mixed-valence Eu-MOF (L₄Eu^III₂Eu^II). Compared with the sensitization of other substances, the similar ion radius and configuration of the extranuclear electron between Eu²⁺ and Eu³⁺ make sensitization easier and more efficient. The sensitization of Eu²⁺ to Eu³⁺ is of great assistance for the self-enhanced luminescence of L₄Eu^III₂Eu^II, the longer luminous time, and the more stable electrochemiluminescence (ECL) signal. Simultaneously, L₄Eu^III₂Eu^II possesses near-infrared (NIR) fluorescence of around 900 nm and a mighty self-luminous characteristic, which render it useful as a NIR fluorescent probe and as a luminophore to establish a NIR ECL biosensor. This NIR biosensor can greatly reduce the damage to the detected samples and even achieve a nondestructive test and improve the detection sensitivity by virtue of strong susceptibility and environmental suitability of NIR. In addition, the CeO₂@Co₃O₄ triple-shelled microspheres further enhanced the ECL intensity due to two redox pairs of Ce³⁺/Ce⁴⁺ and Co²⁺/Co³⁺. The NIR ECL biosensor based on these strategies owns an ultrasensitive detection ability of CYFRA 21-1 with a low limit of detection of 1.70 fg/mL and also provides a novel idea for the construction of a highly effective nondestructive immunodetection biosensor.