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 (L4EuIII2EuII). 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 L4EuIII2EuII, the longer luminous time, and the more stable electrochemiluminescence (ECL) signal. Simultaneously, L4EuIII2EuII 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.