Dual-Ligand Ruthenium Coordination Polymer-Derived Self-Enhanced Electrochemiluminescent Emitters for Sensitive Detection of Procalcitonin.

Ru-based electrochemiluminescence (ECL) coordination polymers are widely employed for bioanalysis and medical diagnosis. However, commonly used Ru-based coordination polymers face the limitation of low efficiency due to the long distance between the ECL reagent and the coreactant dispersed in detecting solution. Herein, we report a dual-ligand self-enhanced ECL coordination polymer, composed of tris(4,4'-dicarboxylic acid-2,2'-bipyridyl) ruthenium(II) dichloride (Ru(dcbpy)32+) as ECL reactant ligand and ethylenediamine (EDA) as corresponding coreactant ligand into Zn2+ metal node, termed Zn-Ru-EDA. Zn-Ru-EDA shows excellent ECL performance which is attributed to the effective intramolecular electron transport between the two ligands. Furthermore, the dual-ligand polymer allows an anodic low excitation potential (+1.09 V) luminescence. The shift in the energy level of the highest occupied molecular orbital (HOMO) upward after the synthesis of the Zn-Ru-EDA has resulted in a reduced excitation potential. The low excitation potential reduced biomolecular damage and the destruction of the modified electrodes. The ECL biosensor has been constructed using Zn-Ru-EDA with high ECL efficiency for the ultrasensitive detection of a bacterial infection and sepsis biomarker, procalcitonin (PCT), in the range from 1.00 × 10-6 to 1.00 × 10 ng·mL-1 with outstanding selectivity, and the detection limit was as low as 0.47 fg·mL-1. Collectively, the dual-ligand-based self-enhanced polymer may provide an ideal strategy for high ECL efficiency improvement as well as designing new self-enhanced multiple-ligand-based coordination in sensitive biomolecular detection for early disease diagnostics.

Quadrilateral Nucleic Acid Frame-Accelerating DNAzyme Walker Kinetics for Biosensing Based on Host-Guest Recognition-Enhanced Electrochemiluminescence.

Depending on the reaction between walkers and tracks, DNA walker is able to output signals continuously, which has attracted great attention from the bioanalytical community. Therefore, how to improve its reaction kinetics for efficient signal readout is of great significance. Herein, a quadrilateral DNAzyme walker was fabricated by colocalizing one walker and three DNA tracks in the quadrilateral nucleic acid frame to form a reaction unit (abbreviated as qDNA walker). Impressively, in contrast to the common free DNAzyme walker, the reaction kinetics of the qDNA walker was 2.3 times faster, which could achieve microRNA detection within 30 min. Meanwhile, an electrochemiluminescence (ECL) emitter of anthracene-cucurbituril supramolecular nanocrystals (Ant-CB SNCs) was obtained based on the self-assembly of cucurbituril (CB, host molecule) and anthracene (Ant, guest molecule). Benefiting from the host-guest recognition effect, the prepared Ant-CB SNCs exhibited enhanced ECL efficiency due to the supramolecular interaction between CB and Ant, which could inhibit vibration and rotation of the Ant molecules. We defined this new enhanced ECL phenomenon as "host-guest recognition-enhanced ECL." As a proof of concept, an ECL biosensor for microRNA-21 (miRNA-21) was constructed by combining the high-efficiency DNAzyme walker and the advanced ECL emitter of Ant-CB SNCs, which showed a linear range from 50 aM to 50 pM with a low limit of detection (11 aM), highlighting the great potential in clinical diagnosis.