High AIECL performance of tetraphenylethene derivatives originated from the linear increasing of benzene ring and solvent regulation for sensitive measurement of melatonin

Abstract

The efficiency of aggregation-induced electrochemiluminescence (AIECL) in tetraphenylethene (TPE) derivatives were significantly enhanced by combining the regulation of molecular structure and solvent. Firstly, the linear increase of the benzene ring resulted in enhanced molecular aggregation and promoted the electrochemical reaction of the anode, due to increased molecular conjugation and higher lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO). The ECL efficiency of 4,4,4,4-(Ethene-1,1,2,2-tetrayl) tetrakis (([1,1,4,1-terphenyl]-4-carbaldehyde)) (T3) nanoparticles (NPs) with more benzene rings were 5558 times that of 4,4,4,4-(ethene-1,1,2,2-tetrayl) tetrabenzaldehyde (T1) NPs, and its relative ECL efficiency of T3 NPs reached 55.58% compared to the [Ru (bpy)3]2+/tripropylamine (TPrA) system. Furthermore, solvents with different polarities played a crucial role in modulating the degree of molecular aggregation, which also effectively facilitated the AIE process and reduced the aggregation-caused quenching (ACQ) effect caused by excessively dense aggregation. This aspect had often been overlooked in previous AIECL studies. T3 NPs demonstrated optimal ECL performance at fw = 70% (fw was the H2O content in tetrahydrofuran (THF)/H2O), and its ECL efficiency was 232 times greater than fw = 100% and 1853 times greater than fw = 0%. Additionally, it was found that melatonin (MT), one of the hormones widely used to treat insomnia, exhibited antioxidant and free radical scavenging properties, which exerted a significant quenching effect on the ECL of the T3 NPs/TPrA system. Consequently, a sensitive sensing platform was developed for MT with a low detection limit of 8.78 × 10−10 mol L−1, which promoted the application of AIECL in efficient ultra-sensitive biosensing.