Key Laboratory of Luminescence Analysis and Molecular Sensing (Southwest University), Ministry of Education, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, PR China.
Key Laboratory of Luminescence Analysis and Molecular Sensing (Southwest University), Ministry of Education, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, PR China.
Biosens Bioelectron. 2023 Oct 1;237:115544. doi: 10.1016/j.bios.2023.115544. Epub 2023 Jul 27.
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)]/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 f = 70% (f was the HO content in tetrahydrofuran (THF)/HO), and its ECL efficiency was 232 times greater than f = 100% and 1853 times greater than f = 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 mol L, which promoted the application of AIECL in efficient ultra-sensitive biosensing.
四苯乙烯（TPE）衍生物的聚集诱导电化学发光（AIECL）效率通过结合分子结构和溶剂的调节得到了显著提高。首先，苯环的线性增加导致分子聚集增强，并促进了阳极的电化学反应，这是由于分子共轭增加以及最低未占据分子轨道（LUMO）和最高占据分子轨道（HOMO）更高。具有更多苯环的 4,4,4,4-(乙烯-1,1,2,2-四基)四[([1,1,4,1-四联苯]-4-甲酰基))(T3)纳米粒子（NPs）的 ECL 效率是具有 4,4,4,4-(乙烯-1,1,2,2-四基)四苯甲醛（T1）NPs 的 5558 倍，并且 T3 NPs 的相对 ECL 效率与[Ru（bpy）]/三丙胺（TPrA）体系相比达到 55.58%。此外，具有不同极性的溶剂在调节分子聚集程度方面起着至关重要的作用，这也有效地促进了 AIE 过程，并减少了由于过度密集聚集引起的聚集猝灭（ACQ）效应。这一方面在以前的 AIECL 研究中经常被忽视。T3 NPs 在 f = 70%（f 是四氢呋喃（THF）/HO 中的 HO 含量）时表现出最佳的 ECL 性能，其 ECL 效率比 f = 100%时高 232 倍，比 f = 0%时高 1853 倍。此外，发现褪黑素（MT），一种广泛用于治疗失眠的激素之一，表现出抗氧化和自由基清除特性，对 T3 NPs/TPrA 体系的 ECL 产生了显著的猝灭作用。因此，开发了一种用于 MT 的灵敏传感平台，其检测限低至 8.78×10 mol L，这促进了 AIECL 在高效超灵敏生物传感中的应用。
