所报道的用于检测各种标记物的有机电化学发光(ECL)发光体通常遭受分子间π-π堆叠诱导的发光体猝灭。在这里,我们展示了一种新的聚集诱导电化学发光(AIECL)发射体的一锅法合成(即,TPE@SiO2/rGO复合材料)用于微囊藻毒素亮氨酸精氨酸(MC-LR)的灵敏测量。通过将二氧化硅封装的1,1,2,2-四(4-羧基苯基)乙烯(TPE)嵌入还原的氧化石墨烯中来构建TPE@SiO2/rGO复合材料。与单体TPE相比,这种复合材料表现出高的发光效率和强的ECL发射,因为由SiO2笼中的空间限制效应触发的AIECL现象引起分子内部运动和振动的限制。值得注意的是,这种复合材料具有易于制备的独特优点,简单的功能化,和稳定的发光。尤其是,基于TPE@SiO2/rGO的ECL-RET系统具有69.7%的高淬火效率(ΦET)。当目标MC-LR存在时,它触发DNA链置换反应(SDR),由于TPE@SiO2/rGO复合材料与亚甲基蓝(MB)之间的ECL共振能量转移,导致TPE@SiO2/rGO复合材料的ECL信号猝灭。所提出的生物传感器使高灵敏度,低成本,和MC-LR的强大测量,具有7个数量级的大动态范围和3.78fg/mL的检测极限,它在复杂的生物基质中显示出优异的检测性能,在食品安全和水监测方面具有潜在的应用。
The reported organic electrochemiluminescence (ECL) luminophors for the detection of various markers often suffer from intermolecular π-π stacking-induced luminophore quenching. Herein, we demonstrate one-pot synthesis of a new aggregation-induced electrochemiluminescence (AIECL) emitter (i.e., TPE@SiO2/rGO composite) for sensitive measurement of microcystin-leucine arginine (MC-LR). The TPE@SiO2/rGO composite is constructed by embedding the silica-encapsuled 1,1,2,2-tetra(4-carboxylphenyl)ethylene (TPE) in the reduced graphene oxide. In comparison with the monomer TPE, this composite exhibit high luminescence efficiency and strong ECL emission, because the AIECL phenomenon triggered by the spatial confinement effect in the SiO2 cage induces the restriction of the internal motion and vibration of molecules. Notably, this composite has distinct advantages of easy preparation, simple functionalization, and stable luminescence. Especially, the TPE@SiO2/rGO-based ECL-RET system exhibits a high quenching efficiency (ΦET) of 69.7%. When target MC-LR is present, it triggers DNA strand displacement reaction (SDR), inducing the quenching of the ECL signal of TPE@SiO2/rGO composite due to ECL resonance energy transfer between TPE@SiO2/rGO composite and methylene blue (MB). The proposed biosensor enables highly sensitive, low-cost, and robust measurement of MC-LR with a large dynamic range of 7 orders of magnitude and a detection limit of 3.78 fg/mL, and it displays excellent detection performance in complex biological matrices, holding potential applications in food safety and water monitoring.