Research On Aggregation-induced Emission Micellar Chemiluminescence System And Its Analytical Application

Chemiluminescence（CL）has gradually developed into a powerful analytical tool with the advantages of eliminating the need for an external excitation light source.Its kinetic curve includes two factors,intensity and lifetime,and the improvement of CL intensity and the extension of CL emission time to obtain better analytical performance are current research hotspots.The weak signal intensity of the traditional CL system limits the improvement of detection sensitivity,thus it is urgent to develop a new material to amplify the CL intensity.CL imaging has advantages over fluorescence imaging by eliminating autofluorescence interference,but poorly durative property and weak CL emission of present CL probes limit the exploration of CL imaging system with high performance.In this thesis,the introduction of aggregation-induced emission（AIE）surfactant,intensive and long-lasting luminol CL systems have been constructed through the AIE micelle-mediated reactants enrichment,CL resonance energy transfer（CRET）,and controlled diffusion of reaction reagents.This not only greatly enhances the sensitivity of CL-based detection,but also carries great significance for extending the application of CL system in bioimaging fields.The main research contents are listed as follows:1.Based on dodecyltrimethylammonium bromide,a cationic surfactant molecule C₈-TPE-C₄TAB with AIE properties was synthesized by inserting the tetraphenylethylene（TPE）group to location between the 4th and 5th carbon atom from the quaternary ammonium head.The successful synthesis of C₈-TPE-C₄TAB was verified by nuclear magnetic and mass spectrometry characterization,and the optical and hydrophilic properties of C₈-TPE-C₄TAB were also studied.It was found that C₈-TPE-C₄TAB micelles could improve the CL intensity of the luminol-horseradish peroxidase-H₂O₂ system by nearly 9times,which was attributed to the synergistic effect of AIE micelle-induced surface enrichment and CRET.The linear range,detection limit,selectivity,anti-interference and reproducibility of H₂O₂ detection with this system were investigated,and it was successfully applied to the H₂O₂ detection in snowwater samples.In this work,a CL sensing platform for highly sensitive detection of H₂O₂ was developed with a detection limit as low as 0.1μM（S/N=3）.2.It was found that the luminol-Co²⁺-H₂O₂ system（p H=7.4）displayed intensive and long-lasting glow-type luminescence kinetics in the presence of low concentration（80μM）of C₈-TPE-C₄TAB.In comparison to several conventional quaternary ammonium surfactants,C₈-TPE-C₄TAB with ultralow critical micelle concentration（CMC）could form micelle at very low concentration,which promoted the surface enrichment and CRET and enhanced the CL intensity of luminol-Co²⁺-H₂O₂ system.In contrast,long-lasting emission was mainly because the H₂O₂ in the neutral solution slowly became peroxide anion（HO₂^-）and diffused to the surface of the AIE micelle to ensure the continuous generation of active oxygen species.Moreover,the AIE micelle increased the viscosity of the solution,which helped to slow down the diffusion rate.The CL emission of C₈-TPE-C₄TAB-luminol-Co²⁺-H₂O₂ system lasted over 1 h in the dark environment,which has great application potential in biological imaging field.