Aggregation-Induced Emission Effect within Peroxyoxalate-Loaded Mesoporous Silica Nanoparticles for Efficient Harvest of Chemiluminescence Energy in Aqueous Solutions.

Abstract

Aggregation-induced emission (AIE) molecules that can avoid the aggregation-caused quenching (ACQ) effect and break the concentration limit have been widely used for biosensing. Similar to fluorescence dyes, AIE molecules can be chemiexcited simply by a peroxyoxalate-based chemiluminescence (CL) reaction, but the hydrolysis of peroxyoxalate is often a problem in an aqueous solution. Herein, we report an AIE effect within peroxyoxalate-loaded silica nanoparticles (PMSNs) for an efficient harvest of CL energy as well as alleviation of bis(2,4,5-trichloro-6-carbopentoxyphenyl) oxalate (CPPO) hydrolysis. Peroxyoxalate (i.e., CPPO) and AIE molecules (i.e., 1,2-benzothiazol-2-triphenylamino acrylonitrile, BTPA) were loaded together within the mesoporous silica nanoparticles (MSNs) to synthesize the BTPA-PMSN nanocomposite. The BTPA-PMSNs not only allowed CPPO to be dispersed well in an aqueous solution but also avoided the hydrolysis of CPPO. Meanwhile, the proximity between BTPA and CPPO molecules in the mesopores of MSNs facilitated the BTPA aggregate to harvest the energy from CL intermediates. Hence, the CL system of BTPA-PMSNs can work efficiently in aqueous solutions at a physiological pH. The CL quantum yield of the BTPA-PMSN system was measured to be 9.91 × 10-5, about 20 000-fold higher than that obtained in the rhodamine B (RhB, a typical ACQ dye)-PMSN system. Using BTPA-PMSNs for H2O2 sensing, a limit of detection (LOD) as low as 5 nM can be achieved, 1000-fold lower than that achieved in the RhB-PMSNs system. Due to the feasibility of working at a physiological pH, this CL system is also quite suitable for the detection of oxidase substrates such as glucose and cholesterol. This BTPA-PMSN CL system with the merits of high CL quantum yield at a physiological pH is appealing for biosensing.