Mn-doped ZnS quantum dot imbedded two-fragment imprinting silica for enhanced room temperature phosphorescence probing of domoic acid.

A novel strategy was presented to construct the enhanced molecularly imprinted polymer (MIP)-based room temperature phosphorescence (RTP) probe by combining the RTP of Mn-doped ZnS quantum dots (Mn-ZnS QDs) and two-fragment imprinting. Two fragments or structurally similar parts of the target analytes were used as the dummy templates. Polyethyleneimine capped Mn-ZnS (PEI-Mn-ZnS) QDs, offering the binding sites to interact with the carboxyl groups of templates, were imbedded into MIPs by the hydrolysis of tetraethoxysilane. The rebinding of the target analytes to their fragments' cavities (recognition sites) modulated the selective aggregation of Mn-ZnS QDs in QDs-MIPs and resulted in the RTP enhancement. This new method was suitable for the selective enhanced RTP detection of nonphosphorescent analytes without any derivatization and inducers. The proposed methodology was applied to construct the high selective enhanced MIP-based RTP probe for domoic acid (DA) detection. The RTP enhancement of two-fragment imprinting silica was about 2 times of one-fragment imprinting silica and 4 times of the nonimprinting silica. The two-fragment imprinting silica exhibited the linear RTP enhancement to DA in the range of 0.25-3.5 μM in buffer and 0.25-1.5 μM in shellfish sample. The precision for 11 replicate detections of 1.25 μM DA was 0.65% (RSD), and the limit of detection was 67 nM in buffer and 2.0 μg g(-1) wet weight (w/w) in shellfish sample.