a b s t r a c tA novel molecular imprinting-based turn-on ratiometric fluorescence sensor was constructed via a facile sol-gel polymerization for detection of 2,4-dichlorophenoxyacetic acid (2,4-D) on the basis of photoinduced electron transfer (PET) by using nitrobenzoxadiazole (NBD) as detection signal source and quantum dots (QDs) as reference signal source. With the presence and increase of 2,4-D, the amine groups on the surface of QDs@SiO 2 could bind with 2,4-D and thereby the NBD fluorescence intensities could be significantly enhanced since the PET process was inhibited, while the QDs maintained constant intensities. Accordingly, the ratio of the dual-emission intensities of green NBD and red QDs could be utilized for turn-on fluorescent detection of 2,4-D, along with continuous color changes from orange-red to green readily observed by the naked eye. The as-prepared fluorescence sensor obtained high sensitivity with a low detection limit of 0.14 μM within 5 min, and distinguished recognition selectivity for 2,4-D over its analogs. Moreover, the sensor was successfully applied to determine 2,4-D in real water samples, and high recoveries at three spiking levels of 2,4-D ranged from 95.0% to 110.1% with precisions below 4.5%. The simple, rapid and reliable visual sensing strategy would not only provide potential applications for high selective ultratrace analysis of complicated matrices, but also greatly enrich the research connotations of molecularly imprinted sensors.
We propose a novel molecular imprinting fluorescence nanosensor via a facile surface imprinting polymerization one-pot synthesis strategy for highly selective and sensitive recognition and detection of 4-nitrophenol (4-NP) on the basis of electron transfer induced fluorescence quenching mechanism. By combining the high selectivity of molecularly imprinted polymers (MIPs) and the strong fluorescence property of quantum dots (QDs), the QD@MIPs nanosensor was demonstrated highly selective and sensitive towards 4-NP, with satisfactory rapidity, accuracy, reliability and practicality. This sensing platform is readily constructed in solution without any other labeling or modification steps, and demonstrated remarkable advantages such as simplicity, rapidity and universality, high selectivity and sensitivity, and good reliability and practicability. This work focuses on the microanalysis of trace 4-NP in complicated environmental water samples by using a kind of new high-effective nanoscale sensing material. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59
Phycocyanin with important physiological/environmental significance has attracted increasing attention; versatile molecularly imprinted polymers (MIPs) have been applied to diverse species, but protein imprinting is still quite difficult. Herein, using phycocyanin as template via a sol−gel process, we developed a novel fluorescent probe for specific recognition and sensitive detection of phycocyanin by quantum dots (QDs) based mesoporous structured imprinting microspheres (SiO 2 @QDs@ms-MIPs), obeying electron-transfer-induced fluorescence quenching mechanism. When phycocyanin was present, a Meisenheimer complex would be produced between phycocyanin and primary amino groups of QDs surface, and then the photoluminescent energy of QDs would be transferred to the complex, leading to the fluorescence quenching of QDs. As a result, the fluorescent intensity of the SiO 2 @QDs@ms-MIPs was significantly decreased within 8 min, and accordingly a favorable linearity within 0.02−0.8 μM and a high detectability of 5.9 nM were presented. Excellent recognition specificity for phycocyanin over its analogues was displayed, with a high imprinting factor of 4.72. Furthermore, the validated probe strategy was successfully applied to seawater and lake water sample analysis, and high recoveries in the range of 94.0−105.0% were attained at three spiking levels of phycocyanin, with precisions below 5.3%. The study provided promising perspectives to develop fluorescent probes for convenient, rapid recognition and sensitive detection of trace proteins from complex matrices, and further pushed forward protein imprinting research.
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