Kanamycin (Kana) is widely used as a veterinary medicine and its abuse causes a serious threat to human health, raising the urgent demand for detection of residual Kana in animalderived food with high specificity and sensitivity. Here, we developed a photoelectrochemical (PEC) biosensor for rapid quantification of Kana, with lead sulfide quantum dots/titanium dioxide nanoparticles (PbS QDs/TiO 2 NPs) as a photosensitive composite, a Kana-specific DNA aptamer as a functional sensor, and ruthenium(III) hexaammine (Ru(NH 3 ) 6 3+ ) as a signal booster. To prepare the PEC aptasensor, TiO 2 NPs, PbS QDs, and polyethyleneimine (PEI) were respectively used to modify the indium tin oxide electrode, and then the amine-terminated aptamer probe was connected to the PEI via glutaraldehyde. Finally, Ru(NH 3 ) 6 3+ was attached on the surface of the aptamer to increase the photocurrent intensity. When Kana binds competitively with Ru(NH 3 ) 6 3+ to the aptamer immobilized on the surface of the aptasensor, Ru(NH 3 ) 6 3+ will be released from the aptamer, resulting in a decrease of the photocurrent signal. This PEC aptasensor exhibits a good linear relationship between the photocurrent shift and the logarithm of Kana concentration within the range of 1.0−300.0 nmol L −1 , and the detection limit is 0.161 nmol L −1 . Importantly, the PEC aptasensor presented good detection selectivity owing to specific interaction with Kana and was successfully implemented to quantify Kana in honey and milk, suggesting that the PEC aptasensor has the potential of rapid detection of residual Kana in animal-derived foods.
In this study, a high fluorescence sensitivity and selectivity, molecularly imprinted nanofluorescent polymer sensor (MIP@SiO 2 @QDs) was prepared using a reverse microemulsion method. 2,4,6-Trichlorophenol (2,4,6-TCP) was detected using fluorescence quenching. Tetraethyl orthosilicate (TEOS), quantum dots (QDs) and 3aminopropyltriethoxysilane (APTS) were used as cross-linker, signal sources and functional monomer respectively. The sensor (MIP@SiO 2 @QDs) and the non-imprinted polymer sensor (NIP@SiO 2 @QDs) were characterized using infra-red (IR) analysis, X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The selectivity of MIP@SiO 2 @QDs was examined by comparing 2,4,6-TCP with other similar functional substances including 2,4-dichlorophenol (2,4-DCP), 2,6-dichlorophenol (2,6-DCP) and 4-chlorophenol (4-CP). Results showed that MIP@SiO 2 @QDs had better selectivity for 2,4,6-TCP than the other compounds.Fluorescence quenching efficiency displayed a good linear response at the 2,4,6-TCP concentration range 5-1000 μmol/L. The limit of detection (LOD) was 0.9 μmol/L (3σ, n = 9). This method was equally applicable for testing actual samples with a recovery rate of 98.0-105.8%. The sensor had advantages of simple pretreatment, good sensitivity and selectivity, and wide linear range and could be applied for the rapid detection of 2,4,6-TCP in actual samples. Sample 2,4,6-TCP spiked (μmol L −1 ) Detected concentration ( x¯± s n ¼ 3 ð Þμmol L −1 ) Recovery (%)
Polymer dots (Pdots) represent newly developed semiconductor polymer nanoparticles and exhibit excellent characteristics as fluorescent probes. To improve the sensitivity and biocompatibility of Pdots ratiometric pH biosensors, we synthesized 3 types of water-soluble Pdots: Pdots-PF, Pdots-PP, and Pdots-PPF by different combinations of fluorescent dyes poly(9,9-dioctylfluorenyl-2,7-diyl) (PFO), poly[(9,9-dioctyl-fluorenyl-2,7-diyl)-co-(1,4-benzo-{2,1′,3}-thiadazole)] (PFBT), and fluorescein isothiocyanate (FITC). We found that Pdots-PPF exhibits optimal performance on pH sensing. PFO and FITC in Pdots-PPF produce pH-insensitive (λ = 439 nm) and pH-sensitive (λ = 517 nm) fluorescence respectively upon a single excitation at 380 nm wavelength, which enables Pdots-PPF ratiometric pH sensing ability. Förster resonance energy transfer (FRET) together with the use of PFBT amplify the FITC signal, which enables Pdots-PPF robust sensitivity to pH. The emission intensity ratio (I517/I439) of Pdots-PPF changes linearly as a function of pH within the range of pH 3.0 to 8.0. Pdots-PPF also possesses desirable reversibility and stability in pH measurement. More importantly, Pdots-PPF was successfully used for cell imaging in Hela cells, exhibiting effective cellular uptake and low cytotoxicity. Our study suggests the promising potential of Pdots-PPF as an in vivo biomarker.
A tetraphenylporphyrin (TPP) doped PFBT polymer quantum dots (TP-Pdots) were synthesized via the reprecipitation method for photoelectrochemical (PEC) aptasensor detection of tetracycline (TC). The TP-Pdots exhibit a superior cathode photocurrent signal. TP-Pdots increase the separation of photo-generated charges, and improve photocurrent conversion efficiency, resulting in enhanced photocurrent response. The aptamer was used as a recognition element and TP-Pdots as a photoactive material to prepare a PEC aptasensor for sensitivity detection of TC. The PEC aptasensor was constructed by immobilizing TP-Pdots on ITO electrode and combining it with aptamer by EDC coupling. After the TC reacts specifically with the aptamer, causing the aptamer to fall off from the TP-Pdots /ITO electrodes surface and the photocurrent intensity restored. This PEC aptamer sensor possesses a wide linear range from 1.0 nmol.l−1 to 1.0 × 10 4 nmol.l−1 with the detection limit of 0.26 nmol.l−1. Meanwhile, the PEC aptasensor was successfully used for the detection of tetracycline in honey.
A dual recognition system with a fluorescence quenching of quantum dots (QDs) and specific recognition of molecularly imprinted polymer (MIP) for the detection of chloramphenicol (CAP) was constructed. MIP@SiO2@QDs was prepared by reverse microemulsion method with 3-aminopropyltriethoxysilane (APTS), tetraethyl orthosilicate (TEOS) and QDs being used as the functional monomer, cross-linker and signal sources, respectively. MIP can specifically recognize CAP, and the fluorescence of QDs can be quenched by CAP due to the photo-induced electron transfer reaction between CAP and QDs. Thus, a method for the trace detection of CAP based on MIP@SiO2@QDs fluorescence quenching was established. The fluorescence quenching efficiency of MIP@SiO2@QDs displayed a desirable linear response to the concentration of CAP in the range of 1.00~4.00 × 102 μmol × L−1, and the limit of detection was 0.35 μmol × L−1 (3σ, n = 9). Importantly, MIP@SiO2@QDs presented good detection selectivity owing to specific recognition for CAP, and was successfully applied to quantify CAP in lake water with the recovery ranging 102.0~104.0%, suggesting this method has the promising potential for the on-site detection of CAP in environmental waters.
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