β-Cyclodextrin and its derivatives can selectively bind to various organic molecules in its cavity and provide good applications in sample preparation. Surface-enhanced Raman spectroscopy is a sensitive technique and has received increasing attention in the last decade. Herein, 3,5-dimethyl phenyl carbamoylated β-cyclodextrin bonded silica gel was used as a ssorbent in solid-phase extraction to selectively enrich forchlorfenuron and thidiazuron followed by determination with surface-enhanced Raman spectroscopy. It showed excellent selectivity for forchlorfenuron and thidiazuron and the adsorption capacities were 40.0 and 30.0 μg/g, respectively. A rapid and sensitive method based on the modified β-cyclodextrin solid-phase extraction coupled with surface-enhanced Raman spectroscopy was developed. The linear ranges were 30.0-300.0 μg/L for forchlorfenuron and thidiazuron at 1005 and 640 cm(-1) , respectively. Both of the limits of detection were 15.0 μg/L, which were significantly lower than the maximum permitted by the National Standard. The recoveries of forchlorfenuron and thidiazuron were 78.9-87.9% for the spiked grape, kiwi, cucumber and tomato, with relative standard deviations of 8.1-13.2%. The results show that this method is sensitive, selective, and relatively time saving, and has great potential in the analysis of trace amounts of plant growth regulators in fruits and vegetables.
Magnetic solid-phase extraction is a powerful sample preparation tool. Combined with covalent organic polymers, this technique permits an excellent extraction performance. We present a sensitive, efficient, and easy operating magnetic- covalent organic polymer solid-phase extraction method. By using the magnetic covalent organic polymer nanoparticles yielded by a one-pot reaction, five fluorescent whitening agents were successfully preconcentrated and separated. The saturated extraction amounts of the magnetic covalent organic polymer nanoparticles for the five fluorescent whitening agents were in the range of 97-155 nmol/mg. Coupled with high-performance liquid chromatography, the limit of detection of the fluorescent whitening agent was improved by at least an order of magnitude compared to current literature records. Under the optimal conditions, the linear ranges of these five fluorescent whitening agents were up to 0.5-100 ng/L, the limit of detection was as low as 0.1 ng/L, and the recoveries were in the range of 78.2-105% with relative standard deviations lower than 5.5%. Meanwhile, a trace level of 7-diethylamino-4-methylcoumarin was found in a typical cosmetic sample by using this magnetic-covalent organic polymer solid-phase extraction method when coupling with high-performance liquid chromatography. Moreover, this sensitive, efficient, and easy operating sample preparation method can be extended to analysis of other analytes that have a π-π conjugated structure.
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