目的: 开发1种基于磁性碳纳米管的固相萃取-高效液相色谱联用技术,用于快速、简便、高效地测定唾液中的诺氟沙星。方法: 合成1种以传统的碳纳米管材料为基础的新型磁性碳纳米管材料,作为固相萃取吸附剂,采用傅立叶红外光谱(FT-IR)、X射线衍射(XRD)、场发射透射电镜(TEM)对其物性进行表征;经萃取条件优化后,利用其吸附性能分离富集唾液中的诺氟沙星,联合HPLC,采用 C18色谱柱,以 0.025 mol·L-1磷酸水溶液-乙腈(87∶13)为流动相,在278 nm检测波长下,测定诺氟沙星浓度。结果: 本研究制备的磁性碳纳米管磁性反应灵敏,吸附率大于90%,重复使用12次性能良好,与HPLC联用测定人工唾液中诺氟沙星含量,质量浓度在0.4~20 μg·mL-1范围内线性关系良好(r2=0.999 8),该方法下的检测限为0.01 ng·mL-1,定量限为0.025 ng·mL-1,日内和日间精密RSD均小于5%,萃取回收率RSD小于2%,测得诺氟沙星唾液样品浓度为1.902 μg·mL-1。结论: 以磁性碳纳米管为吸附剂的磁性固相萃取技术结合高效液相色谱的方法可用于唾液中诺氟沙星的分离富集及检测,该方法萃取过程简便、快速,含量测定精密度高,准确度良好。
Objective: To establish an high performance liquid chromatography (HPLC) coupled with solid phase extraction based on magnetic carbon nanotubes (MCNTs) for the rapid, simple, and efficient determination of norfloxacin in saliva. Methods: First, a new type of magnetic carbon nanotube material based on traditional carbon nanotube material was synthesized as a solid-phase extraction adsorbent. Fourier infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and transmission electron microscopy (TEM) were used to characterize its physical properties. After optimization of extraction conditions, the adsorption performance of MCNTs was applied to enrich norfloxacin in saliva. Then,combined with HPLC, the concentration of norfloxacin was determined by using a C18 column, and a mobile phase of 0.025 mol·L-1 phosphate solution-acetonitrile (87∶13) at a detection wavelength of 278 nm were used. Results: The MCNTs prepared in this study have the characteristics of responsiveness, high adsorption rategreater than 90%, and excellent re-use performance after 12 cycles. In conjunction with HPLC, the content of nofloxacin in saliva was determined at a good linear relationship in the range of 0.4-20 μg·mL-1(r2=0.999 8), which the detection limit was 0.01 ng·mL-1, the quantitative limit was 0.025 ng·mL-1. RSDs of the intra-day and inter-day precision values were both less than 5%, and RSDs of the extraction recovery rate was less than 2%. The concentration of nofloxacin in saliva was 1.902 μg·mL-1. Conclusion: The magnetic solid-phase extraction technology with magnetic carbon nanotubes as adsorbent can be used for the separation, enrichment and detection of norfloxacin in saliva by combining HPLC. The extraction process of this method established is simple, fast, and the content determination is precise and accurate.
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