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    基于MnO2的开关型荧光碳点纸基微流控芯片测定金银花中绿原酸的含量

    Determination of Chlorogenic Acid in Honeysuckle Using MnO2-Based “On-Off ” Fluorescent Carbon Dots Paper-Based Microfluidic Chip

    • 摘要: MnO2纳米颗粒可使柠檬酸与尿素制备的碳点荧光猝灭,体系被“关闭”;加入绿原酸后,绿原酸可与MnO2发生氧化还原反应,碳点的荧光恢复,体系被“打开”,恢复的荧光强度与绿原酸的质量浓度呈相关性。以滤纸为纸基材料,采用剪切粘贴法获得亲疏水区,于亲水区滴加碳点溶液和MnO2纳米颗粒溶液,干燥后获得基于MnO2的开关型荧光碳点纸基微流控芯片,直接点样后,在365 nm紫外光下拍照,分析显色斑点的红(R)、绿(G)、蓝(B)值,优化上述纸基微流控芯片的制备条件和检测条件。结果表明,在碳点质量浓度0.50 g·L−1、MnO2质量浓度0.087 g·L−1、点样体积4 μL、显色时间25 min的优化条件下,绿原酸的质量浓度在0.06~0.70 g·L−1内与样品显色斑点的B/(B+G+R)值呈线性关系,检出限(3s/k)为0.059 mg·L−1。按照标准加入法进行回收试验,回收率为90.8%~99.6%。采用本方法对实际金银花样品平行分析5次,测定值的相对标准偏差不大于6.5%,所得的测定结果与高效液相色谱法测定结果接近。

       

      Abstract: MnO2 nanoparticles can quench the fluorescence of carbon dots(CDs) synthesized from citric acid and urea, thereby turning the system "off". Upon the additon of chlorogenic acid(CGA), the oxidation-reduction reaction between CGA and MnO2 occurred, reducing MnO2 and restoring CDs fluorescence, thus switching the system "on". The recovered fluorescence intensity correlated positively with CGA mass concentration. A paper-based microfluidic chip was fabricated using filter paper as the substrate, with hydrophilic/hydrophobic patterns created by a cut-and-paste method. CDs and MnO2 nanoparticle solutions were deposited onto the hydrophilic zones and dried to form a MnO2-based "on-off" fluorescent sensing platform. After direct sample application, the paper-based microfluidic chip was imaged under the UV light of 365 nm, and the red(R), green(G), and blue(B) values of the coloring spots were quantitatively analyzed. The preparation and detection conditions of the above paper-based microfluidic chip were optimized. As shown by the results, under these optimized conditions of CDs mass concentration of 0.50 g·L−1, MnO2 mass concentration of 0.087 g·L−1, spotting volume of 4 μL, and the color development time of 25 min, linear relationship between values of B/(R+G+B) of sample coloring spots and mass concentration of CGA was kept in the range of 0.06‒0.70 g·L−1, with detection limit(3s/k) of 0.059 mg·L-1. Test for recovery was made by the standard addition method, giving results in the range of 90.8%‒99.6%. This method was applied for parallel analysis of actual honeysuckle samples 5 times, with RSDs of the determined values not greater than 6.5%, and the determined results were close to those obtained by high performance liquid chromatography.

       

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