单一材料诱导磷光荧光双发射及其比值法抗温度干扰葡萄糖检测研究

Rapid and accurate determination of glucose concentration is particularly important for the diagnosis of diabetes. The main means of glucose detection-electrochemical methods cannot meet the requirements due to current interference and complexity and other issues. Room temperature phosphorescence is widely used due to its high sensitivity, selectivity, and anti-interference from background light, which can measure glucose concentration by measuring oxygen consumption during enzymatic reactions. Based on the ratio system of phosphorescence analysis signal and fluorescence reference signal, the detection accuracy can be effectively improved, but it is difficult to obtain phosphorescence and fluorescence simultaneously from a single material. This project proposes a glucose detection method based on the phosphorescence fluorescence ratio of dual-rare earth doped sinoporphyrin sodium against temperature interference. In this project, gadolinium ion is used to induce phosphorescence of sinoporphyrin sodium, and other rare earth ions are designed to co-dope to keep the fluorescence of sinoporphyrin sodium. The phosphorescence fluorescence ratio is used to detect the glucose concentration accurately. Usually, the luminescence is easily affected by temperature. The phosphorescent probe with different wavelength will be used to measure the temperature accurately and the temperature of the glucose concentration measurement was corrected. The three-layer optical fiber structure of glucose oxidase layer, oxygen sensor film layer and temperature correction film layer was designed and the temperature-corrected glucose concentration will be given using an automatical procedure. The ultimate aim of this project is to detect glucose accurately and rapidly for early diagnosis of diabetic patients.

葡萄糖的主要检测手段-电化学方法因电流干扰及复杂性等问题不能满足精度要求。室温磷光可通过测量酶反应过程的氧消耗检测葡萄糖浓度且灵敏度高、选择性强、不受背景干扰。基于磷光分析信号和荧光参考信号的比值系统，可有效提高检测精度，但难以从单一材料同时获得磷光和荧光，降低了室温磷光法的精度并限制了其在葡萄糖检测中的应用。本项目提出在具有特殊双环结构的卟啉-华卟啉钠中引入两种稀土金属诱导磷光荧光双发射，并利用磷光荧光比值进行抗温度干扰的葡萄糖检测，提高葡萄糖检测精度。利用钆诱导磷光发射，设计其他稀土离子共掺以保留荧光，利用磷光荧光比值准确检测葡萄糖浓度；引入与葡萄糖探针波长不同的磷光探针对温度进行精准测量，并对葡萄糖浓度测量结果进行温度修正；设计葡萄糖氧化酶、氧传感薄膜和温度修正薄膜的三层光纤结构，利用自动化程序给出温度修正后的葡萄糖浓度。实现葡萄糖的准确检测，为糖尿病患者提供早期精确诊断。

本项目利用稀土钆诱导华卟啉钠发射磷光，同时利用稀土镨进行共掺保留了华卟啉钠荧光，获得了磷光和荧光共存且强度相当的比值氧探针；研究了水溶液中金属卟啉与葡萄糖氧化酶在密封条件下对葡萄糖的检测，加入葡萄糖和葡萄糖氧化酶后，产生了葡萄糖氧化酶催化的葡萄糖与氧的反应，氧被消耗，磷光得到提升，基于磷光强度和葡萄糖浓度的关系实现了对葡萄糖浓度的定量检测，检测限低至10 μM，响应时间为15 min，由于基于葡萄糖氧化酶催化作用，具有非常好的选择性。利用再生纤维素膜消除了与进行葡萄糖传感的稀土卟啉发射波长不同的钯卟啉的磷光对氧的响应，实现了磷光只对温度响应，目前正在进行经温度修正后的葡萄糖浓度检测。在本项目的资助下，共发表SCI论文7篇，其中大类分区一区1篇，二区5篇，授权国家发明专利2项。