新型黄酮醇类肼探针的设计、合成与应用  

Design and synthesis of a novel flavone-based fluorescent probe for hydrazine detection and its application

作　　者：延永 靳颜颜 张亦琳 王学军 YAN Yong;JIN Yanyan;ZHANG Yilin;WANG Xuejun(College of Biomedical and Food Engineering,Shangluo University,Shangluo,726000,China)

机构地区：[1]商洛学院生物医药与食品工程学院,商洛726000

出　　处：《环境化学》2024年第6期2069-2076,共8页Environmental Chemistry

基　　金：国家自然科学基金(22173056);陕西省教育厅专项科研计划项目(21JK0612);商洛市科技计划项目(2022-Z0019);陕西秦岭特色生物资源产业技术研究院有限公司(23HKY033);陕西省大学生创新创业训练计划项目(S202311396049)资助.

摘　　要：以黄酮醇[2-(4-(二甲基氨基)苯)-3-4-氧代苯并吡喃]为荧光母核,设计合成一种新型黄酮醇类肼(N2H4)探针[2-(4-(二甲基氨基)苯基)-3-(4-氟苯甲酸酯)-4-氧代苯并吡喃,TZ],并利用核磁共振(^(1)H NMR、^(13)C NMR)和质谱(MS)确证其结构.通过测定探针TZ的选择性、竞争性、浓度梯度、Job’s曲线和pH对探针分子荧光强度的影响,发现在pH=7.4的条件下,当肼加入探针体系后,探针溶液荧光显著增强,探针对F^(−)、Cl^(−)、Br^(−)、I^(−)、PO_(4)3^(−)、Ac^(−)、SO_(4)2^(−)、HSO_(3)^(−)、SO_(3)^(2−)、CO_(3)^(2−)、NO_(3)^(−)、SCN^(−)、Ca^(2+)、Mg^(2+)、Cu^(2+)、Fe^(3+)、NH_(2)CONH_(2)、NH_(3)、N_(2)H_(4),具有非常强的抗干扰性.机理验证表明,进入探针体系的肼与探针TZ发生盖布瑞尔反应,生成的2-(4-(二甲基氨基)苯)-3-羟基黄酮具有较强荧光.探针TZ检测肼的检出限为0.1103μmol·L^(−1),在肼浓度为20—300μmol·L^(−1)时呈现良好的线性关系,实测水样品肼回收率在97.00%—102.67%范围之间.该探针具备定性、定量检测生物机体或者环境中痕量肼的潜力,为肼的荧光检测提供了一种新的选择方法.A novel Flavonol-based Fluorescent Probe[2-(4-(dimethylamino)phenyl)-4-oxo-4H-chromen-3-yl-4-fluorobenzoate,TZ]was designed and synthesized with the Flavonol[2-(4-(dimethylamino)phenyl)-3-hydroxy-4H-chromen-4-one]as fluorescent parent nucleus,and the structure was characterized by 1H NMR,13C NMR and mass spectrometer(MS).Then,we measured the selectivity,competition,concentration gradient,Job’s curve,and pH on the fluorescence intensity.The results demonstrated a significant enhancement in the fluorescence intensity of the probe solution when the hydrazine sample was introduced into the pH 7.4 probe system.The probe exhibited robust resistance to F^(−)、Cl^(−)、Br^(−)、I^(−)、PO_(4)3^(−)、Ac^(−)、SO_(4)2^(−)、HSO_(3)^(−)、SO_(3)^(2−)、CO_(3)^(2−)、NO_(3)^(−)、SCN^(−)、Ca^(2+)、Mg^(2+)、Cu^(2+)、Fe^(3+)、NH_(2)CONH_(2)、NH_(3) and N_(2)H_(4),which was demonstrated the strong anti-interference capability of probe TZ.The mechanism verification revealed that the main source of strong fluorescence was 2-(4-(dimethylamino)benzene)-3-hydroxyflavone produced by the Gabriel reaction upon hydrazine introducted into the probe system.The probe exhibited a strong linear correlation within the concentration range of 20—300μmol·L^(−1)and the detection limit for hydrazine is 0.1103μmol·L^(−1),with hydrazine recovery ranging from 97.00%to 102.67%.The probe possesses the potential for qualitative and quantitative detection of trace hydrazine in organisms or the environment,thereby offering an new alternative approach for chemical detection of hydrazine.

关 键 词：探针 肼 黄酮醇 检测 功能分子 

分 类 号：X-1[环境科学与工程] O6[理学—化学]