纯水中检测汞离子与银离子的菲啰啉类荧光探针
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摘要
合成了菲啰啉类化合物探针1,并通过核磁共振波谱(NMR)、质谱(MS)、红外光谱(IR)对其结构进行了表征。利用荧光发射光谱考察了探针1对Hg~(2+)及Ag~+的识别性能。结果表明,探针1在纯水介质中以荧光猝灭的方式识别Hg~(2+)和Ag~+,其结合比分别为1∶1和2∶1,检测的线性范围分别为9.0×10~(-7)～1.1×10~(-5)和8.0×10~(-7)～7.0×10~(-6) mol/L,相关系数(r~2)均大于0.99,检出限均低至10~(-8)mol/L。根据探针1识别前后荧光强度的剧烈变化,建立了裸眼检测Hg~(2+)和Ag~+的可视化分析方法。通过等温量热滴定与~1H NMR滴定考察了识别过程的热力学参数和作用机理。该研究对生物体及环境领域中Hg~(2+)和Ag~+的实时监测具有潜在的应用价值。
A phenanthroline based fluorescent probe 1 was synthesized.The structure of the probe was characterized by nuclear magnetic resonance spectroscopy(NMR),masss pectrometry(MS) and infrared spectroscopy(IR),and the recognition performance of the probe toward Hg~(2+) and Ag~+ was investigated by fluorescence emission spectroscopy.Results indicated that Hg~(2+) and Ag~+ in pure water medium were recognized by the probe via fluorescence quenching with the ratios of 1 ∶1 and 2 ∶1,respectively.There were linear relationships for Hg~(2+) and Ag~+ in the concentration ranges of 9.0×10~(-7)-1.1×10~(-5)mol/L and 8.0×10~(-7)-7.0×10~(-6)mol/L,respectively,with their correlation coefficients(r~2) larger than 0.99.The limits of detection were both as low as 10~(-8) mol/L.A visual analysis method was established for the detection of trace Hg~(2+) and Ag~+ using the probe based on the obvious changes of fluorescence intensity.The thermodynamic parameters and recognition mechanism were evaluated using isothermal titration calorimetry(ITC) and 1 H NMR titration.This method has a potential application value for the real-time monitoring of Hg~(2+) and Ag~+ in the biological and environmental fields.
A phenanthroline based fluorescent probe 1 was synthesized.The structure of the probe was characterized by nuclear magnetic resonance spectroscopy(NMR),masss pectrometry(MS) and infrared spectroscopy(IR),and the recognition performance of the probe toward Hg~(2+) and Ag~+ was investigated by fluorescence emission spectroscopy.Results indicated that Hg~(2+) and Ag~+ in pure water medium were recognized by the probe via fluorescence quenching with the ratios of 1 ∶1 and 2 ∶1,respectively.There were linear relationships for Hg~(2+) and Ag~+ in the concentration ranges of 9.0×10~(-7)-1.1×10~(-5)mol/L and 8.0×10~(-7)-7.0×10~(-6)mol/L,respectively,with their correlation coefficients(r~2) larger than 0.99.The limits of detection were both as low as 10~(-8) mol/L.A visual analysis method was established for the detection of trace Hg~(2+) and Ag~+ using the probe based on the obvious changes of fluorescence intensity.The thermodynamic parameters and recognition mechanism were evaluated using isothermal titration calorimetry(ITC) and 1 H NMR titration.This method has a potential application value for the real-time monitoring of Hg~(2+) and Ag~+ in the biological and environmental fields.
引文
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[2] Nolan E M,Lippard S J.Chem.Rev.,2008,108(9):3443-3480.
[3] Mason R P,Morel F M M,Hemond H F.Water,Air,Soil Pollut.,1995,80(1/4):775-787.
[4] Boening D W.Chemosphere,2000,40(12):1335-1351.
[5] Li D H,Shen J S,Chen N,Ruana Y B,Jiang Y B.Chem.Commun.,2011,47(20):5900-5902.
[6] Li J,Zuo G,Pan X,Wei W,Qi X,Su T,Dong W.Luminescence,2018,33(1):243-248.
[7] Zheng H,Yan M,Fan X X,Sun D,Yang S Y,Yang L J,Li J D,Jiang Y B.Chem.Commun.,2012,48(16):2243-2245.
[8] El-Shekheby H A,Mangood A H,Hamza S M,Al-Kady A S,Ebeid E-Z M.Luminescence,2014,29(2):158-167.
[9] Cizdziel J V,Gerstenberger S.Talanta,2004,64(4):918-921.
[10] Lopez-Garc?a I,Campillo N,Arnau-Jerez I.Spectrochim.Acta B,2003,58(9):1715-1721.
[11] Amiri N,Rofouei M K,Ghasemi J B.Anal.Methods,2016,8(5):1111-1119.
[12] Bosch P,Catalina F,Corrales T,Peinado C.Chem.-Eur.J.,2005,11(15):4314-4325.
[13] Ghosh M,Mandal S,Ta S,Das D.Sens.Actuators B,2017,249:339-347.
[14] Tao W B,Hu N,Liang W H.Chin.J.Appl.Chem.(陶文波,胡乃,梁王辉.应用化学),2010,27(6):732-736.
[15] Li J,Zhao Y H,Mu L,Zeng X,Zhang J X,Wei G.Chin.J.Inorg.Chem.(李俊,赵远会,牟兰,曾晞,张建新,卫钢.无机化学学报),2014,30(8):1855-1862.
[16] Li Y,Feng J K,Ren A M.J.Org.Chem.,2005,70(15):5987-5996.
[17] Shao J,Qiao Y,Lin H,Lin H.J.Fluoresc.,2009,19(1):183-188.
[18] Li Y,Shi L,Qin L,Qu L,Jing C,Lan M,Jamesb D T,Long Y.Chem.Commun.,2011,47(15):4361-4363.
[19] Algi M P.J.Fluoresc.,2016,26(2):487-496.
[20] Alreja P,Saini D,Gautam S S,Navneet K.Inorg.Chem.Commun.,2016,(70):125-128.
[21] Yao Y H,Tian H Y,Pei X L,Chen Y,Zhang W B,Qian J H.J.Instrum.Anal.(姚余华,田海玉,裴晓良,陈扬,张维冰,钱俊红.分析测试学报),2018,37(4):397-403.
[22] GB 5749-2006.Standards for Drinking Water Quality.National Standards of the People?s Republic of China(生活饮用水卫生标准.中华人民共和国国家标准).
[23] GB 8978-1996.Intgrated Wastwater Discharge Standard.National Standards of the People?s Republic of China(污水综合排放标准.中华人民共和国国家标准).
[24] Liu D H,Zhang X Y,Feng Y S,Du X L,Xue L Q,Du J S,Zhang G R,Yang Q B,Li Y X.Chem.J.Chin.Univ.(刘大海,张雪妍,冯玉沙,杜显龙,薛龙启,杜建时,张桂荣,杨清彪,李耀先.高等学校化学学报),2018,39(7):1412-1419.
[25] Huang L,Yang Z,Zhou Z,Li Y,Tang S,Xiao W,Hu M,Peng C,Chen Y,Gu B,Li H.Dyes Pigments,2019,163:118-125.
[26] Liu J,Tan G H,Wang H,Du M M.J.Chem.Eng.Chin.Univ.(刘静,谈光华,王欢,杜咪咪.高校化学工程学报),2018,4(32):949-955.
[27] Zhang Y M,Chen X P,Liang G Y,Zhong K P,Lin Q,Yao H,Wei T B.New J.Chem.,2018,42(12):10148-10152.