基于稀土铕离子配合物的时间分辨荧光pH探针的合成及应用
The Synthesis and Application of Time-Resolved Fluorescence pH Probe Based on Rare Earth Europium Ion Complex
摘 要
以4,7-二苯基-1,10-菲啰啉(母体)和2-噻吩甲酰三氟丙酮为协同剂和β-二酮配体,合成了一种稀土三元铕离子配合物,其荧光寿命为0.544 0 ms,并以其为荧光探针对水环境的pH进行时间分辨荧光测定。荧光探针的时间分辨荧光强度在pH 7.00~8.95时达到最大值并保持较好的稳定性;在pH小于7.00和pH大于8.95时,荧光探针的时间分辨荧光强度随着pH变化而变化;在pH 2.50~7.00和pH 9.91~14.00时,荧光探针的时间分辨荧光猝灭率与pH呈线性关系。溶解氧浓度和离子强度变化对pH测定结果无影响。采用荧光探针测定实际水样的pH,结果与玻璃电极的测定结果相符,测定值的相对标准偏差(n=8)在4.3%~8.1%之间。
时间分辨荧光分析法
探针
pH测定
Europium ion complex
Time-resolved fluorescence analysis
Probe
Determination of pH
Abstract
A rare earth ternary europium ion complex with fluorescent lifetime of 0.544 0 ms was synthesized by using 4,7-diphenyl-1,10-phenanthroline and 2-thenoyltrifluoroacetone as synergic agents and β-diketone ligands. The complex was used as fluorescent probe for pH determination of environmental water samples by time-resolved fluorescence analysis. The fluorescent probe showed the maximum and stable time-resolved fluorescence intensity when the pH ranged from 7.00 to 8.95, while the time-resolved fluorescence intensity changed obviously in acidic (pH<7.00) and strong alkaline (pH>8.95) conditions. The time-resolved fluorescence quenching of the fluorescent probe showed linear response toward pH in the range of 2.50-7.00 or 9.91-14.00. The prepared fluorescent probe was insensitive to dissolved oxygen and ionic strength. The prepared fluorescent probe was used to determine pH of real water samples, giving results in consistent with those obtained by glass electrode and RSDs (n=8) in the range of 4.3%-8.1%.
中图分类号 O561.3 DOI 10.11973/lhjy-hx201607001
所属栏目 试验与研究
基金项目 国家自然科学基金(21507034);广州市产学研协同 创新重大专项(201508020078);中央级公益性科研院所基本科研 业务费(2006001001009)
收稿日期 2015/6/11
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备注黄大伟(1985-),男,湖南常德人,助理研究员,博 士,主要从事功能化长寿命荧光材料的制备及应用。
引用该论文: HUANG Da-wei,BING Yong-xin,HONG Wei,CUI Kai,GUO Qing-wei. The Synthesis and Application of Time-Resolved Fluorescence pH Probe Based on Rare Earth Europium Ion Complex[J]. Physical Testing and Chemical Analysis part B:Chemical Analysis, 2016, 52(7): 745～749
黄大伟,邴永鑫,洪 伟,崔 恺,虢清伟. 基于稀土铕离子配合物的时间分辨荧光pH探针的合成及应用[J]. 理化检验－化学分册, 2016, 52(7): 745～749
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参考文献
【1】HAN J Y, BURGESS K. Fluorescent indicators for intracellular pH［J］. Chem Rev, 2010,110(5):2709-2728．
【2】KIM H N, SWAMY K M K, YOON J. Study on various fluorescein derivatives as pH sensors［J］. Tetrahedron Lett, 2011,52(18):2340-2343．
【3】AIGNER D, BORISOV S M, ORRIACH FERNNDEZ F J, et al. New fluorescent pH sensors based on covalently linkable PET rhodamines［J］. Talanta, 2012,99:194-201．
【4】MARTZ T R, CARR J J, FRENCH C R, et al. A submersible autonomous sensor for spectrophotometric pH measurements of natural waters［J］. Anal Chem, 2003,75(8):1844-1850．
【5】FUH M R S, BURGESS L W, HIRSCHFELD T, et al. Single fibre optic fluorescence pH probe［J］. Analyst, 1987,112(8):1159-1163．
【6】SAFAVI A, ABDOLLAHI H. Optical sensor for high pH values［J］. Anal Chim Acta, 1998,367(1/3):167-173．
【7】李芳,孙向英,吴凯,等.以异硫氰酸荧光素为指示剂的pH荧光自组装传感膜［J］.分析化学, 2013,41(7):1097-1011．
【8】ZHANG W S, TANG B, LIU X, et al. A highly sensitive acidic pH fluorescent probe and its application to HepG2 cells［J］. Analyst, 2009,134:367-371．
【9】CUI D W, QIAN X H, LIU F Y, et al. Novel fluorescent pH sensors based on intramolecular hydrogen bonding ability of naphthalimide［J］. Org Lett, 2004,6(16):2757-2760．
【10】TANG B, YU F B, LI P. A near-infrared neutral pH fluorescent probe for monitoring minor pH changes: imaging in living HepG2 and HL-7702 cells［J］. J Am Chem Soc, 2009,131(8):3016-3023．
【11】GUO B C, PENG X J, CUI A J, et al. Synthesis and spectral properties of new boron dipyrromethene dyes［J］. Dyes Pigments, 2007,73(2):206-210．
【12】LU H G, XU B, DONG Y J, et al. Novel fluorescent pH sensors and a biological probe based on anthracene derivatives with aggregation-induced emission characteristics［J］. Langmuir, 2010,26(9):6838-6844．
【13】NIU C G, GUI X Q, ZENG G M, et al. Fluorescence ratiometric pH sensor prepared from covalently immobilized porphyrin and benzothioxanthene［J］. Anal Bioanal Chem, 2005,383(2):349-357．
【14】LI Z Z, NIU C G, ZENG G M, et al. A novel fluorescence ratiometric pH sensor based on covalently immobilized piperazinyl-1,8-napthalimide and benzothioxanthene［J］. Sens Actuators B, 2006,114(1):308-315．
【15】YE T X, DU Y Y, HE C Y, et al. Preparation of novel core-shell silica particles for pH sensing using ratiometric fluorescence approach［J］. Anal Methods,2012,4:1001-1004．
【16】LIN H J, SZMACINSKI H, LAKOWICZ J R. Lifetime-based pH sensors: indicators for acidic environments［J］. Anal Biochem, 1999,269(1):162-167．
【17】KOSCH U, KLIMANT I, WOLFBEIS O S. Long-lifetime based pH micro-optodes without oxygen interference［J］. Fresenius J Anal Chem. 1999,364(1/2):48-53．
【18】MA L Y, WANG H Y, XIE H, et al. A long lifetime chemical sensor: study on fluorescence property of fluorescein isothiocyanate and preparation of pH chemical sensor［J］. Spectrochim Acta Part A, 2004,60(8/9):1865-1872．
【19】MA L J, CAO W G, LIU J L, et al. A highly selective and sensitive fluorescence dual-responsive pH probe in water［J］. Sens Actuators B, 2012,169:243-247．
【20】GEORGIEV N I, ASIRI A M, QUSTI A H, et al. Design and synthesis of pH-selective fluorescence sensing PAMAM light-harvesting dendrons based on 1,8-naphthalimides［J］. Sens Actuators B, 2014,190:185-198．
【21】NGUYEN T H, VENUGOPALA T, CHEN S, et al. Fluorescence based fibre optic pH sensor for the pH 10-13 range suitable for corrosion monitoring in concrete structures［J］. Sens Actuators B, 2014,191:498-507．
【22】王炳帅,王丽,吴彤,等. 苯乙烯类菁染料pH探针的合成与活细胞成像［J］.高等学校化学学报, 2010,31(6):1148-1151．
【23】BINNEMANS K. Lanthanide-based luminescent hybrid materials［J］. Chem Rev, 2009,109(9):4283-4374．
【24】MIZUKAMI S, TONAI K, KANEKO M, et al. Lanthanide-based protease activity sensors for time-resolved fluorescence measurements［J］. J Am Chem Soc, 2008,130(44):14376-14377．
【2】KIM H N, SWAMY K M K, YOON J. Study on various fluorescein derivatives as pH sensors［J］. Tetrahedron Lett, 2011,52(18):2340-2343．
【3】AIGNER D, BORISOV S M, ORRIACH FERNNDEZ F J, et al. New fluorescent pH sensors based on covalently linkable PET rhodamines［J］. Talanta, 2012,99:194-201．
【4】MARTZ T R, CARR J J, FRENCH C R, et al. A submersible autonomous sensor for spectrophotometric pH measurements of natural waters［J］. Anal Chem, 2003,75(8):1844-1850．
【5】FUH M R S, BURGESS L W, HIRSCHFELD T, et al. Single fibre optic fluorescence pH probe［J］. Analyst, 1987,112(8):1159-1163．
【6】SAFAVI A, ABDOLLAHI H. Optical sensor for high pH values［J］. Anal Chim Acta, 1998,367(1/3):167-173．
【7】李芳,孙向英,吴凯,等.以异硫氰酸荧光素为指示剂的pH荧光自组装传感膜［J］.分析化学, 2013,41(7):1097-1011．
【8】ZHANG W S, TANG B, LIU X, et al. A highly sensitive acidic pH fluorescent probe and its application to HepG2 cells［J］. Analyst, 2009,134:367-371．
【9】CUI D W, QIAN X H, LIU F Y, et al. Novel fluorescent pH sensors based on intramolecular hydrogen bonding ability of naphthalimide［J］. Org Lett, 2004,6(16):2757-2760．
【10】TANG B, YU F B, LI P. A near-infrared neutral pH fluorescent probe for monitoring minor pH changes: imaging in living HepG2 and HL-7702 cells［J］. J Am Chem Soc, 2009,131(8):3016-3023．
【11】GUO B C, PENG X J, CUI A J, et al. Synthesis and spectral properties of new boron dipyrromethene dyes［J］. Dyes Pigments, 2007,73(2):206-210．
【12】LU H G, XU B, DONG Y J, et al. Novel fluorescent pH sensors and a biological probe based on anthracene derivatives with aggregation-induced emission characteristics［J］. Langmuir, 2010,26(9):6838-6844．
【13】NIU C G, GUI X Q, ZENG G M, et al. Fluorescence ratiometric pH sensor prepared from covalently immobilized porphyrin and benzothioxanthene［J］. Anal Bioanal Chem, 2005,383(2):349-357．
【14】LI Z Z, NIU C G, ZENG G M, et al. A novel fluorescence ratiometric pH sensor based on covalently immobilized piperazinyl-1,8-napthalimide and benzothioxanthene［J］. Sens Actuators B, 2006,114(1):308-315．
【15】YE T X, DU Y Y, HE C Y, et al. Preparation of novel core-shell silica particles for pH sensing using ratiometric fluorescence approach［J］. Anal Methods,2012,4:1001-1004．
【16】LIN H J, SZMACINSKI H, LAKOWICZ J R. Lifetime-based pH sensors: indicators for acidic environments［J］. Anal Biochem, 1999,269(1):162-167．
【17】KOSCH U, KLIMANT I, WOLFBEIS O S. Long-lifetime based pH micro-optodes without oxygen interference［J］. Fresenius J Anal Chem. 1999,364(1/2):48-53．
【18】MA L Y, WANG H Y, XIE H, et al. A long lifetime chemical sensor: study on fluorescence property of fluorescein isothiocyanate and preparation of pH chemical sensor［J］. Spectrochim Acta Part A, 2004,60(8/9):1865-1872．
【19】MA L J, CAO W G, LIU J L, et al. A highly selective and sensitive fluorescence dual-responsive pH probe in water［J］. Sens Actuators B, 2012,169:243-247．
【20】GEORGIEV N I, ASIRI A M, QUSTI A H, et al. Design and synthesis of pH-selective fluorescence sensing PAMAM light-harvesting dendrons based on 1,8-naphthalimides［J］. Sens Actuators B, 2014,190:185-198．
【21】NGUYEN T H, VENUGOPALA T, CHEN S, et al. Fluorescence based fibre optic pH sensor for the pH 10-13 range suitable for corrosion monitoring in concrete structures［J］. Sens Actuators B, 2014,191:498-507．
【22】王炳帅,王丽,吴彤,等. 苯乙烯类菁染料pH探针的合成与活细胞成像［J］.高等学校化学学报, 2010,31(6):1148-1151．
【23】BINNEMANS K. Lanthanide-based luminescent hybrid materials［J］. Chem Rev, 2009,109(9):4283-4374．
【24】MIZUKAMI S, TONAI K, KANEKO M, et al. Lanthanide-based protease activity sensors for time-resolved fluorescence measurements［J］. J Am Chem Soc, 2008,130(44):14376-14377．
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