荧光素衍生物水杨醛荧光素腙的合成及对铜(Ⅱ)离子的检测

引用本文: 武鑫, 马骏, 南明, 双少敏, 董川. 荧光素衍生物水杨醛荧光素腙的合成及对铜(Ⅱ)离子的检测[J]. 应用化学, 2016, 33(3): 357-363. doi: 10.11944/j.issn.1000-0518.2016.03.150238 shu

Citation: WU Xin, MA Jun, NAN Ming, SHUANG Shaomin, DONG Chuan. Synthesis of a Fluorescein Derivative 5-Bromosalicylicaldehyde Fluorescein Hydrazone and the Detection for Copper(Ⅱ) Ion[J]. Chinese Journal of Applied Chemistry, 2016, 33(3): 357-363. doi: 10.11944/j.issn.1000-0518.2016.03.150238 shu

荧光素衍生物水杨醛荧光素腙的合成及对铜(Ⅱ)离子的检测

武鑫 ^a,b, ,
马骏 ^a, ,
南明 ^a, ,
双少敏 ^a, ,
董川 ^{a,
,}

a.
a. 山西大学环境科学研究所，化学化工学院太原 030006;
b.
b. 山西农业大学文理学院山西太谷 030801

通讯作者: 董川,教授;Tel:0351-7018246;Fax:0351-7011011;E-mail:dc@sxu.edu.cn;研究方向:环境分析化学

基金项目:
国家自然科学基金资助项目（21405099，21575084)

山西省归国人员留学基金资助

摘要: 以荧光素酰肼与5-溴水杨醛反应合成了一种新型荧光素衍生物5-溴水杨醛荧光素腙（BSFH），采用红外、核磁、质谱、元素分析等技术手段对其进行了表征。通过吸收光谱考察了在水溶液中BSFH对常见金属离子的选择性响应，发现BSFH在可见光区几乎无吸收，当加入常见金属离子时，吸收光谱上除了Cu²⁺之外的其它金属离子在496 nm处出现非常弱的吸收，而当Cu²⁺存在时，可以裸眼看到溶液颜色迅速从无色变为黄色，吸收光谱上在496 nm处出现了相对很强的吸收峰，并且随着Cu²⁺浓度的增加溶液的吸收强度不断增强，说明在水溶液中BSFH对Cu²⁺有很好的选择性。实验结果表明，该化合物与Cu²⁺的化学计量比为1∶1，Cu²⁺浓度线性范围为0.30～10 μmol/L，许多常见的金属离子不干扰Cu²⁺的测定，检测限为0.30 μmol/L，说明在水溶液中BSFH对铜离子具有很高的灵敏度。据此，BSFH可以简单、快速、灵敏地在水溶液中识别和检测低浓度的铜离子。

关键词:

English

Synthesis of a Fluorescein Derivative 5-Bromosalicylicaldehyde Fluorescein Hydrazone and the Detection for Copper(Ⅱ) Ion

WU Xin ^a,b, ,
MA Jun ^a, ,
NAN Ming ^a, ,
SHUANG Shaomin ^a, ,
DONG Chuan ^{a,
,}

a.
a. Institute of Environmental Science, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China;
b.
b. School of Arts and Sciences, Shanxi Agricultural University, Taigu, Shanxi 030801, China

Corresponding author: 董川,教授;Tel:0351-7018246;Fax:0351-7011011;E-mail:dc@sxu.edu.cn;研究方向:环境分析化学

Received Date: 09 July 2015
Fund Project:
国家自然科学基金资助项目（21405099，21575084)

山西省归国人员留学基金资助

Abstract: A novel fluorescein derivative, 5-bromosalicylicaldehyde fluorescein hydrazone(BSFH), has been synthesized by reacting fluorescein hydrazine with 5-bromosalicylicaldehyde and characterized by IR, NMR, MS, elemental analysis. The selectivity of BSFH to common metal ions in aqueous solution was investigated by absorption spectroscopy. BSFH has almost no absorption in visible region and very low absorption at 496 nm with addition of other metal ions except Cu²⁺. However, in the presence of Cu²⁺, a rapid color change of BSFH from colorless to yellow along with a very obvious absorption appears at 496 nm in the absorption spectrum. The absorbance of BSFH at 496 nm increases gradually with the increase of Cu²⁺. The selective binding of BSFH to Cu²⁺ over other metal ions is remarkably high in the aqueous solution. Experimental results indicate that the chemical stoichiometric ratio between BSFH and Cu²⁺ is 1:1, the linear range of detecting Cu²⁺ concentration is 0.30~10 μmol/L, common metal ions do not show any interference on the determination of Cu²⁺, the detection limit is 0.30 μmol/L, and BSFH is highly sensitive to Cu²⁺ in the aqueous solution. Therefore, BSFH can be utilized to detect Cu²⁺ at low concentration with simple, rapid and sensitive method.

Key words:

fluorescein derivative
/ bromosalicylicaldehyde fluorescein hydrazone
/ cupper(Ⅱ) ion
/ absorption spectrum
/ detection

1. [1] Egawa T,Koide Y,Hanaoka K,et al. Development of a Fluorescein Analogue, TokyoMagenta, as a Novel Scaffold for Fluorescence Probes in Red Region[J]. Chem Commun,2011,47:4162-4164.[1] Egawa T,Koide Y,Hanaoka K,et al. Development of a Fluorescein Analogue, TokyoMagenta, as a Novel Scaffold for Fluorescence Probes in Red Region[J]. Chem Commun,2011,47:4162-4164.
2. [2] Li T,Yang Z,Li Y,et al. A Novel Fluorescein Derivative as a Colorimetric Chemosensor for Detecting Copper(Ⅱ) Ion[J]. Dyes Pigm,2011,88(1):103-108.[2] Li T,Yang Z,Li Y,et al. A Novel Fluorescein Derivative as a Colorimetric Chemosensor for Detecting Copper(Ⅱ) Ion[J]. Dyes Pigm,2011,88(1):103-108.
3. [3] Huo F J,Yin C X,Yang Y T,et al. Ultraviolet-visible Light(UV-Vis)-reversible but Fluorescence-irreversible Chemosensor for Copper in Water and Its Application in Living Cells[J]. Anal Chem,2012,84(5):2219-2223.[3] Huo F J,Yin C X,Yang Y T,et al. Ultraviolet-visible Light(UV-Vis)-reversible but Fluorescence-irreversible Chemosensor for Copper in Water and Its Application in Living Cells[J]. Anal Chem,2012,84(5):2219-2223.
4. [4] Jin X,Hao L,Hu Y,et al. Two Novel Fluorescein-based Fluorescent Probes for Hypochlorite and Its Real Applications in Tap Water and Biological Imaging[J]. Sens Actuators,B,2013,186:56-60.[4] Jin X,Hao L,Hu Y,et al. Two Novel Fluorescein-based Fluorescent Probes for Hypochlorite and Its Real Applications in Tap Water and Biological Imaging[J]. Sens Actuators,B,2013,186:56-60.
5. [5] Zhang X,Zhang Y,Zhu Z. A Fluorescein Semicarbazide-based Fluorescent Probe for Highly Selective and Rapid Detection of Hypochlorite in Aqueous Solution[J]. Anal Methods,2012,4:4334.[5] Zhang X,Zhang Y,Zhu Z. A Fluorescein Semicarbazide-based Fluorescent Probe for Highly Selective and Rapid Detection of Hypochlorite in Aqueous Solution[J]. Anal Methods,2012,4:4334.
6. [6] Ma X,Liu C,Shan Q,et al. A Fluorescein-based Probe with High Selectivity and Sensitivity for Sulfite Detection in Aqueous Solution[J]. Sens Actuators,B,2013,188:1196-1200.[6] Ma X,Liu C,Shan Q,et al. A Fluorescein-based Probe with High Selectivity and Sensitivity for Sulfite Detection in Aqueous Solution[J]. Sens Actuators,B,2013,188:1196-1200.
7. [7] Yang X F,Wang L,Xu H,et al. A Fluorescein-based Fluorogenic and Chromogenic Chemodosimeter for the Sensitive Detection of Sulfide Anion in Aqueous Solution[J]. Anal Chim Acta,2009,631(1):91-95.[7] Yang X F,Wang L,Xu H,et al. A Fluorescein-based Fluorogenic and Chromogenic Chemodosimeter for the Sensitive Detection of Sulfide Anion in Aqueous Solution[J]. Anal Chim Acta,2009,631(1):91-95.
8. [8] Huo F J,Zhang J J,Yang Y T,et al. A Fluorescein-based Highly Specific Colorimetric and Fluorescent Probe for Hypochlorites in Aqueous Solution and Its Application in Tap Water[J]. Sens Actuators,B,2012,166/167:44-49.[8] Huo F J,Zhang J J,Yang Y T,et al. A Fluorescein-based Highly Specific Colorimetric and Fluorescent Probe for Hypochlorites in Aqueous Solution and Its Application in Tap Water[J]. Sens Actuators,B,2012,166/167:44-49.
9. [9] Yang X F,Li Y,Bai Q. A Highly Selective and Sensitive Fluorescein-based Chemodosimeter for Hg²⁺ Ions in Aqueous Media[J]. Anal Chim Acta,2007,584(1):95-100.[9] Yang X F,Li Y,Bai Q. A Highly Selective and Sensitive Fluorescein-based Chemodosimeter for Hg²⁺ Ions in Aqueous Media[J]. Anal Chim Acta,2007,584(1):95-100.
10. [10] Muthuraj B,Deshmukh R,Trivedi V,et al. Highly Selective Probe Detects Cu²⁺ and Endogenous NO Gas in Living Cell[J]. ACS Appl Mater Interfaces,2014,6(9):6562-6569.[10] Muthuraj B,Deshmukh R,Trivedi V,et al. Highly Selective Probe Detects Cu²⁺ and Endogenous NO Gas in Living Cell[J]. ACS Appl Mater Interfaces,2014,6(9):6562-6569.
11. [11] Kulchat S,Chaicham A,Ekgasit S,et al. Self-assembled Coordination Nanoparticles from Nucleotides and Lanthanide Ions with Doped-boronic Acid-fluorescein for Detection of Cyanide in the Presence of Cu in Water[J]. Talanta,2012,89:264-269.[11] Kulchat S,Chaicham A,Ekgasit S,et al. Self-assembled Coordination Nanoparticles from Nucleotides and Lanthanide Ions with Doped-boronic Acid-fluorescein for Detection of Cyanide in the Presence of Cu in Water[J]. Talanta,2012,89:264-269.
12. [12] Hyman L M,Stephenson C J,Dickens M G,et al. Toward the Development of Prochelators as Fluorescent Probes of Copper-mediated Oxidative Stress[J]. Dalton Trans,2010,39(2):568-576.[12] Hyman L M,Stephenson C J,Dickens M G,et al. Toward the Development of Prochelators as Fluorescent Probes of Copper-mediated Oxidative Stress[J]. Dalton Trans,2010,39(2):568-576.
13. [13] Chen X T,Li Z F,Xiang Y,et al. Salicylaldehyde Fluorescein Hydrazone:A Colorimetric Logic Chemosensor for pH and Cu(Ⅱ)[J]. Tetrahedron Lett,2008,49(32):4697-4700.[13] Chen X T,Li Z F,Xiang Y,et al. Salicylaldehyde Fluorescein Hydrazone:A Colorimetric Logic Chemosensor for pH and Cu(Ⅱ)[J]. Tetrahedron Lett,2008,49(32):4697-4700.
14. [14] Jiang L,Wang L,Guo M,et al.Fluorescence Turn-on of Easily Prepared Fluorescein Derivatives by Zinc Cation in Water and Living Cells[J]. Sens Actuators,B,2011,156(2):825-831.[14] Jiang L,Wang L,Guo M,et al.Fluorescence Turn-on of Easily Prepared Fluorescein Derivatives by Zinc Cation in Water and Living Cells[J]. Sens Actuators,B,2011,156(2):825-831.
15. [15] Zhang J,Zhang L,Wei Y,et al. A Selectively Fluorescein-based Colorimetric Probe for Detecting Copper(Ⅱ) Ion[J]. Spectrochim Acta,Part A,2014,122:731-736.[15] Zhang J,Zhang L,Wei Y,et al. A Selectively Fluorescein-based Colorimetric Probe for Detecting Copper(Ⅱ) Ion[J]. Spectrochim Acta,Part A,2014,122:731-736.
16. [16] Yang Y,Huo F,Yin C,et al.Combined Spectral Experiment and Theoretical Calculation to Study the Chemosensors of Copper and Their Applications in Anion Bioimaging[J]. Sens Actuators,B,2013,177:1189-1197.[16] Yang Y,Huo F,Yin C,et al.Combined Spectral Experiment and Theoretical Calculation to Study the Chemosensors of Copper and Their Applications in Anion Bioimaging[J]. Sens Actuators,B,2013,177:1189-1197.
17. [17] Que E L,Domaille D W ,Chang C J. Metals in Neurobiology:Probing Their Chemistry and Biology with Molecular Imaging[J]. Chem Rev,2008,108(5):1517-1549.[17] Que E L,Domaille D W ,Chang C J. Metals in Neurobiology:Probing Their Chemistry and Biology with Molecular Imaging[J]. Chem Rev,2008,108(5):1517-1549.
18. [18] YUE Kong,XIA Yan. Review on Study About Untidecay Treatment in Wood[J]. Wood Process Machin,2007,(6):50-53(in Chinese).岳孔,夏炎.木质材料防腐朽菌败坏研究综述[J]. 木材加工机械,2007,(6):50-53.[18] YUE Kong,XIA Yan. Review on Study About Untidecay Treatment in Wood[J]. Wood Process Machin,2007,(6):50-53(in Chinese).岳孔,夏炎.木质材料防腐朽菌败坏研究综述[J]. 木材加工机械,2007,(6):50-53.
19. [19] Qu L J,Yin C X,Huo F J,et al. A Pyridoxal-based Dual Chemosensor for Visual Detection of Copperion and Ratiometric Fluorescent Detection of Zinc Ion[J]. Sens Actuators,B,2014,191:158-164.[19] Qu L J,Yin C X,Huo F J,et al. A Pyridoxal-based Dual Chemosensor for Visual Detection of Copperion and Ratiometric Fluorescent Detection of Zinc Ion[J]. Sens Actuators,B,2014,191:158-164.
20. [20] YUAN Yuehua,TIAN Maozhong,FENG Feng,et al.Rhodamine-Based Fluorescent Probes for Cations[J]. Prog Chem,2010,22(10):1929-1939(in Chinese).袁跃华,田茂忠,冯峰,等. 罗丹明类阳离子荧光探针[J]. 化学进展,2010,22(10):1929-1939.[20] YUAN Yuehua,TIAN Maozhong,FENG Feng,et al.Rhodamine-Based Fluorescent Probes for Cations[J]. Prog Chem,2010,22(10):1929-1939(in Chinese).袁跃华,田茂忠,冯峰,等. 罗丹明类阳离子荧光探针[J]. 化学进展,2010,22(10):1929-1939.
21. [21] Wuhan University. Analytical Chemistry[M]. 5nd Ed. Beijing:China Higher Education Press,2007:11-13(in Chinese).武汉大学. 分析化学[M]. 第5版. 北京:高等教育出版社,2007:11-13.[21] Wuhan University. Analytical Chemistry[M]. 5nd Ed. Beijing:China Higher Education Press,2007:11-13(in Chinese).武汉大学. 分析化学[M]. 第5版. 北京:高等教育出版社,2007:11-13.
22. [22] Zhang L,Zhang X. A Selectively Fluorescein-based Colorimetric Probe for Detecting Copper(Ⅱ) Ion[J]. Spectrochim Acta,Part A,2014,133:54-59.[22] Zhang L,Zhang X. A Selectively Fluorescein-based Colorimetric Probe for Detecting Copper(Ⅱ) Ion[J]. Spectrochim Acta,Part A,2014,133:54-59.

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沈阳化工大学材料科学与工程学院沈阳 110142

荧光素衍生物水杨醛荧光素腙的合成及对铜(Ⅱ)离子的检测

通讯作者: 董川,教授;Tel:0351-7018246;Fax:0351-7011011;E-mail:dc@sxu.edu.cn;研究方向:环境分析化学

English

Synthesis of a Fluorescein Derivative 5-Bromosalicylicaldehyde Fluorescein Hydrazone and the Detection for Copper(Ⅱ) Ion

Corresponding author: 董川,教授;Tel:0351-7018246;Fax:0351-7011011;E-mail:dc@sxu.edu.cn;研究方向:环境分析化学

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

荧光素衍生物水杨醛荧光素腙的合成及对铜(Ⅱ)离子的检测

通讯作者: 董川,教授;Tel:0351-7018246;Fax:0351-7011011;E-mail:dc@sxu.edu.cn;研究方向:环境分析化学

English

Synthesis of a Fluorescein Derivative 5-Bromosalicylicaldehyde Fluorescein Hydrazone and the Detection for Copper(Ⅱ) Ion

Corresponding author: 董川,教授;Tel:0351-7018246;Fax:0351-7011011;E-mail:dc@sxu.edu.cn;研究方向:环境分析化学

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

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