基于偶氮苯酚类的比色传感器识别阴离子

doi:10.11944/j.issn.1000-0518.2019.12.190084

摘要/Abstract

摘要：

设计合成了3个含酚羟基数量不同的偶氮苯化合物S1、S2和S3作为传感分子,研究S1、S2和S3对阴离子的比色识别,并探讨传感分子的结构与识别阴离子能力之间的联系。结果表明:传感分子S1、S2和S3对F^-、H₂PO4-和AcO^-比色识别灵敏度高。在CH₃CN中S1、S2和S3的F^-检测限达到1.25×10^-73.62×10^-7 mol/L,S2、S3对H₂PO4-和AcO^-的检测限也达同一数量级。 S1、S2和S3对阴离子F^-、H₂PO4-和AcO^-比色识别能力取决于阴离子的空间构型、电荷密度和碱性共同作用的结果。 ¹H NMR滴定结果表明,识别机理是S1、S2和S3的酚羟基与阴离子形成了分子间的氢键。

关键词: 偶氮苯, 比色识别, 阴离子, 化学传感器, 酚羟基

Abstract:

Three colorimetric sensors S1, S2 and S3 based on azobenzene containing different numbers of active phenolic hydroxyl groups have been designed and synthesized. The sensors in CH₃CN exhibit high sensitivity toward F^-, H₂PO4- and AcO^-. The detection limit of S1, S2 and S3 was determined to be 1.25×10^-73.62×10^-7 mol/L for F^-. The sensitivity of sensors S1, S2 and S3 for anions were affected by the configuration, charge density and basicity of anions. ¹H NMR titration has been performed to study reaction mechanism, which was considered to be direct consequence of hydrogen-bonding between the phenolic group of sensor and anion.

Key words: azobenzene, colorimetric recognition, anion, chemosensors, phenolic hydroxyl group

林声声, 何清运, 周嘉敏, 招铭朋, 冯宗财, 余彪, 宋秀美. 基于偶氮苯酚类的比色传感器识别阴离子[J]. 应用化学, 2019, 36(12): 1447-1455.

LIN Shengsheng, HE Qingyun, ZHOU Jiamin, ZHAO Mingpeng, FENG Zongcai, YU Biao, SONG Xiumei. Colorimetric Sensors for Anion Recognition Based on Benzeneazophenol[J]. Chinese Journal of Applied Chemistry, 2019, 36(12): 1447-1455.

参考文献

[1]	Gale P A.Anion Receptor Chemistry[J]. Chem Comun,2011,47(1):82-86.
[2]	Sun H,Dong X,Liu S,et al. Excellent BODIPY Dye Containing Dimesitylboryl Groups as Pet Based Fluorescent Probes for Fluoride[J]. J Phys Chem C,2011,115(40):19947-19954.
[3]	Li S,Zhang C,Huang S,et al. Highly Selective Colorimetric and Fluorescent Sensors for the Fluoride Anion Based on Imidazo[4,5-f]-1,10-phenanthroline Metal-Complexes[J]. RCS Adv,2012,2:4215-4219.
[4]	Yong X,Su M,Wan W,et al. 2-Thiohydantoin Containing OH and NH Recognition Subunits:A Fluoride Ion Selective Colorimetric Sensor[J]. New J Chem,2013,37(5):1591-1594.
[5]	Li X G,Zhang D, Li J.Emission “Off-On” Effect from Curopium Complexes Triggered by AcO Anion:Synthesis, Characterization and Sensing Performance[J]. Spectrochim Acta,Part A,2014,127:1-9.
[6]	Khan S S,Riaz M.Determination of UV Active Inorganic Anions in Potable and High Salinity Water by Ion Pair Reversed Phase Liquid Chromatography[J]. Talanta,2014,122:209-213.
[7]	Hu B B,Lu P,Wang Y G.A Highly Selective and Real-Time Ratiometric Fluorescent Chemosensor for Fluoride Anion Detection under Either Neutral or Basic Condition[J]. Sens Actuators,B,2014,195:320-323.
[8]	Guha S,Saha S.Fluoride Ion Sensing by an Anion-π Interaction[J]. J Am Chem Soc,2010,132(50):17674-17677.
[9]	Xu W,Liu S,Sun H,et al. FRET-Based Probe for Fluoride Based on a Phosphorescent Rridium(Ⅲ) Complex Containing Triarylboron Groups[J]. J Mater Chem,2011,21(21):7572-7581.
[10]	Baker J L,Sudarsan N,Weinberg Z,et al. Widespread Genetic Switches and Toxicity Resistance Proteins for Fluoride[J]. Science,2012,335(6065):233-235.
[11]	Aboubakr H,Brisset H,Siri O,et al. Highly Specific and Reversible Fluoride Sensor Based on an Organic Semiconductor[J]. Anal Chem,2013,85(20):9968-9974.
[12]	Iniya M,Jeyanthi D,Krishnaveni K,et al. A Bifunctional Chromogenic and Fluorogenic Probe for F- and Al3+ Based on Azo-Benzimidazole Conjugate[J]. J Lumin,2015,157:383-389.
[13]	Padhan S K,Podh M B,Sahu P K,et al. Optical Discrimination of Fluoride and Cyanide Ions by Coumarin-Salicylidene Based Chromofluorescent Probes in Organic and Aqueous Medium[J]. Sens Actuators,B,2018,255:1376-1390.
[14]	Li Z Y,Su H K,Tong H X,et al. Calix[4]arene Containing Thiourea and Coumarin Functionality as Highly Selective Fluorescent and Colorimetric Chemosensor for Fluoride Ion[J]. Spectrochim Acta,Part A,2018,200:307-312.
[15]	Lin Q,Yang Q P,Sun B,et al. A Highly Selective and Sensitive Fluorescence Turn-On Fluoride Ion Sensor[J]. RSC Adv,2015,5:11786-11790.
[16]	Kumar G G V,Kesavan M P,Sivaraman G,et al. Colorimetric and NIR Fluorescence Receptors for F- Ion Detection in Aqueous Condition and Its Live Cell Imaging[J]. Sens Actuators,B,2018,255:3194-3206.
[17]	Wang R,Ma Y S,Zhao J F,et al. Novel Hydroxyl-Substituted Perylene-3,4,9,10-Tetracarboxylic Acid Diimides for Selective Recognition of Fluoride[J]. Sens Actuators,B,2018,260:719-726.
[18]	Ashokkumar P,Ramakrishnan V T,Ramamurthy P.Fluorescence Spectroscopic Evidence for Hydrogen Bonding and Deprotonation Equilibrium Between Fluoride and a Thiourea Derivative[J]. Chem Eur J,2010,44(16):13271-13277.
[19]	Mahapatra A K,Karmakar P,Roy J,et al. Colorimetric and Ratiometric Fluorescent Chemosensor for Fluoride Ions Based on Phenanthroimidazole(PI):Spectroscopic, NMR and Density Functional Studies[J]. RSC Adv,2015,47(5):37935-37942.
[20]	Wu Y C,You J Y,Jiang K,et al. Colorimetric and Ratiometric Fluorescent Sensor for F- Based on Benzimidazole-Naphthalene Conjugate:Reversible and Reusable Study & Design of Logic Gate Function[J]. Dyes Pigm,2017,140:47-55.
[21]	Wu Y C,Huo J P,Cao L,et al. Design and Application of Tri-Benzimidazolyl Star-Shape Molecules as Fluorescent Chemosensors for the Fast-Response Detection of Fluoride Ion[J]. Sens Actuators,B,2016,237:865-875.
[22]	Singh H,Bhargava G,Kumar S,et al. Microstructural (Self-assembly) and Optical Based Discrimination of Hg2+, CN- and Hg(CN)2 Ion-Pair; Hg2+ Promoted-ESIPT Assisted Guanylation of Thiourea[J]. Sens Actuators,B,2018,272:43-52.
[23]	Wang S X,Meng X M,Zhu M Z.A Naked-eye Rhodamine-Based Fluorescent Probe for Fe(Ⅲ) and Its Application in Living Cells[J]. Tetrahedron Lett,2011,52(22):2840-2843.
[24]	Bera R K,Raj C R.Naked Eye Sensing of Melamine Using Rationally Tailored Gold Nanoparticles:Hydrogen-Bonding and Charge-Transfer Recognition[J]. Analyst,2011,136(8):1644-1648.
[25]	Bao Y,Liu B,Wang H,et al. A “Naked Eye” and Ratiometric Fluorescent Chemosensor for Rapid Detection of F- Based on Combination of Desilylation Reaction and Excited-State Proton Transfer[J]. Chem Commun,2011,47(13):3957-3959.
[26]	Zhou X,Yan W,Zhao T,et al. Rhodamine Based Derivative and Its Zinc Complex:Synthesis and Recognition Behavior Toward Hg(Ⅱ)[J]. Tetrahedron,2013,69(46):9535-9539.
[27]	Kim K B,Kim H,Song E J,et al. A Cap-Type Schiff Base Acting as a Fluorescence Sensor for Zinc(Ⅱ) and a Colorimetric Sensor for Iron(Ⅱ), Copper(Ⅱ), and Zinc(Ⅱ) in Aqueous Media[J]. Dalton Trans,2013,42(47):16569-16577.
[28]	Shyamaprosad G,Maity S,Das A K,et al. Remarkable ESIPT Induced NIR Emission by a Selective Colorimetric Dibenzimidazolo Diimine Sensor for Acetate[J]. Tetrahedron Lett,2013,54(38):5232-5235.
[29]	Gong Y N,Lu T B.Fast Detection of Oxygen by the Naked Eye Using a Stable Metal-Organic Framework Containing Methyl Viologen Cations[J]. Chem Commun,2013,49(70):7711-7713.
[30]	Zhu J,Yang X,Zhang L,et al. A Visible Multi-Digit DNA Keypad Lock Based on Split G-Quadruplex DNAzyme and Silver Microspheres[J]. Chem Commun,2013,49(48):5459-5461.
[31]	Pandurangan K,Kitchen J A,Gunnlaugsson T.Colorimetric Naked-eye' Sensing of Anions Using a Thiosemicarbazide Receptor:A Case Study of Recognition Through Hydrogen Bonding Versus Deprotonation[J]. Tetrahedron Lett,2013,54(22):2770-2775.
[32]	Vinithra G,Suganya S,Velmathi S.Naked Eye Sensing of Anions Using Thiourea Based Chemosensors with Real Time Application[J]. Tetrahedron Lett,2013,54(41):5612-5615.
[33]	Batista R M F,Oliveira E,Costa S P G,et al. Cyanide and Fluoride Colorimetric Sensing by Novel Imidazo-Anthraquinones Functionalized with Indole and Carbazole[J]. Supramol Chem,2014,26(2):71-80.
[34]	Ding L,Wu M J,Li Y R,et al. New Fluoro- and Chromogenic Chemosensors for the Dual-channel Detection of Hg2+ and F-[J]. Tetrahedron Lett,2014,55(34):4711-4715.
[35]	Satheshkumar A,El-Mossalamy E H,Manivannan R,et al. Anion Induced Azo-Hydrazone Tautomerism for the Selective Colorimetric Sensing of Fluoride Ion[J]. Spectrochim Acta,Part A,2014,128:798-805.
[36]	Parthiban C,Elango K P.Amino-Naphthoquinone and Its Metal Chelates for Selective Sensing of Fluoride Ions[J]. Sens Actuators,B,2015,215:544-552.
[37]	Liu X M,Li Y P,Zhang Y H,et al. Ratiometric Fluorescence Detection of Fluoride Ion by Indole-Based Receptor[J]. Talanta,2015,131:597-602.
[38]	Yang X F,Zheng L Y,Xie L J,et al. Colorimetric and On-Off Fluorescent Chemosensor for Fluoride Ion Based on Diketopyrrolopyrrole[J]. Sens Actuators B,2015,207:9-24.
[39]	Choi Y W,Lee J J,You G R,et al. Chromogenic Naked-Eye Detection of Copper Ion and Fluoride[J]. RSC Adv,2015,5(105):86463-86472.
[40]	Yeung M C L,Yam V W W. Luminescent Cation Sensors:From Host-Guest Chemistry, Supramolecular Chemistry to Reaction-Based Mechanisms[J]. Chem Soc Rev,2015,44(13):4192-4202.
[41]	Lee H,Lee S S.Thiaoxaaza-Macrocyclic Chromoionphores as Mercury(Ⅱ) Sensors:Synthesis and Color Modulation[J]. Org Lett,2009,11(6):1393-1396.
[42]	Suganya S,Velmathi S.Simple Azo-Based Salicylaldimine as Colorimetric and Fluorescent Probe for Detecting Anions in Semi-aqueous Medium[J]. J Mol Recognit,2013,26(6):259-267.
[43]	Hamid K,Khatereh R.Naked-Eye Detection of Inorganic Fluoride in Aqueous Media Using a New Azo-Azomethine Colorimetric Receptor Enhanced by Electron Withdrawing Groups[J]. RSC Adv,2014,4(2):1032-1038.
[44]	Udhayakumari D,Velmathi S.Azo Linked Thiourea Based Effective Dual Sensor and Its Real Samples Application in Aqueous Medium[J]. Sens Actuators,B,2015,209:462-469.
[45]	Simon D,Kannapiran R K.A Symmetrical Luminol Based Azo Derivative for Trimodal Ratiometric Hg2+ Sensing and Its Application to Bioimaging in Living Cells[J]. J Photochem Photobiol A,2018,364:773-786.
[46]	Lee K H,Lee H Y,Lee D H,et al. Fluoride-Selective Chromogenic Sensors Based on Azophenol[J]. Terahedron Lett,2001,42(32):5447-5449.
[47]	SONG Xiumei,FENG Zongcai,WANG Zhaoyang,et al. Synthesis, Characterization and Photochromic Properties of D-π-A Azobenzene Derivatives[J]. J Funct Mater,2015,46(9):09114-09119(in Chinese). 宋秀美,冯宗财,汪朝阳,等. D-π-A型偶氮苯衍生物合成、表征及其光致变色性能一种超支化偶氮聚氨酯的合成及其光致变色性能[J]. 功能材料,2015,46(9):09114-09119.
[48]	SONG Xiumei,FENG Zongcai,WANG Yuechuan,et al. Synthesis and Photoisomerization of Film Containing 2,4,2'-Trihydroxyazobenzene[J]. Polym Mater Sci Eng,2014,30(6):38-41(in Chinese). 宋秀美,冯宗财,王跃川,等. 2,4,2'-三羟基偶氮苯的合成及掺杂薄膜的光致异构性能[J]. 高分子材料科学与工程,2014,30(6):38-41.
[49]	Niu H,Shu Q H,Jin S H,et al. A Simple Ratiometric and Colorimetric Chemosensor for the Selective Detection of Fluoride in DMSO Buffered Solution[J]. Spectrochim Acta,Part A,2016,153:194-198.
[50]	Sarkar A,Bhattacharyya S,Mukherjee A.Colorimetric Detection of Fluoride Ions by Anthraimidazoledione Based Sensors in the Presence of Cu(Ⅱ) Ions[J]. Dalton Trans,2016,45:1166-1175.
[51]	Gupta N,Singhal D,Singh A K.Highly Selective Colorimetric and Reversible Fluorometric Turn-Off Sensors Based on the Pyrimidine Derivative:Mimicking Logic Gate Operation and Potential Applications[J]. New J Chem,2016,40:641-650.