苯并噻唑基修饰的开链Cu~(2+)比色探针的合成及性能
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摘要
以N-苯基二乙醇胺和2-巯基苯并噻唑为原料通过亲核取代反应合成了一种新型的苯并噻唑基修饰的开链冠醚类化合物1,并用核磁共振氢谱,核磁共振碳谱及元素分析方法对合成产物进行了表征。利用紫外光谱仪考察了化合物1与多种金属离子(Mn~(2+)、Co~(2+)、Cu~(2+)、Zn~(2+)、Ni~(2+)、Fe~(3+)、 Hg~(2+)、Cr~(3+)、Al~(3+))在乙腈溶液中的光谱变化,并探究了化合物1处理过的滤纸条在水溶液中对金属离子的识别效果,通过核磁共振氢谱讨论了化合物1与金属离子形成配合物的作用机理。实验发现,化合物1的乙腈溶液中添加Cu~(2+)后溶液颜色变为棕色,明显区别于添加其他离子;在水溶液中,特制的滤纸条遇到Cu~(2+)会呈现黄色,而遇其他离子均无颜色变化。结果表明,化合物1仅对Cu~(2+)具有选择性,且能通过裸眼进行识别,是一种高效、简便的Cu~(2+)探针。
A novel heteroatomic alkyl chain compound 1 with bis-benzothiazole groups was synthesized facilely by nucleophilic substitution reaction using N-phenyldiethanolamine and 2-mercapto benzothiazole as raw materials, and its structure was characterized by1 H NMR,13 C NMR and elemental analysis. The spectral changes of compound 1 with many metal cations(Mn~(2+)、Co~(2+)、Cu~(2+)、Zn~(2+)、Ni~(2+)、Fe~(3+)、 Hg~(2+)、Cr~(3+)、Al~(3+)) had been investigated by the UV-vis spectrophotometry, and the recognition performance of filter papers treated by compound 1 with many metal cations in aqueous solution was explored, finally the mechanism of forming complexes with metal cations was discussed by1 H NMR. It was found that the color of solution of compound 1 in acetonitrile was changed to brown after adding Cu~(2+),which was obviously different from adding other cations; the special filter paper will become yellow when it encounters Cu~(2+)in aqueous solution, and no color change was observed in case of other cations. The results showed that compound 1 only exhibited the selective recognition to Cu~(2+)and it could be clearly detected by our naked eyes. In a word, compound 1 is a highly efficient and simple probe for Cu~(2+).
A novel heteroatomic alkyl chain compound 1 with bis-benzothiazole groups was synthesized facilely by nucleophilic substitution reaction using N-phenyldiethanolamine and 2-mercapto benzothiazole as raw materials, and its structure was characterized by1 H NMR,13 C NMR and elemental analysis. The spectral changes of compound 1 with many metal cations(Mn~(2+)、Co~(2+)、Cu~(2+)、Zn~(2+)、Ni~(2+)、Fe~(3+)、 Hg~(2+)、Cr~(3+)、Al~(3+)) had been investigated by the UV-vis spectrophotometry, and the recognition performance of filter papers treated by compound 1 with many metal cations in aqueous solution was explored, finally the mechanism of forming complexes with metal cations was discussed by1 H NMR. It was found that the color of solution of compound 1 in acetonitrile was changed to brown after adding Cu~(2+),which was obviously different from adding other cations; the special filter paper will become yellow when it encounters Cu~(2+)in aqueous solution, and no color change was observed in case of other cations. The results showed that compound 1 only exhibited the selective recognition to Cu~(2+)and it could be clearly detected by our naked eyes. In a word, compound 1 is a highly efficient and simple probe for Cu~(2+).
引文
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[2] MUMMIDIVARAPU V V, BANDARU S, YARRAMALA D S, et al.Binding and ratiometric dual ion recognition of Zn2+and Cu2+by 1,3,5-tris-amidoquinoline conjugate of calix[6]arene by spectroscopy and its supramolecular features by microscopy[J]. Analytical Chemistry, 2015,87(9):4988-95.
[3] SCHEIBER I F, MERCER J F, DRINGEN R. Metabolism and functions of copper in brain[J]. Progress in Neurobiology, 2014, 116(5):33-57.
[4] DAVIES K M, MERCER J F, CHEN N, et al. Copper dyshomoeostasis in Parkinson's disease:implications for pathogenesis and indications for novel therapeutics[J]. Clinical Science, 2016, 130(8):565.
[5] HONG G L, KIM K B, PARK G J, et al. An anthracene-based fluorescent sensor for sequential detection of zinc and copper ions[J].Inorganic Chemistry Communications, 2014, 39:61-65.
[6] AWUAL M R, YAITA T, OKAMOTO Y. A novel ligand based dual conjugate adsorbent for cobalt(Ⅱ)and copper(Ⅱ)ions capturing from water[J]. Sensors&Actuators B:Chemical, 2014, 203:71-80.
[7] KELLY M. Mining and the freshwater environment[M]//Mining and the Freshwater Environment. Amsterdam:Elsevier Applied Science,1988.
[8] COTRUVO J A, ARON A T, RAMOSTORRES K M, et al. Synthetic fluorescent probes for studying copper in biological systems[J].Chemical Society Reviews, 2015, 44(13):4400-4414.
[9] WANG Z, VON D B A, KABADI P K, et al. Biological and environmental transformations of copper-based nanomaterials[J]. ACS Nano, 2013, 7(10):8715.
[10] YUAN X, LUO Z, YU Y, et al. Luminescent noble metal nanoclusters as an emerging optical probe for sensor development[J]. Chemistry:An Asian Journal, 2013, 8(5):858-871.
[11] QIAO Y, ZHANG Y, ZHANG C, et al. Water-soluble gold nanoclusters-based fluorescence probe for highly selective and sensitive detection of Hg2+[J]. Sensors and Actuators B:Chemical,2016, 224:458-464.
[12] SHE M, ZHENG Y, HAO L, et al. A novel approach to study the structure-property relationships and applications in living systems of modular Cu2+fluorescent probes[J]. Scientific Reports, 2016, 6:28972.
[13] TIAN J, LIU Q, ASIRI A M, et al. Ultrathin graphitic carbon nitride nanosheet:a highly efficient fluorosensor for rapid, ultrasensitive detection of Cu2+[J]. Analytical Chemistry, 2013, 85(11):5595-5599.
[14] DONG Y, WANG R, LI G, et al. Polyamine-functionalized carbon quantum dots as fluorescent probes for selective and sensitive detection of copper ions[J]. Analytical Chemistry, 2012, 84(14):6220-6224.
[15] WANG H, ZHOU G, CHEN X. iminofluorescein-Cu2?ensemble probe for selective detection of thiols[J]. Sensors&Actuators B:Chemical,2013, 176(1):698-703.
[16] NIU L Y, GUAN Y S, CHEN Y Z, et al. A turn-on fluorescent sensor for the discrimination of cystein from homocystein and glutathione[J].Chemical Communications, 2013, 49(13):1294-1296.
[17]林奇,刘昕,陈佩,等.氰根离子比色、荧光传感器研究新进展[J].化学进展, 2013, 25(12):2131-2146.LIN Qi, LIU Xin, CHEN Pei, et al. Colorimetric and fluorescent cyanide anion sensors[J]. Progress in Chemistry, 2013, 25(12):2131-2146.
[18]张鹏,张有明,林奇,等.金属离子响应型金属离子响应型荧光传感分子的设计原理及研究进展及研究进展[J].有机化学, 2014, 37(7):1300-1321.ZHANG Peng, ZHANG Youming, LIN Qi, et al. Principle and the research progress of fluorescent chemosensors for cations recognition[J]. Chinese Journal of Organic Chemistry, 2014, 37(7):1300-1321.
[19] ROUBINET B, RENARD P Y, ROMIEU A. New insights into the water-solubilization of thiol-sensitive fluorogenic probes based on long-wavelength 7-hydroxycoumarin scaffolds[J]. Dyes&Pigments,2014, 110(6):270-284.
[20] ALI F, A H A, TAVE N, et al. A fluorescent probe for specific detection of cysteine in the lipid dense region of cells[J]. Chemical Communications, 2015, 51(95):16932-16935.
[21] TANG L, LI S, HAN F, et al. SERS-active Au@Ag nanorod dimers for ultrasensitive dopamine detection[J]. Biosensors&Bioelectronics,2015, 71:7-12.
[22] LIU X, LIN Q, WEI T B, et al. A highly selective colorimetric chemosensor for detection of nickel ions in aqueous solution[J]. New Journal of Chemistry, 2014, 38(4):1418-1423.
[23]林奇,陈佩,刘娟,等.汞离子荧光、比色传感器[J].化学进展, 2013,25(7):1177-1186.LIN Qi, CHEN Pei, LIU Juan, et al. Colorimetric and fluorescent chemosensors for Hg2+ions[J]. Progress in Chemistry, 2013, 25(7):1177-1186.