基于Au3+和I–构建的单-(6-二乙烯三胺-6-去氧)-β-环糊精超分子荧光开关

doi:10.6023/cjoc202111024

有机化学 ›› 2022, Vol. 42 ›› Issue (5): 1474-1482.DOI: 10.6023/cjoc202111024 上一篇下一篇

研究论文

基于Au³⁺和I^–构建的单-(6-二乙烯三胺-6-去氧)-β-环糊精超分子荧光开关

鲁佳佳, 杨俊丽, 古捷, 杨举, 高振杰苏丽娇, 陶欣, 袁明伟^*(), 杨丽娟^*(), Lijuan Yang^*

云南民族大学化学与环境学院云南省高校智能超分子化学重点实验室生物基材料绿色制备技术国家地合工程中心昆明 650500

收稿日期:2021-11-15 修回日期:2022-01-17 发布日期:2022-01-27
通讯作者: 袁明伟, 杨丽娟, Lijuan Yang
基金资助:
国家自然科学基金(21762051); 云南省高校有机功能分子及材料科技创新团队和云南省教育厅科学研究基金资助项目

Mono-(6-diethylenetriamine-6-deoxy)-β-cyclodextrin Supramolecular Fluorescent Switch Constructed Based on Au³⁺ and I^–

Jiajia Lu, Junli Yang, Jie Gu, Ju Yang, Zhenjie Gao, Lijiao Su, Xin Tao(), Mingwei Yuan(), Lijuan Yang

Key Laboratory of Intelligent Supramolecular Chemistry at the University of Yunnan Province, National and Local Joint Engineering Research Center for Green Preparation Technology of Biobased Materials, School of Chemistry & Environment, Yunnan Minzu University, Kunming 650500

Received:2021-11-15 Revised:2022-01-17 Published:2022-01-27
Contact: Xin Tao, Mingwei Yuan, Lijuan Yang
Supported by:
National Natural Science Foundation of China(21762051); Program for Innovative Research Team (in Science and Technology) in University of Yunnan Province and Yunnan Provincial Department of Education Science Research Fund

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摘要/Abstract

选用绿色高效的方法合成了具有较好水溶性的单-(6-二乙烯三胺-6-去氧)-β-环糊精(3N-β-CD), 通过核磁共振氢谱(¹H NMR)和高分辨质谱(HRMS)对其结构进行表征. 用合成的3N-β-CD作为荧光探针对水溶液中的27种离子进行检测, 发现Au³⁺和I^–能使3N-β-CD的荧光猝灭. 进一步通过荧光滴定、Job曲线、核磁共振、红外光谱、离子干扰、时间响应对3N-β-CD检测Au³⁺和I^–的性能进行了研究. 结果表明, Au³⁺的最低检测限为2.73×10^–6 mol/L, 与3N-β-CD络合的化学计量比为1∶1; I^–的最低检测限为1.44×10^–6 mol/L, 与3N-β-CD络合的化学计量比为2∶1; 表明该探针可以灵敏地检测Au³⁺和I^–. 此外, 当I^–加入3N-β-CD与Au³⁺的混合溶液中, 3N-β-CD的荧光强度会逐渐恢复; 有趣的是, 当Au³⁺加入3N-β-CD与I^–的混合溶液中, 3N-β-CD的荧光强度也会逐渐恢复. 表明Au³⁺与I^–可作为荧光“开-关”来控制3N-β-CD的荧光发光行为, 从而使Au³⁺和I^–实现互相检测. 并在此基础上设计了控制3N-β-CD荧光开-关的逻辑门. 该研究为3N-β-CD作为荧光“开-关”传感器的研究与应用提供了新的实验思路.

关键词: 单-(6-二乙烯三胺-6-去氧)-β-环糊精, 金离子, 碘离子, 荧光开-关, 逻辑门

Mono-(6-diethylenetriamine-6-deoxy)-β-cyclodextrin (3N-β-CD) with the good water solubility was synthesized by a green and efficient method, and its structure was characterized by ¹H NMR and HRMS. 3N-β-CD was used as a fluorescent probe to detect 27 kinds of ions in aqueous solution. The results showed that the fluorescence of 3N-β-CD was quenched by Au³⁺ and I^–. The performance of 3N-β-CD for detecting Au³⁺ and I^– was further explored by fluorescence titration, Job curve, nuclear magnetic resonance, infrared spectroscopy, ion interference and time response. The results diplayed that the minimum detection limit of 3N-β-CD for Au³⁺ was 2.73×10^–6 mol/L and the binding stoichiometry ratios of 3N-β-CD with Au³⁺ was 1∶1, while the minimum detection limit of 3N-β-CD for I^– was 1.44×10^–6 mol/L and the binding stoichiometry ratios of 3N-β-CD with I^– was 2∶1. In addition, the fluorescence intensity of 3N-β-CD gradually recovered when I^– was added into the mixed solution of 3N-β-CD and Au³⁺. Interestingly, the fluorescence intensity of 3N-β-CD also gradually recovered when Au³⁺ was added into the mixed solution of 3N-β-CD and I^–. The results exhibited that Au³⁺ and I^– could be used as fluorescence “on-off-on” to control the fluorescence behavior of 3N-β-CD, and thus enabled Au³⁺ and I^– to detect each other. On this basis, the logic gate controlling 3N-β-CD fluorescence switch was designed. This work provides a new apporach for the research and application of 3N-β-CD as a fluorescence “on-off-on” sensor.

Key words: mono-6-diethylenetriamine-β-cyclodextrin, gold ion, iodine ion, fluorescent switch, logic gate

引用此文

鲁佳佳, 杨俊丽, 古捷, 杨举, 高振杰苏丽娇, 陶欣, 袁明伟, 杨丽娟, Lijuan Yang. 基于Au³⁺和I^–构建的单-(6-二乙烯三胺-6-去氧)-β-环糊精超分子荧光开关[J]. 有机化学, 2022, 42(5): 1474-1482.

Jiajia Lu, Junli Yang, Jie Gu, Ju Yang, Zhenjie Gao, Lijiao Su, Xin Tao, Mingwei Yuan, Lijuan Yang. Mono-(6-diethylenetriamine-6-deoxy)-β-cyclodextrin Supramolecular Fluorescent Switch Constructed Based on Au³⁺ and I^–[J]. Chinese Journal of Organic Chemistry, 2022, 42(5): 1474-1482.

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图/表 13

图1. 3N-β-CD结构示意图

Figure 1. Schematic diagram of 3N-β-CD structure

图2. 单-(6-二乙烯三胺-6-去氧)-β-环糊精与Au3+、I–构建的超分子荧光传感示意图

Figure 2. Schematic diagram of supramolecular fluorescence sensing constructed by mono-(6-diethylenetriamine-6-deoxy)-β-cyclodextrin and Au3+, I–

图3. 探针3N-β-CD与阳离子和阴离子的荧光光谱图

Figure 3. Fluorescence spectra of probe 3N-β-CD with cations and anions

图4. (A) Au3+浓度对3N-β-CD的荧光强度影响光谱图; (B) Au3+浓度与3N-β-CD的荧光强度线性拟合曲线图; (C) I–浓度对3N-β-CD的荧光强度影响光谱图; (D) I–浓度与3N-β-CD的荧光强度线性拟合曲线图

Figure 4. (A) Spectra of the effect of Au3+ concentration on fluorescence intensity of 3N-β-CD; (B) Linear fitting curve of fluorescence intensity between Au3+concentration and 3N-β-CD; (C) Spectra of the effect of I– concentration on the fluorescence intensity of 3N-β- CD; (D) Linear fitting curve of fluorescence intensity between I– concentration and 3N-β-CD

图5. (A) 3N-β-CD与Au3+和I–的Job曲线; (B) 3N-β-CD与Au3+和I–的结合模式图

Figure 5. (A) Job curve of 3N-β-CD and Au3+ and I–; (b) The binding mode of 3N-β-CD with Au3+ and I–

图6. 3N-β-CD检测Au3+和I–的时间响应

Figure 6. Time response of Au3+ and I– detected by 3N-β-CD

图7. (A) 26种离子对3N-β-CD检测Au3+的干扰图; (B) 26种离子对3N-β-CD检测I–的干扰图

Figure 7. (A) Interference pattern of 26 ions on 3N-β-CD detection of Au3+; (B) Interference pattern of 26 ions on 3N-β-CD detection of I–

图8. (A) I–浓度对3N-β-CD与Au3+混合水溶液的荧光强度影响光谱图; (B) Au3+浓度与3N-β-CD与I–混合水溶液的荧光强度影响光谱图

Figure 8. (A) Effect of I– concentration on the fluorescence intensity of 3N-β-CD and Au3+aqueous solution; (B) Fluorescence intensity of Au3+ concentration and 3N-β-CD and I– mixed aqueous solution affected the spectra

图9. 3N-β-CD与Au3+、I–的核磁共振氢谱

Figure 9. 1H-NMR spectra of 3N-β-CD and Au3+、I– (a) 3N-β-CD+I– (1.5×10–2 mol•L–1)+Au3+ (3.0×10–2 mol•L–1); (b) 3N-β-CD+I– (1.5×10–2 mol•L–1); (c) 3N-β-CD (1.5×10–2 mol•L–1); (d) 3N-β-CD+Au3+(3.0×10–2 mol•L–1); (e) 3N-β-CD+Au3+(3.0×10–2 mol•L–1)+I– (3.0×10–2 mol•L–1)

图10. 3N-β-CD, 3N-β-CD与Au3+混合, 3N-β-CD与I–混合的红外光谱图

Figure 10. IR spectra of 3N-β-CD, 3N-β-CD mixed with Au3+, 3N-β-CD mixed with I–

图11. IMPLICATION的逻辑电路图

Figure 11. Logical circuit diagram of IMPLICATION

Input	Output Fluorescence single
Au³⁺	I^–
0	0	1
1	0	0
0	1	0
1	1	1

表1. IMPLICATION逻辑门的真值表

Table 1. Truth table for the IMPLICATION logic gate

图12. 逻辑门中的荧光响应

Figure 12. Fluorescence response in logic gates

参考文献 45

[1]	Hutchings, G. J.; Brust, M.; Schmidbaur, H. Chem. Soc. Rev. 2008, 37, 1759. doi: 10.1039/b810747p pmid: 18762825
[2]	Hee, K. N.; Miae, W.; Seung, K. J.; Youngbuhm, H.; Dokyoung, K. Dyes Pigm. 2019, 160, 647. doi: 10.1016/j.dyepig.2018.06.036
[3]	Min, K. K.; Yun, S. N.; Yeonhee, L.; Kang, B. L. J. Anal. Methods Chem. 2018, 8, 1.
[4]	Ding, Y.; Jiang, Z.; Saha, K.; Kim, C. S.; Kim, S. T.; Landis, R. F.; Rotello, V. M. Mol. Ther. 2014, 22, 1075. doi: S1525-0016(16)30696-7 pmid: 24599278
[5]	Shahzadi, S.; Noshin, Z.; Saira, R.; Rehana, S.; Jawad, N.; Shahzad, N. Nanomaterials 2016, 6, 71. doi: 10.3390/nano6040071
[6]	Cao, J.-T.; Yang, J.-J.; Zhao, L.-Z.; Wang, Y.-L.; Wang, H.; Liu, Y.-M.; Ma, S.-H. Biosens. Bioelectron. 2018, 99, 92. doi: 10.1016/j.bios.2017.07.050
[7]	Ren, X.-F.; An, M.-Z. RSC Adv. 2018, 8, 2667. doi: 10.1039/C7RA13115A
[8]	Nabih, S.; Hassn, S. S. Life Sci. 2021, 272, 119262. doi: 10.1016/j.lfs.2021.119262
[9]	Zhang, X.; Xie, X.-L.; Xiong, L.-K.; Peng, Y. Chem. J. Chin. Univ. 2021, 42, 2824. (in Chinese)
	(张想, 谢旭岚, 熊力堃, 彭扬, 高等学校化学学报, 2021, 42, 2824.)
[10]	Zeng, S.-W.; Yong, K.-T.; Roy, I.; Dinh, X.-Q.; Xia, Y.; Luan, F. Plasmonics 2011, 6, 491. doi: 10.1007/s11468-011-9228-1
[11]	Zhang, W.; Deng, W. Chin. J. Org. Chem. 2018, 38, 3002. (in Chinese) doi: 10.6023/cjoc201803038
	(张薇, 邓维, 有机化学, 2018, 38, 3002.) doi: 10.6023/cjoc201803038
[12]	Muhammad, R. Y.; He, G.; Gurram, B.; Lin, J.; Huang, P. Adv. NanoBiomed. Res. 2021, 1, 2100029. doi: 10.1002/anbr.202100029
[13]	Xue, J.; Cao, X.-W.; Liu, Y.-F.; Wang, M. Chem. J. Chin. Univ. 2021, 42, 2393. (in Chinese)
	(薛谨, 曹小卫, 刘依帆, 王敏, 高等学校化学学报, 2021, 42, 2393.)
[14]	Court, K. A.; Yu, H.-J.; Chan, D.; Blanco, E.; Ziemys, A.; Holder, A. M. Adv. NanoBiomed. Res. 2021, 1, 2100036. doi: 10.1002/anbr.202100036
[15]	Ge, H.-Y.; Du, J.-J.; Long, S.-R.; Sun, W.; Fan, J.-L.; Peng, X.-J. Chem. J. Chin. Univ. 2021, 42, 1202. (in Chinese)
	(葛浩英, 杜健军, 龙飒然, 孙文, 樊江莉, 彭孝军, 高等学校化学学报, 2021, 42, 1202.)
[16]	Andrea, C. D. V.; Yeh, C. K.; Huang, Y.-F. Adv. Healthcare Mater. 2020, 9, 2000864. doi: 10.1002/adhm.202000864
[17]	Fan, J.-N.; Cheng, Y.-Q.; Sun, M.-T. Chem. Rec. 2020, 20, 1474. doi: 10.1002/tcr.202000087
[18]	Xiao, S.; Wang, S.-J.; Wang, X.; Xu, P. Nano Select. 2021, 2, 1437. doi: 10.1002/nano.202000291
[19]	Melissa, G. H.; Zhang, J.-Z. WIREs Nanomed. Nanobiotechnol. 2021, 13, e1694.
[20]	Lee, C. S.; Yu, S.-H.; Kim, T. H. Nanomaterials 2018, 8, 17. doi: 10.3390/nano8010017
[21]	Tan, X.-P.; He, S.-H.; Liu, X.; Zhao, G.-F.; Huang, T.; Yang, L. Microchim. Acta 2019, 186.
[22]	Tan, X.-P.; Liu, X.; Zeng, W.-J.; Zhao, G.-F.; Zhang, Z.; Huang, T.; Yang, L. Anal. Chim. Acta 2019, 1078, 60. doi: 10.1016/j.aca.2019.06.021
[23]	Goodman, C. M.; Mccusker, C. D.; Yilmaz, T.; Rotello, V. M. Bioconjugate Chem. 2004, 15, 897. doi: 10.1021/bc049951i
[24]	Liu, Y.; Lin, L.-Q.; Han, Y.-H.; Liu, Y.-J. Chin. J. Org. Chem. 2020, 40, 4216. (in Chinese) doi: 10.6023/cjoc202004053
	(刘洋, 林立青, 韩莹徽, 刘颖杰, 有机化学, 2020, 40, 4216.) doi: 10.6023/cjoc202004053
[25]	Quan, J.-N.; He, X.-X.; Yan, X.-H.; Li, X.-Q.; Xu, X.-S. Chin. J. Org. Chem. 2020, 40, 1033. (in Chinese)
	(全积宁, 何小雪, 严新焕, 李小青, 许响生, 有机化学, 2020, 40, 1033.) doi: 10.6023/cjoc201909027
[26]	Cui, S. Chin. J. Control Endem. Dis. 2021, 36, 23. (in Chinese)
	(崔生, 中国地方病防治杂志, 2021, 36, 23.)
[27]	Feng, L.-P.; Sun, Z.-Z.; Liu, H.; Liu, M.; Jiang, Y.; Fan, C.; Cai, Y.-Y., Zhang, S.; Xu, J.-H.; Wang, H. Chem. Commun. 2017, 9466.
[28]	Tang, X.; Wang, Y.; Han, J.; Ni, L.; Zhang, H.-Q.; Li, C.; Li, J.; Qiu, Y. Dalton Trans. 2018, 47, 3378. doi: 10.1039/c7dt04629d pmid: 29423469
[29]	Hou, P.; Wang, J.; Fu, S.; Liu, L.; Chen, S. Anal. Bioanal. Chem. 2018, 411, 935. doi: 10.1007/s00216-018-1525-5
[30]	Ren, S.-H.; Liu, S.-G.; Ling, Y.; Shi, Y.; Li, N.-B.; Luo, H.-Q. Anal. Bioanal. Chem. 2019, 411, 3301. doi: 10.1007/s00216-019-01796-0
[31]	Yao, H.; Wang, J.; Song, S.-S.; Fan, Y.-Q.; Guan, X.-W.; Zhou, Q.; Wei, T.-B.; Lin, Q.; Zhang, Y.-M. New J. Chem. 2018, 42, 18059. doi: 10.1039/C8NJ04160A
[32]	Tamil, S. G.; Chitra, V.; Tamil, S. R.; Enoch, I.; Mosae, S. P. ACS Omega 2018, 3, 7985. doi: 10.1021/acsomega.8b00748
[33]	Yang, Y.-H.; Bao, Q.-L.; Luo, J.-P.; Yang, J.-L.; Li, C.-H.; Wei, K.-K.; Chuan, Y.-M.; Yang, L.-J. Chin. J. Org. Chem. 2020, 40, 1680. (in Chinese) doi: 10.6023/cjoc201911008
	(杨云汉, 保秋连, 罗建萍, 杨俊丽, 李灿花, 魏可可, 钏永明, 杨丽娟, 有机化学, 2020, 40, 1680.) doi: 10.6023/cjoc201911008
[34]	Maniyazagan, M.; Mohandoss, S.; Sivakumar, K.; Stalin, T. Spectrochim. Acta A 2014, 133, 73. doi: 10.1016/j.saa.2014.04.183 pmid: 24929318
[35]	Hu, M.; Yang, Y.; Gu, X.-Y.; Hu, Y.; Huang, J.; Wang, C.-Y. RSC Adv. 2014, 4, 62446. doi: 10.1039/C4RA11491D
[36]	Sivakumar, K.; Parameswari, M.; Stalin, T. J. Carbohydr. Chem. 2016, 35, 118. doi: 10.1080/07328303.2016.1149713
[37]	Chattii, M.; Sarkar, S.; Mahalingam, V. Microchim. Acta 2016, 183, 133. doi: 10.1007/s00604-015-1610-9
[38]	Wan, L.; Fan, Y.-Q.; Guan, X.-W.; Qu, W.-J.; Lin, Q.; Yao, H.; Wei, T.-B.; Zhang, Y.-M. Tetrahedron 2018, 74, 4005. doi: 10.1016/j.tet.2018.06.006
[39]	Yang, K.; Chang, Y.-C.; Wen, J.; Lu, Y.-C.; Pei, Y.-X.; Cao, S.-P.; Wang, F.; Pei, Z.-C. Chem. Mater. 2016, 28, 1990. doi: 10.1021/acs.chemmater.6b00696
[40]	Shahd, M.; Srivastava, P.; Razi, S. S.; Ali, R.; Misra, A. J. Inclusion Phenom. Macrocyclic Chem. 2013, 77, 241. doi: 10.1007/s10847-012-0238-1
[41]	Chinta, J. P.; Dessingou, J.; Rao, C. P. J. Chem. Sci. 2013, 125, 1455. doi: 10.1007/s12039-013-0500-0
[42]	Zhang, Y.-M.; Zhu, W.; Qu, W.-J.; Zhong, K.-P.; Chen, X.-P.; Yao, H.; Wei, T.-B.; Lin, Q. Chem. Commun. 2018, 54, 4549. doi: 10.1039/C8CC00814K
[43]	Li, W.-T. M.S. Thesis, Northwest Normal University, Lanzhou, 2017. (in Chinese)
	(李文婷, 硕士论文, 西北师范大学, 兰州, 2017.)
[44]	Wang, X.-J.; Zhang, C.-H.; L.-H.; Zhang, L.-W. Sens. Actuators, B 2011, 156, 463.
[45]	Jiang, R.-J. M.S. Thesis, Kunming University of Science and Technology, Kunming, 2014. (in Chinese)
	(蒋锐剑, 硕士论文, 昆明理工大学, 昆明, 2014.)

基于Au³⁺和I^–构建的单-(6-二乙烯三胺-6-去氧)-β-环糊精超分子荧光开关

Mono-(6-diethylenetriamine-6-deoxy)-β-cyclodextrin Supramolecular Fluorescent Switch Constructed Based on Au³⁺ and I^–

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