稀土超分子荧光有序聚集体在离子液体中聚集及荧光性能的研究

doi:10.6023/A25010009

摘要/Abstract

基于离子液体构建的稀土荧光有序聚集体可赋予稀土材料更优异的荧光性能和丰富的结构形态. 与此同时, 环糊精凭借其动态可逆的调控特性, 在超分子聚集体相关研究领域受到广泛地关注. 本工作旨在利用β-环糊精(β-CD)主客体包结的调控作用, 实现在离子液体中构建荧光性能优异且形貌可调控的稀土荧光有序聚集体. 通过将稀土两亲配合物与离子液体型表面活性剂在β-CD的主客体作用下共组装, 进而在硝酸乙基铵中制备得到了菱形片状、小型微米管和罕见的四方棱柱微米管三种形貌的聚集体. 该聚集体中稀土配合物的荧光强度提升了3~8倍, 荧光寿命也显著长于同溶剂中其它结构的稀土有序聚集体. 并且, 通过α-淀粉酶的添加实现了该聚集体荧光和形貌的酶响应调控.

关键词: 稀土, 环糊精, 超分子, 离子液体, 酶响应

Rare earth fluorescent ordered aggregates constructed based on ionic liquids can endow rare earth materials with superior fluorescence performance and rich structural morphologys. At the same time, cyclodextrins have received considerable attention in the research field of supramolecular aggregates due to their dynamic and reversible regulatory properties. In this work, an ionic liquid-type rare earth europium β-diketone amphiphilic complex [C₁₂mim][Eu(TTA)₄] (C₁₂mim=1-dodecyl-3-methylimidazole, TTA=4-methyltrifluoroacetophenone, abbreviated as C₁₂-Eu) was synthesized. Through the cooperative assembly of the ionic liquid-type surfactant (1-dodecyl-3-methylimidazolium bromide) and the host-guest interaction of β-cyclodextrin (abbreviated as β-CD), rare earth supramolecular fluorescent ordered aggregates with different morphologies were constructed in a protic ionic liquid, ethylammonium nitrate. The fluorescence properties and aggregation structures of aggregates were characterized by fluorescence spectroscopy, UV-vis spectroscopy, infrared spectroscopy, time-resolved fluorescence spectroscopy, laser confocal microscopy, and fluorescence microscopy. After assembling into ordered aggregates, the fluorescence intensity of the obtained materials increased significantly (by 3~8 times) and the lifetimes were much longer compared with those of other assemblies in the same solvent. Meanwhile, the fluorescence microscopy results demonstrated the successful doping of C₁₂-Eu and the formation of three distinct types of red fluorescent supramolecular aggregates: flakes, mini microtubes, and rare hollow tetragonal prismatic microtubes with square cross-sections. Furthermore, α-amylase was introduced to investigate the changes in fluorescence and aggregation structure of the aggregates over time. It was demonstrated that the aggregates were formed through inclusion complexes of cyclodextrins, and the enzyme-responsive regulation of the aggregates was also achieved.

Key words: rare earth, cyclodextrin, supramolecular, ionic liquid, enzyme response

引用此文

李菲, 伊思静, 王姣, 刘晓霞, 高文梅, 李婧婧, 张海峰. 稀土超分子荧光有序聚集体在离子液体中聚集及荧光性能的研究[J]. 化学学报, 2025, 83(5): 453-462.

Fei Li, Sijing Yi, Jiao Wang, Xiaoxia Liu, Wenmei Gao, Jingjing Li, Haifeng Zhang. Study on the Assembling and Fluorescence Properties of Rare Earth Supramolecular Fluorescent Ordered Aggregates in Ionic Liquids[J]. Acta Chimica Sinica, 2025, 83(5): 453-462.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 11

图1. 由[C12mim]Br, C12-Eu和β-CD组装的稀土超分子荧光聚集体形成示意图

Figure 1. Illustration for the construction of rare earth supramolecular fluorescent aggregates assembled by [C12mim]Br, C12-Eu and β-CD

图2. (a) C12-Eu-[C12mim]Br-β-CD三元体系样品(C12-Eu 0.001 mol/L, [C12mim]Br-β-CD 0~0.18 mol/L)在365 nm紫外灯照射下的图片; 三元体系样品在405 nm激发下得到的激光共聚焦明场和暗场图片, 其中, C12-Eu的浓度为0.001 mol/L, [C12mim]Br-β-CD的添加浓度依次为: (b, c) 0.09 mol/L; (d, e) 0.12 mol/L; (f, g) 0.18 mol/L

Figure 2. (a) The image of the C12-Eu-[C12mim]Br-β-CD ternary system (C12-Eu 0.001 mol/L, [C12mim]Br-β-CD 0~0.18 mol/L) under 365 nm ultraviolet lamp irradiation; Laser confocal bright field and dark field images under excitation at 405 nm of ternary system. The concentration of C12-Eu was 0.001 mol/L, and the [C12mim]Br-β-CD was added at concentrations of (b, c) 0.09 mol/L; (d, e) 0.12 mol/L; (f, g) 0.18 mol/L

图3. C12-Eu-[C12mim]Br-β-CD三元体系光学显微镜的放大图. 其中, C12-Eu的浓度为0.001 mol/L, [C12mim]Br-β-CD的添加浓度依次为: (a)片层(0.09 mol/L); (b)小微米管(0.12 mol/L); (c, d)方型微米管(0.18 mol/L); (e)多片层结构(0.09 mol/L); (f)正在组装的方型微米管(0.18 mol/L)

Figure 3. Optical microscope magnified image of C12-Eu-[C12mim]Br-β-CD ternary system. The concentration of C12-Eu was 0.001 mol/L, and the [C12mim]Br-β-CD was added at concentrations of (a) flake (0.09 mol/L); (b) mini microtube (0.12 mol/L); (c, d) square microtube (0.18 mol/L); (e) multi- layer stacked structure (0.09 mol/L); (f) assembling square microtubes (0.18 mol/L)

图4. C12-Eu-[C12mim]Br-β-CD三元体系相图(C12-Eu 0.001 mol/L, [C12mim]Br-β-CD 0~0.18 mol/L)

Figure 4. Phase diagram of C12-Eu-[C12mim]Br-β-CD ternary system (C12-Eu 0.001 mol/L, [C12mim]Br-β-CD 0~0.18 mol/L)

图5. C12-Eu-[C12mim]Br-β-CD三元体系(固定C12-Eu的浓度为0.001 mol/L, [C12mim]Br-β-CD的添加浓度为0~0.24 mol/L)的激发(a, 插图为LMCT峰相对于f-f跃迁的荧光强度变化曲线, λEM=613 nm)和发射(b, 插图为5D0→7F2跃迁的荧光强度变化曲线, λEX=395 nm)光谱

Figure 5. Excitation (a, inset: fluorescence intensity variation curve of LMCT peak relative to f-f transition, λEM=613 nm) and emission (b, inset: fluorescence intensity variation curve of 5D0→7F2 transition, λEX=395 nm) spectra of C12-Eu-[C12mim]Br-β-CD ternary system (C12-Eu 0.001 mol/L, [C12mim]Br-β-CD 0~0.24 mol/L)

图6. C12-Eu-[C12mim]Br-β-CD三元体系(C12-Eu 0.001 mol/L, [C12mim]Br-β-CD 0~0.18 mol/L)在395 nm激发时613 nm处得到的荧光衰减曲线

Figure 6. Fluorescence decay curves of C12-Eu-[C12mim]Br-β-CD ternary system (C12-Eu 0.001 mol/L, [C12mim]Br-β-CD 0~0.18 mol/L) under excitation at 395 nm and observed at 613 nm

图7. 不同体系在395 nm激发时613 nm处的荧光发射强度值的比较: C12-Eu (0.001 mol/L), C12-Eu-[C12mim]Br (C12-Eu 0.001 mol/L, [C12mim]Br 0~0.18 mol/L), C12-Eu-β-CD (C12-Eu 0.001 mol/L, β-CD 0~0.18 mol/L), C12-Eu-[C12mim]Br-β-CD (C12-Eu 0.001 mol/L, [C12mim]Br-β-CD 0~0.18 mol/L)

Figure 7. Comparison of fluorescence emission intensity values under excitation at 395 nm and observed at 613 nm for different systems of C12-Eu (0.001 mol/L), C12-Eu-[C12mim]Br (C12-Eu 0.001 mol/L, [C12mim]Br 0~0.18 mol/L), C12-Eu-β-CD (C12-Eu 0.001 mol/L, β-CD 0~0.18 mol/L), C12-Eu-[C12mim]Br-β-CD (C12-Eu 0.001 mol/L, [C12mim]Br-β-CD 0~0.18 mol/L)

Concentration/ (mol•L^-1)	τ/ms
Concentration/ (mol•L^-1)	C₁₂-Eu-β-CD	C₁₂-Eu-[C₁₂mim]Br	C₁₂-Eu-[C₁₂mim]Br-β-CD
0 0.03	0.202 0.225	0.202 0.274	0.202 0.202(84%), 0.537(16%)
0.06	0.214	0.299	0.193(49%), 0.771(51%)
0.09	0.212	0.333	0.197(17%), 0.824(83%)
0.12	0.265	0.380	0.198(16%), 0.822(84%)
0.15 0.18	0.277 0.298	0.395 0.397	0.184(5%), 0.831(96%) 0.177(2%), 0.825(98%)

表1. 稀土配合物(0.001 mol/L)在添加不同浓度[C12mim]Br/β-CD(二元体系, [C12mim]Br/β-CD 0~0.18 mol/L)或[C12mim]Br-β-CD(三元体系, [C12mim]Br-β-CD 0~0.18 mol/L)的荧光寿命τ值

Table 1. Fluorescence lifetime values (τ) for rare earth complexes (0.001 mol/L) under the addition of different concentrations of [C12mim]Br/β-CD (binary system, [C12mim]Br/β-CD 0~0.18 mol/L) or [C12mim]Br-β-CD (ternary system, [C12mim]Br-β-CD 0~0.18 mol/L)

图8. C12-Eu-[C12mim]Br-β-CD三元体系(C12-Eu 0.001 mol/L, [C12mim]Br-β-CD 0~0.18 mol/L)的紫外-可见光谱(a); EAN、β-CD、C12-Eu-[C12mim]Br-β-CD三元体系(C12-Eu 0.001 mol/L, [C12mim]Br- β-CD 0.18 mol/L)和[C12mim]Br的红外光谱(b)

Figure 8. UV-vis spectra of the C12-Eu-[C12mim]Br-β-CD ternary system (a, C12-Eu 0.001 mol/L, [C12mim]Br-β-CD 0~0.18 mol/L); FT-IR spectra of EAN, β-CD, C12-Eu-[C12mim]Br-β-CD ternary system (C12-Eu 0.001 mol/L, [C12mim]Br-β-CD 0.18 mol/L) and [C12mim]Br (b)

图9. 不同形貌的聚集体在加入α-淀粉酶(400 U/mL)后随时间的荧光强度猝灭曲线(T=37 ℃): 片层(C12-Eu 0.001 mol/L, [C12mim]Br-β-CD 0.09 mol/L)、小微米管(C12-Eu 0.001 mol/L, [C12mim]Br-β-CD 0.12 mol/L)和方形微米管(C12-Eu 0.001 mol/L, [C12mim]Br-β-CD 0.18 mol/L)

Figure 9. The fluorescence intensity quenching curves over time (T=37 ℃) after adding α-amylase (400 U/mL) of aggregates with structure of flake (C12-Eu 0.001 mol/L, [C12mim]Br-β-CD 0.09 mol/L), mini microtube (C12-Eu 0.001 mol/L, [C12mim]Br-β-CD 0.12 mol/L), and square microtube (C12-Eu 0.001 mol/L, [C12mim]Br-β-CD 0.18 mol/L)

图10. 稀土超分子聚集体二次组装示意图

Figure 10. Schematic diagram of secondary assembly of rare earth supramolecular aggregates

参考文献 44

[1]	Zhong, Y. W.; Qian, X. N.; Ma, C.; Liu, K.; Zhang, H. J. Acta Chim. Sinica. 2023, 81, 1624. (in Chinese)
	(钟越文, 钱希宁, 马超, 刘凯, 张洪杰, 化学学报, 2023, 81, 1624.) doi: 10.6023/A23070323
[2]	Li, P.; Li, H. R. Coord. Chem. Rev. 2021, 441, 213988.
[3]	Armelao, L.; Quici, S.; Barigelletti, F.; Accorsi, G.; Bottaro, G.; Cavazzini, M.; Tondello, E. Coord. Chem. Rev. 2010, 254, 487.
[4]	Zeng, Z. C.; Huang, B. L.; Wang, X.; Lu, L.; Lu, Q. Y.; Sun, M. J.; Wu, T.; Ma, T. F.; Xu, J.; Xu, Y. S.; Wang, S. A.; Du, Y. P.; Yang, C. H. Adv. Mater. 2020, 32, 2004506.
[5]	Bünzli, J. C. G. Coord. Chem. Rev. 2015, 293, 19.
[6]	Wang, C.; Li, H.; Dong, J. T.; Chen, Y. X.; Luan, X. K.; Li, X. N.; Du, X. Z. Chem. - Eur. J. 2022, 28, e202202050.
[7]	Wang, J. Y.; de Kool, R. M.; Velders, A. H. Langmuir. 2015, 31, 12251.
[8]	Harris, M.; Carron, S.; Vander Elst, L.; Laurent, S.; Parac‐Vogt, T. N. Eur. J. Inorg. Chem. 2015, 2015, 4572.
[9]	Liu, R. M.; Feng, Y. H.; Li, Z.; Lu, S.; Guan, T. Y.; Li, X. J.; Liu, Y.; Chen, Z.; Chen, X. Y. Acta Chim. Sinica. 2022, 80, 423. (in Chinese)
	(刘若湄, 冯艳辉, 李卓, 卢珊, 关天用, 李幸俊, 刘䶮, 陈卓, 陈学元, 化学学报, 2022, 80, 423.) doi: 10.6023/A22010001
[10]	Xu, L. M.; Feng, L. Z.; Han, Y. C.; Jing, Y. Y.; Xian, Z. Y.; Liu, Z.; Huang, J. B.; Yan, Y. Soft Matter. 2014, 10, 4686.
[11]	Liu, J.; Morikawa, M.; Kimizuka, N. J. Am. Chem. Soc. 2011, 133, 17370.
[12]	Fang, G. H.; Yang, X. W.; Chen, S. M.; Wang, Q. X.; Zhang, A. W.; Tang, B. Coord. Chem. Rev. 2022, 454, 214352.
[13]	Lu, Y. Q.; Zou, H.; Yuan, H.; Gu, S. Y.; Yuan, W. Z.; Li, M. Q. Eur. Polym. J. 2017, 91, 396.
[14]	Dan, Z. L.; Cao, H. Q.; He, X. Y.; Zeng, L. J.; Zou, L. L.; Shen, Q.; Zhang, Z. W. Int. J. Pharm. 2015, 483, 63.
[15]	Zhou, C. C.; Cheng, X. H.; Zhao, Q.; Yan, Y.; Wang, J. D.; Huang, J. B. Langmuir. 2013, 29, 13175.
[16]	Wei, Z. Y.; Wu, Z. K.; Ru, S.; Ni, L. B.; Wei, Y. G. Chem. J. Chinese Universities. 2022, 43, 190. (in Chinese)
	(魏哲宇, 吴志康, 茹诗, 倪鲁彬, 魏永革, 高等学校化学学报, 2022, 43, 190.)
[17]	Yuan, Y.; Nie, T. Q.; Fang, Y. F.; You, X. R.; Huang, H.; Wu, J. J. Mater. Chem. B. 2022, 10, 2077.
[18]	Zhang, Y. M.; Liu, Y. H.; Liu, Y. Adv. Mater. 2020, 32, 1806158.
[19]	Xiao, X.; Huang, J. B. Langmuir. 2024, 40, 15407.
[20]	Liu, K.; Ma, C.; Wu, T. Y.; Qi, W. L.; Yan, Y.; Huang, J. B. Curr. Opin. Colloid Interface Sci. 2020, 45, 44.
[21]	Wang, Y. F.; He, L. L.; Ding, L. L.; Zhao, X. Y.; Ma, H.; Luo, Y. H.; Ma, S. S.; Xiong, Y. M. Chem. Mater. 2023, 35, 5723.
[22]	Zhou, W. L.; Chen, Y.; Liu, Y. Acta Chim. Sinica. 2020, 78, 1164. (in Chinese)
	(周维磊, 陈湧, 刘育, 化学学报, 2020, 78, 1164.) doi: 10.6023/A20100486
[23]	Xu, W.; Liang, W.; Wu, W.; Fan, C.; Rao, M.; Su, D.; Zhong, Z.; Yang, C. Chem. Eur. J. 2018, 24, 16677.
[24]	Samanta, S. K.; Ghorai, S. K.; Ghosh, S. J. J. Photochem. Photobiol., A. 2013, 252, 145.
[25]	Zhang, W. J.; Chen, Y.; Zhang, S. P.; Tang, S. K.; Chen, X. Q.; Cui, G. Y. C. J. Inorg. Organomet. Polym. Mater. 2018, 28, 1294.
[26]	Ribeiro, A. O.; Serra, O. A. J. Inclusion Phenom. Macrocyclic Chem. 2010, 67, 281.
[27]	Lei, N. N.; Shen, D. Z.; Wang, X. F.; Wang, J.; Li, Q. T.; Chen, X. J. Colloid Interface Sci. 2018, 529, 122.
[28]	Dutta, R.; Kundu, S.; Sarkar, N. Biophys. Rev. 2018, 10, 861.
[29]	Adawiyah, N.; Moniruzzaman, M.; Hawatulaila, S.; Goto, M. Med. Chem. Commun. 2016, 7, 1881.
[30]	Prodius, D.; Mudring, A. V. Coord. Chem. Rev. 2018, 363, 1.
[31]	Yi, S. J.; Yao, M. H.; Wang, J.; Chen, X. Phys. Chem. Chem. Phys. 2016, 18, 27603.
[32]	Li, Q. R.; Yi, S. J.; Chen, X. ACS Omega. 2019, 4, 9843.
[33]	Yi, S. J.; Wang, J.; Chen, X. Chem. Chem. Phys. 2015, 17, 20322.
[34]	Li, Q. R.; Song, S. H.; Feng, Z. Y.; Qiu, J.; Sun, M.; Chen, X. Langmuir. 2020, 36, 2911.
[35]	Zhang, J. J.; Shen, X. H. J. Phys. Chem. B. 2013, 117, 1451.
[36]	Zhou, C. C.; Cheng, X. H.; Yan, Y.; Wang, J. D.; Huang, J. B. Langmuir. 2014, 30, 3381.
[37]	Xiao, X.; Xu, Z. R.; Wang, W. K.; Sun, S. Y.; Qiao, Y.; Jiang, L. X.; Yan, Y.; Huang, J. B. Langmuir. 2021, 37, 8348. doi: 10.1021/acs.langmuir.1c01226 pmid: 34210141
[38]	Wang, J.; Wang, T.; Hu, Y. M.; Zhang, X. N.; Ma, Y. Y.; Lv, H. M.; Xu, S. S.; Wang, Y. L.; Jiang, Z. K. J. Mater. Sci. 2021, 56, 10979.
[39]	Guo, Y. W.; Liu, J.; Tang, Q. L.; Li, C. C.; Zhang, Y. Y.; Wang, Y.; Wang, Y. X.; Bi, Y. P.; Snow, C. D.; Kipper, M. J.; Belfiore, L. A.; Tang, J. G. Int. J. Mol. Sci. 2022, 23, 6597.
[40]	Hao, Q.; Kang, Y. T.; Xu, J. F.; Zhang, X. Langmuir. 2021, 37, 6062. doi: 10.1021/acs.langmuir.1c00781 pmid: 33961441
[41]	Shen, J. L.; Song, L. F.; Xin, X.; Wu, D.; Wang, S. B.; Chen, R. Colloids Surf., A. 2016, 509, 512.
[42]	Kang, Y. T.; Cai, Z. G.; Tang, X. Y.; Liu, K.; Wang, G. T.; Zhang, X. ACS Appl. Mater. Interfaces. 2016, 8, 4927.
[43]	Siva, S.; Nayaki, S. K.; Rajendiran, N. Carbohydr. Polym. 2015, 122, 123.
[44]	Zhang, J. J.; Shen, X. H.; Wu, A. H.; Zhang, C. F.; Chen, Q. D.; Gao, H. C. Sci. China: Chem. 2010, 53, 2019.