An Excited-State Intramolecular Proton Transfer (ESIPT) Plus Ag-gregation Induced Emission (AIE) Phenanthro[9, 10-d]imidazole-Based Fluorescence Probe for Detection of Fe3+ in Living Cells

doi:10.6023/cjoc201904078

Chinese Journal of Organic Chemistry ›› 2019, Vol. 39 ›› Issue (11): 3250-3257.DOI: 10.6023/cjoc201904078 Previous Articles Next Articles

Special Issue: 荧光探针-生物传感合辑；有机超分子化学合辑

基于激发态分子内质子转移(ESIPT)和聚集诱导发光(AIE)活性的菲并咪唑Fe³⁺荧光探针及细胞成像研究

何玉倩^a, 赵冰^a*(), 阚伟^a*(), 王丽艳^a, 宋波^a, 殷广明^a, 毕野^a, 陈书文^b*()

^a齐齐哈尔大学化学与化学工程学院黑龙江齐齐哈尔 161006
^b 辽宁科技大学材料与冶金学院辽宁鞍山 114051

收稿日期:2019-04-30 发布日期:2019-06-19
通讯作者: 赵冰,阚伟,陈书文 E-mail:zhao_submit@aliyun.com;kan_submit@aliyun.com;anshancsw@126.com
基金资助:
国家自然科学基金(21506106);黑龙江省科学基金(LC2017004);黑龙江省高校基本业务费(135209209);黑龙江省高校基本业务费(YSTSXK201853);黑龙江省高校基本业务费(YSTSXK201859);齐齐哈尔大学研究生创新科研(YJSCX2018-ZD18)

An Excited-State Intramolecular Proton Transfer (ESIPT) Plus Ag-gregation Induced Emission (AIE) Phenanthro[9, 10-d]imidazole-Based Fluorescence Probe for Detection of Fe³⁺ in Living Cells

He Yuqian^a, Zhao Bing^a*(), Kan Wei^a*(), Wang Liyan^a, Song Bo^a, Yin Guangming^a, Bi Ye^a, Chen Shuwen^b*()

^a Chemistry and Chemical Engineering Institute, Qiqihar University, Qiqihar, Heilongjiang 161006
^b School of Materials and Metallurgy, University of Science and Technology Liaoning, Anshan, Liaoning 114051

Received:2019-04-30 Published:2019-06-19
Contact: Zhao Bing,Kan Wei,Chen Shuwen E-mail:zhao_submit@aliyun.com;kan_submit@aliyun.com;anshancsw@126.com
Supported by:
the National Natural Science Foundation of China(21506106);the Natural Science Foundation of Heilongjiang Province(LC2017004);the Fundamental Research Funds in Heilongjiang Provincial Universities(135209209);the Fundamental Research Funds in Heilongjiang Provincial Universities(YSTSXK201853);the Fundamental Research Funds in Heilongjiang Provincial Universities(YSTSXK201859);the Qiqihar University Graduate Innovation Fund Grants(YJSCX2018-ZD18)

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Abstract

Selective detection of Fe³⁺ has considerable importance due to its active involvement in various biological processes. Based on the mechanism of excited-state intramolecular proton transfer (ESIPT) plus aggregation induced emission (AIE), a fluorescence probe of phenanthro[9, 10-d]imidazole modified by the phenolic hydroxyl (PIP-o-OH) had been designed, synthesized and applied in the detection of Fe³⁺. The structure of PIP-o-OH was characterized by ¹H NMR, ¹³C NMR, IR, HRMS and X-ray single diffraction. Furthermore, a clear intramolecular hydrogen bond was observed between hydroxyl O-H and imidazole N atom in X-ray single structure, which improved the impossibility of ESIPT activity. ESIPT and AIE activities of PIP-o-OH were adequately determined by absorption, emission spectra and scanning electron microscope (SEM). The aggregated PIP-o-OH in MeOH/H₂O (V:V=1:9, Hepes 10 μmol/L, pH=7.4) exhibited a good sensitivity towards Fe³⁺ with "turn-off" fluorescence response just after 20 s. The limit of detection (LOD) was calculated as low as 0.49 μmol/L. So it could be utilized to detect Fe³⁺ in biology and environmental samples. In addition, the calculation of the density functional theory (DFT) confirmed the formation of PIP-o-OH-Fe³⁺ complex. Also, PIP-o-OH was successfully applied to monitor Fe³⁺ in HeLa cells by the fluorescence change and quantificationally detect Fe³⁺ in water samples.

Key words: phenanthro[9, 10-d]imidazole, Fe³⁺, fluorescence probe, cell imaging, water samples

Cite this article

He Yuqian, Zhao Bing, Kan Wei, Wang Liyan, Song Bo, Yin Guangming, Bi Ye, Chen Shuwen. An Excited-State Intramolecular Proton Transfer (ESIPT) Plus Ag-gregation Induced Emission (AIE) Phenanthro[9, 10-d]imidazole-Based Fluorescence Probe for Detection of Fe³⁺ in Living Cells[J]. Chinese Journal of Organic Chemistry, 2019, 39(11): 3250-3257.

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Fig. & Tab. 11

Figure 1. Molecule structure (a) and packing arrangement (b) of probe PIP-o-OH

Figure 2. Absorption (a) and fluorescence spectra (b) of PIP-o-OH (20 μmol/L) in different solvents

Figure 3. Changes of fluorescence spectra of PIP-o-OH (20 μmol/L) in different volume ratios of DMF/H2O (a) and MeOH/H2O (b)

Figure 4. "Naked eye" pictures of PIP-o-OH illuminated by daylight (a), UV lamp (b) and red laser pointer (c) in different proportions of DMF/H2O (Hepes 10 μmol/L, pH＝7.4)

Figure 5. SEM images of PIP-o-OH in DMF/H2O (Hepes 10 μmol/L, pH＝7.4) mixtures with different water fraction of 70% (a), 80% (b) and 90% (b)

Figure 6. (a) Changes of emission spectra of PIP-o-OH (20 μmol/L) in MeOH/H2O (V:V＝1:9, Hepes 10 μmol/L, pH＝7.4) solution with various cations (200 μmol/L); (b) fluorescence spectra of PIP-o-OH (20 μmol/L) in MeOH/H2O (V:V＝1:9, Hepes 10 μmol/L, pH＝7.4) solution with Fe3+ (1 mmol/L) and other interfered cations (1 mmol/L)

Figure 7. (a) Fluorescence spectra of PIP-o-OH (20 μmol/L) in MeOH/H2O (V:V＝1:9, Hepes 10 μmol/L, pH＝7.4) solution with the increasing of Fe3+ (0~1 mmol/L); (b) time-dependent fluorescence intensity changes of PIP-o-OH (20 μmol/L) upon addition of Fe3+ (1 mmol/L)

Figure 8. Optimization stationary structures and energy calculation for PIP-o-OH and PIP-o-OH-Fe3+ complex

Figure 9. SEM image of PIP-o-OH-Fe3+ complex

Figure 10. Fluorescence images of HeLa cells treated with PIP-o-OH and PIP-o-OH-Fe3+

水样	c(Fe³⁺)/(μmol?L^－1)		Recovery/%	RSD/%
水样	加入值	测定值	Recovery/%	RSD/%
自来水	1	1.03	103.0	1
	3	2.86	95.3	0.32
	5	4.93	98.6	0.65
瓶装水	1	0.95	95.0	1.12
	3	2.95	98.3	0.52
	5	4.89	97.8	0.23

Table 1. Detection results of Fe3+ in real water samples using the probe PIP-o-OH

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基于激发态分子内质子转移(ESIPT)和聚集诱导发光(AIE)活性的菲并咪唑Fe³⁺荧光探针及细胞成像研究

An Excited-State Intramolecular Proton Transfer (ESIPT) Plus Ag-gregation Induced Emission (AIE) Phenanthro[9, 10-d]imidazole-Based Fluorescence Probe for Detection of Fe³⁺ in Living Cells

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