诺蒎酮基喹唑啉-2-胺型铜离子荧光探针的合成及其应用研究

doi:10.6023/cjoc202008049

有机化学 ›› 2021, Vol. 41 ›› Issue (3): 1168-1176.DOI: 10.6023/cjoc202008049 上一篇下一篇

研究论文

诺蒎酮基喹唑啉-2-胺型铜离子荧光探针的合成及其应用研究

张明光^a, 李明新^a, 杨益琴^a, 徐徐^a, 宋杰^b, 王忠龙^a^,^*(), 王石发^a^,^*()

a 南京林业大学轻工与食品学院南京林业大学林业资源高效加工利用协同创新中心南京 210037
b 密西根大学菲林特分校化学与生物化学系菲林特密西根 48502

收稿日期:2020-08-26 修回日期:2020-10-22 发布日期:2020-11-04
通讯作者: 王忠龙, 王石发
基金资助:
国家自然科学基金(32071707); 江苏省高校重点学科建设资助项目

Synthesis of Nopinone-Based Quinazolin-2-amine Fluorescent Probe for Detection of Cu²⁺ and Its Application Research

Mingguang Zhang^a, Mingxin Li^a, Yiqin Yang^a, Xu Xu^a, Jie Song^b, Zhonglong Wang^a^,^*(), Shifa Wang^a^,^*()

a Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, College of Light Industry and Food,Nanjing Forestry University, Nanjing 210037, China
b Department of Chemistry and Biochemistry, University of Michigan-Flint, Flint, MI 48502, USA

Received:2020-08-26 Revised:2020-10-22 Published:2020-11-04
Contact: Zhonglong Wang, Shifa Wang
About author:
* Corresponding authors. E-mail: wangshifa65@163.com;
wang_zhonglong@njfu.edu.cn
Supported by:
National Natural Science Foundation of China(32071707); Jiangsu Provincial Key Lab for the Chemistry and Utilization of Agro-Forest Biomass, and the Priority Academic Program Development of Jiangsu Higher Education Institutions

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摘要/Abstract

以可再生的β-蒎烯衍生物诺蒎酮为原料, 设计合成了一种新型的诺蒎酮基喹唑啉-2-胺铜离子荧光探针N-苄基- 4-(4-(二乙氨基)苯基)-7,7-二甲基-5,6,7,8-四氢-6,8-桥亚甲基喹唑啉-2-胺(BNQ). 探针BNQ在PBS/THF (V/V=8/2, 10 mmol?L^–1, pH=7.4)溶液中对Cu²⁺表现出高度选择性的荧光猝灭效应, 并能在较宽pH范围(4~10)内有效识别Cu²⁺. 同时, 荧光滴定实验结果表明, 探针BNQ对Cu²⁺具有良好的灵敏度, 其检测限为0.09 μmol?L ^–1, 远低于世界卫生组织(WHO)规定在饮用水中Cu²⁺的最高含量(<30 μmol?L^–1). 而且, 采用高分辨质谱以及密度泛函理论计算确定了探针BNQ与Cu²⁺的络合作用机理. 探针BNQ还可以对不同水环境中的微摩尔级Cu²⁺进行快速检测. 生物成像实验发现, 探针BNQ还可检测斑马鱼体内的Cu²⁺, 并呈现出良好的荧光成像效果.

关键词: 诺蒎酮, 喹唑啉-2-胺, 荧光探针, 铜离子, 生物成像

In this study, a novel nopinone-based quinazolin-2-amine fluorescent probe N-benzyl-4-(4-(diethylamino)phenyl)- 7,7-dimethyl-5,6,7,8-tetrahydro-6,8-methanoquinazolin-2-amine (BNQ) was synthesized from renewable β-pinene derivative nopinone. The probe BNQ exhibited a high selective fluorescence quenching response toward Cu²⁺in PBS/THF (V/V=8/2, 10 mmol?L^–1, pH=7.4) solution, and could effectively recognize Cu²⁺ within a wide pH range (4~10). Meanwhile, the fluorescent titration experiment showed that the probe BNQ was high sensitive for detecting Cu²⁺, and its detection limit was found to be 0.09 μmol?L ^–1, which was much lower than that of stated by World Health Organization (WHO) in drinking water (<30 μmol?L^–1). Furthermore, the coordination mechanism of probe BNQ with Cu²⁺ was confirmed by high resolution mass spectrum (HRMS) and density functional theory (DFT) calculations. The probe BNQ could detect micromolar Cu²⁺ in different environmental water samples. The results of bio-imaging experiment demonstrated that the probe BNQwas also successfully used for monitoring Cu²⁺ in living zebrafish, and showed an excellent fluorescence imaging performance.

Key words: nopinone, quinazolin-2-amine, fluorescent probe, Cu²⁺ ion, bioimaging

引用此文

张明光, 李明新, 杨益琴, 徐徐, 宋杰, 王忠龙, 王石发. 诺蒎酮基喹唑啉-2-胺型铜离子荧光探针的合成及其应用研究[J]. 有机化学, 2021, 41(3): 1168-1176.

Mingguang Zhang, Mingxin Li, Yiqin Yang, Xu Xu, Jie Song, Zhonglong Wang, Shifa Wang. Synthesis of Nopinone-Based Quinazolin-2-amine Fluorescent Probe for Detection of Cu²⁺ and Its Application Research[J]. Chinese Journal of Organic Chemistry, 2021, 41(3): 1168-1176.

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图/表 14

Scheme 1. Synthesis routes of BNQ

Figure 1. (a) UV-Vis absorption and (b) fluorescence emission spectra of BNQ (1 μmol?L –1) with or not Cu2+(10 μmol?L –1) Inset: (a) The responding photographs under day light; (b) The responding photographs under 365 nm UV light

Figure 2. Fluorescence intensity (λem=422 nm) of BNQ (1 μmol?L –1) in the absence and presence of Cu2+ (10 μmol?L –1) in PBS/THF (V/V=8/2, 10 mmol?L–1, pH=7.4) with different pH values

Figure 3. Fluorescence intensity of BNQ (1 μmol?L –1) at 460 nm in the presence of Cu2+ (0, 5, 10 μmol?L –1) in PBS/THF (V/V=8/2, 10 mmol?L–1, pH=7.4)

Figure 4. Fluorescence spectra of 0~15 μmol?L –1 Cu2+ added into 1 μmol?L –1 BNQ solution (λex=350 nm)

Figure 5. Linear fitting curve of emission intensity of BNQ with Cu2+ concentrations (0~15?μmol?L–1)

Figure 6. Fluorescent spectra of BNQ (1 μmol?L –1) with different metal ions (10 μmol?L –1) including Ag+, Na+, K+, Cd2+, Ca2+, Mg2+, Zn2+, Co2+, Ni2+, Fe2+, Pb2+, Hg2+, Cr3+, La3+, Fe3+, Al3+, Ce4+, Zr4+, and Cu2+ in PBS/THF (V/V=8/2, 10 mmol?L–1, pH=7.4)

Figure 7. Fluorescence intensity (λem=422 nm) of BNQ (1 μmol?L –1) with Cu2+ (10 μmol?L –1) in the presence of different competitive anions (10 μmol?L –1) including Ag+, Na+, K+, Cd2+, Ca2+, Mg2+, Zn2+, Co2+, Ni2+, Fe2+, Pb2+, Hg2+, Cr3+, La3+, Fe3+, Al3+, Ce4+, Zr4+ in PBS/THF (V/V=8/2, 10 mmol?L–1, pH=7.4)

Figure 8. 1H NMR spectra analysis of BNQ and Cu2+

Figure 9. Proposed complexation mechanism of BNQ with Cu2+

Figure 10. Optimized structures and frontier molecular orbitals of BNQ and BNQ-Cu2+

Figure 11. (a) Fluorescence intensity of BNQ (1 μmol?L –1) at 422 nm towards different concentration of Cu2+ (0, 2, 5, 10, 15 μmol? L –1); (b) A linear correlation between the fluorescence intensity at 422 nm against Cu2+ concentrations (0, 2, 5, 10, 15 μmol?L –1) in Zihu creek water; (c) A linear correlation between the fluorescence intensity at 422 nm against Cu2+ concentrations (0, 2, 5, 10, 15 μmol?L –1) in Xuanwu lake water; (d) A linear correlation between the fluorescence intensity at 422 nm against Cu2+ concentrations (0, 2, 5, 10, 15 μmol?L –1) in Yangtze river water

Water sample	Added Cu²⁺/ (μmol?L^–1)	Found Cu²⁺/ (μmol?L^–1)	Recovery/%
Zihu Creek water	0	0±0.26	0
	2	1.78±0.32	89.1
	5	5.08±0.23	101.5
	10	10.35±0.34	103.5
	15	14.81±0.30	98.7
Xuanwu Lake water	0	–0.02±0.28	0
	2	1.93±0.30	96.7
	5	4.96±0.24	99.2
	10	10.47±0.34	104.7
	15	14.85±0.26	99.0
Yangtze River water	0	–0.18±0.30	0
	2	1.93±0.24	96.5
	5	5.01±0.22	100.2
	10	10.68±0.28	106.8
	15	14.41±0.33	96.1

Table 1. Determination results of Cu2+ concentration in three real water samples by BNQ.

Figure 12. (a~c) Confocal fluorescence images of zebrafish incubated with BNQ (5 μmol?L –1) for 2 h; (e~g) incubated with BNQ (5 μmol?L –1) for 1 h followed by adding Cu2+ (10 μmol? L –1) for 1 h (emission was collected by blue channel from 405 nm to 460 nm, λex=405 nm); (d) corresponding 2.5D surface plot of merged fluorescence image in Figure 12c; (h) corresponding 2.5D surface plot of merged fluorescence image in Figure 12g

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诺蒎酮基喹唑啉-2-胺型铜离子荧光探针的合成及其应用研究

Synthesis of Nopinone-Based Quinazolin-2-amine Fluorescent Probe for Detection of Cu²⁺ and Its Application Research

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诺蒎酮基喹唑啉-2-胺型铜离子荧光探针的合成及其应用研究

Synthesis of Nopinone-Based Quinazolin-2-amine Fluorescent Probe for Detection of Cu2+ and Its Application Research

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Synthesis of Nopinone-Based Quinazolin-2-amine Fluorescent Probe for Detection of Cu²⁺ and Its Application Research