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

doi:10.6023/cjoc202008049

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (3): 1168-1176.DOI: 10.6023/cjoc202008049 Previous Articles Next Articles

ARTICLES

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

1. cjoc202008049辅助材料.pdf(1369KB)

Abstract

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

Cite this article

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.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 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

References 47

[1]	Chen, S. H.; Pang, C. M.; Chen, X. Y.; Yan, Z. H.; Huang, S. M.; Li, X. D.; Zhong, Y. T.; Wang, C. Y. Chin. J. Org. Chem. 2019, 39, 1846. (in Chinese) doi: 10.6023/cjoc201901033
	(陈思鸿, 庞楚明, 陈孝云, 严智浩, 黄诗敏, 李香弟, 钟雅婷, 汪朝阳, 有机化学, 2019, 39, 1846.)
[2]	Yue, Y.; Huo, F.; Cheng, F. Chem. Soc. Rev. 2019, 48, 4155. doi: 10.1039/c8cs01006d pmid: 31204740
[3]	Ma, C.; Zhong, G.; Zhao, Y. Spectrochim. Acta, Part A 2020,118545.
[4]	Singh, H.; Tiwari, K.; Tiwari, R. Chem. Rev. 2019, 119, 11718. doi: 10.1021/acs.chemrev.9b00379 pmid: 31724399
[5]	Chen, X.; Pradhan, T.; Wang, F. Chem. Rev. 2012, 112, 1910. doi: 10.1021/cr200201z pmid: 22040233
[6]	Cao, D.; Liu, Z.; Verwilst, P. Chem. Rev. 2019, 119, 10403. doi: 10.1021/acs.chemrev.9b00145 pmid: 31314507
[7]	Shi, Y.; Yu, Y. W.; Xue, L.; Wang, Y. F. Chin. J. Org. Chem. 2019, 39, 3414. (in Chinese) doi: 10.6023/cjoc201906015
	(石岩, 于有伟, 薛林, 王延风, 有机化学, 2019, 39, 3414.)
[8]	Zhao, Y.; Luo, Y.; Wang, H. Anal. Chim. Acta 2019, 1065, 134. doi: 10.1016/j.aca.2019.03.029 pmid: 31005146
[9]	Patil, A.; Salunke, G. S. Inorg. Chim. Acta 2018, 482, 99. doi: 10.1016/j.ica.2018.05.026
[10]	Han, Z.; Nan, D.; Yang, H. Sens. Actuators, B 2019, 298, 126842. doi: 10.1016/j.snb.2019.126842
[11]	Murugan, N.; Prakash, M.; Jayakumar, M. Appl. Surf. Sci. 2019, 476, 468. doi: 10.1016/j.apsusc.2019.01.090
[12]	Zhang, Y.; Li, H.; Pu, S. J. Photochem. Photobiol., A 2020,112721.
[13]	Wang, R.; Zhang, L.; Liu, R. Carbohydr. Polym. 2019, 223, 115117. doi: 10.1016/j.carbpol.2019.115117 pmid: 31427014
[14]	Meng, X. J.; Zhao, J. Z.; Ma, W. B. Chin. J. Org. Chem. 2020, 40, 276. (in Chinese) doi: 10.6023/cjoc201908039
	(孟宪娇, 赵晋忠, 马文兵, 有机化学, 2020, 40, 276.)
[15]	Que, E. L.; Domaille, D. W.; Chang, C. J. Chem. Rev. 2008, 108, 1517. doi: 10.1021/cr078203u pmid: 18426241
[16]	Mathie, A.; Sutton, G. L.; Clarke, C. E. Pharmacol. Ther. 2006, 111, 567. doi: 10.1016/j.pharmthera.2005.11.004 pmid: 16410023
[17]	Georgopoulos, A.; Yonone, L. M.; Opiekun, R. E. J. Toxicol. Environ. Health, Part B 2001, 4, 341. doi: 10.1080/109374001753146207
[18]	Barnham, K.; Masters, C.; Bush, A. Nat. Rev. Drug Discovery 2004, 3, 205. doi: 10.1038/nrd1330 pmid: 15031734
[19]	Meng, Q.; Shi, Y.; Wang, C. Org. Biomol. Chem. 2015, 13, 2918. doi: 10.1039/c4ob02178a pmid: 25569711
[20]	Chen, D.; Chen, P.; Zong, L. R. Soc. Open Sci. 2017, 4, 171161. doi: 10.1098/rsos.171161 pmid: 29291102
[21]	Chen, F.; Hou, F.; Huang, L. Dyes Pigm. 2013, 98, 146. doi: 10.1016/j.dyepig.2013.01.026
[22]	Gaggelli, E.; Kozlowski, H.; Valensin, D. Chem. Rev. 2006, 106, 1995. doi: 10.1021/cr040410w pmid: 16771441
[23]	Dell'Acqua, S.; Pirota, V.; Anzani, C.; Rocco, M. M.; Nicolis, S.; Valensin, D.; Monzani, E.; Casella, L. Metallomics 2015, 7, 1091. doi: 10.1039/c4mt00345d pmid: 25865825
[24]	World Health Organization Guidelines for Drinking-Water Quality, 2004.
[25]	Jonas, R. Appl. Environ. Microbiol. 1989, 55, 43. doi: 10.1128/AEM.55.1.43-49.1989 pmid: 16347833
[26]	Xiao, Q.; Gao, H.; Yuan, Q. J. Chromatogr., A 2013, 1274, 145. doi: 10.1016/j.chroma.2012.12.016
[27]	Wang, X.; Luo, C.; Li, L. J. Electroanal. Chem. 2015, 757, 100. doi: 10.1016/j.jelechem.2015.09.023
[28]	Selvarajan, S.; Alluri, N.; Chandrasekhar, R. Biosensors Bioelectron. 2017, 91, 203. doi: 10.1016/j.bios.2016.12.006
[29]	Ahmed, K.; Sengan; Veerappan, A. Sens. Actuators, B 2016, 233, 431. doi: 10.1016/j.snb.2016.04.125
[30]	Li, Y.; Zhou, H.; Yin, S. Sens. Actuators, B 2016, 235, 33. doi: 10.1016/j.snb.2016.05.055
[31]	He, C.; Zhou, H.; Yang, N. New J. Chem. 2018, 42, 2520. doi: 10.1039/C7NJ03911E
[32]	Duan, G.; Zhang, G.; Yuan, S. Spectrochim. Acta, Part A 2019, 219, 173. doi: 10.1016/j.saa.2019.04.057
[33]	Zheng, X.; Ji, R.; Cao, X. Anal. Chim. Acta 2017, 978, 48. doi: 10.1016/j.aca.2017.04.048 pmid: 28595726
[34]	Wang, Y.; Liu, S.; Chen, H. Dyes Pigm. 2017, 142, 293. doi: 10.1016/j.dyepig.2017.03.051
[35]	Liu, S.; Liu, Y.; Pan, H. Tetrahedron Lett. 2.018, 59, 108.
[36]	Feng, Y.; Yang, Y.; Wang, Y. Sens. Actuators, B 2019, 288, 27. doi: 10.1016/j.snb.2019.02.062
[37]	Yin, G.; Yao, J.; Hong, S. Analyst 2019, 144, 6962. doi: 10.1039/c9an01451a pmid: 31621707
[38]	Zhang, X.; Sun, P.; Li, F. Sens. Actuators, B 2018, 255, 366. doi: 10.1016/j.snb.2017.07.196
[39]	Xu, Z.; Wang, H.; Chen, Z. Spectrochim. Acta, Part A 2019, 216, 404. doi: 10.1016/j.saa.2019.03.062
[40]	Zhu, D.; Luo, Y.; Shuai, L. Tetrahedron Lett. 2016, 57, 5326. doi: 10.1016/j.tetlet.2016.10.056
[41]	Choi, M.; Kim, G.; Hong, J. Tetrahedron Lett. 2016, 57, 975.
[42]	Wang, Y.; Zhou, J.; Zhao, L. Dyes Pigm. 2020,108513.
[43]	Huang, C.; Li, H.; Luo, Y. Dalton Trans. 2014, 43, 8102. doi: 10.1039/c4dt00014e pmid: 24723120
[44]	Shen, R.; Yang, J.; Luo, H. Tetrahedron 2017, 73, 373. doi: 10.1016/j.tet.2016.12.016
[45]	Liu, Y.; Yang, L.; Li, P. Spectrochim. Acta, Part A 2020, 227, 117540. doi: 10.1016/j.saa.2019.117540
[46]	Peng, L.; Zhao, Q.; Wang, D. Sens. Actuators, B 2009, 136, 80. doi: 10.1016/j.snb.2008.10.057
[47]	Jiang, Q.; Wang, Z., Li, M. Dyes Pigm. 2019, 171, 107702. doi: 10.1016/j.dyepig.2019.107702

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

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 14

References 47

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Yingzhen Zhang, Dandan Jiang, Juanhua Li, Jingjing Wang, Kunming Liu, Jinbiao Liu. Construction Strategy and Imaging of Highly Selective Selenocysteine Fluorescent Probes [J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 41-53.
[2]	Huanqing Li, Zhaohua Chen, Zujia Chen, Qiwen Qiu, Youcai Zhang, Sihong Chen, Zhaoyang Wang. Research Progress in Mercury Ion Fluorescence Probes Based on Organic Small Molecules [J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3067-3077.
[3]	Binghui Ding, Shaohui Han, Haiqing Xiong, Benhua Wang, Bojun Zuo, Xiangzhi Song. A Highly Selective Ratiometric Fluorescent Probe for the Detection of Hypochlorite in Acute Lung Injury [J]. Chinese Journal of Organic Chemistry, 2023, 43(8): 2878-2884.
[4]	Yifang Li, Yao Wang, Huawei Niu, Xiujin Chen, Zhaozhou Li, Yongguo Wang. Research Progress of Sulfur Dioxide Fluorescent Probe Targeting Mitochondria [J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 1952-1962.
[5]	Feiran Liu, Jing Jing, Xiaoling Zhang. Research Progress of Fluorescent Probes for Cysteine Targeting Cellular Organelles [J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 2053-2067.
[6]	Tiantian Liu, Hongpeng Zhang, Xiaomeng Jiao, Yinjuan Bai. Research Progress of Multi-signal Fluorescent Probes for Simultaneous Detection of Biothiols [J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 2081-2095.
[7]	Zhihua Chen, Yan Hu, Lili Ma, Ziyi Zhang, Chuanxiang Liu. Rational Design of ortho-Vinylhydropyridine-Assisted Amino-fluorophore as Hypochlorite Fluorescent Probe [J]. Chinese Journal of Organic Chemistry, 2023, 43(2): 718-724.
[8]	Hongwei Tang, Chao Wang, Keli Zhong, Shuhua Hou, Lijun Tang, Yanjiang Bian. A Naked-Eye and Fluorescent Dual-Channel Probe for Rapid Detection of Hg²⁺ and Its Multiple Applications [J]. Chinese Journal of Organic Chemistry, 2023, 43(2): 712-717.
[9]	Meng Liu, Yanru Huang, Xiaofei Sun, Lijun Tang. An “Aggregation-Induced Emission+Excited-State Intramolecular Proton Transfer” Mechanisms-Based Benzothiazole Derived Fluorescent Probe and Its ClO^–Recognition [J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 345-351.
[10]	Yangyang Li, Xiaofei Sun, Xiaoling Hu, Yuanyuan Ren, Keli Zhong, Xiaomei Yan, Lijun Tang. Synthesis of Triphenylamine Derivative and Its Recognition for Hg²⁺ with “OFF-ON” Fluorescence Response Based on Aggregation-Induced Emission (AIE) Mechanism [J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 320-325.
[11]	Jidong Zhang, Wanlin Yan, Wenqiang Hu, Dian Guo, Dalong Zhang, Xiaoxin Quan, Xianpan Bu, Siyu Chen. Design and Synthesis of a Zn²⁺ Fluorescent Probe Based on Aggregation Induced Luminescence Properties [J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 326-331.
[12]	Yanhui Ma, Yuqian Wu, Xiaoxu Wang, Gui Gao, Xin Zhou. Research Progress of Near-Infrared Fluorescent Probes Based on 1,3-Dichloro-7-hydroxy-9,9-dimethyl-2(9H)-acridone (DDAO) [J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 94-111.
[13]	Yaxin Yang, Lin Chen, Xiaoling Hu, Keli Zhong, Shidi Li, Xiaomei Yan, Jinglin Zhang, Lijun Tang. Synthesis of a Turn-On Fluorescent Probe for Hydrogen Sulfide and Its Application in Red Wine and Living Cells [J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 308-312.
[14]	Chuntian Shi, Mei Yu, Aibin Wu, Jiangxiong Luo, Xiaojun Li, Ningchen Wang, Wenming Shu, Weichu Yu. A Water-Soluble Naphthalimide-Based Fluorescent Probe for Specific Sensing of Fe³⁺ and $\text{C}{{\text{r}}_{2}}\text{O}_{7}^{2-}$ [J]. Chinese Journal of Organic Chemistry, 2022, 42(9): 2806-2813.
[15]	Yanqin Lai, Xue Chen, Fang Chen, Linchen Ni, Ting Wang, Ziping Zhu, Ju Man, Chunxiao Jiang, Zhenda Xie. A Lysosome-Targeted Far-Red to Near-Infrared Fluorescent Probe for Monitoring Viscosity Change During the Ferroptosis Process [J]. Chinese Journal of Organic Chemistry, 2022, 42(9): 2850-2856.