Citation: Guan Xiaolin, Wang Lin, Li Zhifei, Liu Meina, Wang Kailong, Lin Bin, Yang Xueqing, Lai Shoujun, Lei Ziqiang. Preparation of Multi-stimulus Responsive Polymer Nanospheres Based on AIE Effect and Its Cell Tracing Application[J]. Acta Chimica Sinica, ;2019, 77(10): 1036-1044. doi: 10.6023/A19060226 shu

Preparation of Multi-stimulus Responsive Polymer Nanospheres Based on AIE Effect and Its Cell Tracing Application

Guan Xiaolin ^a,, ,
Wang Lin ^a ,
Li Zhifei ^a ,
Liu Meina ^a ,
Wang Kailong ^a ,
Lin Bin ^a ,
Yang Xueqing ^a ,
Lai Shoujun ^b ,
Lei Ziqiang ^a

a.
Key Laboratory of Eco-Environment-Related Polymer Materials Ministry of Education, Key Laboratory of Polymer Materials Ministry of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, China
b.
School of Chemical Engineering, Lanzhou University of Arts and Science, Lanzhou 730000, China

Corresponding author: Guan Xiaolin, guanxiaolin@nwnu.edu.cn
Received Date: 21 June 2019
Available Online: 13 October 2019
Fund Project: the National Natural Science Foundation of China 21761032the Key Laboratory of Ecological Environment Related Polymer Materials, Ministry of Education Open Fund KF-18-05Project supported by the National Natural Science Foundation of China (Nos. 21761032, 51363019) and the Key Laboratory of Ecological Environment Related Polymer Materials, Ministry of Education Open Fund (KF-18-05)the National Natural Science Foundation of China 51363019

Figures(9)

In recent years, fluorescent bioimaging technology has great advantages in the fields of life science research and medical diagnosis because of its advantages of fast and effective, high sensitivity, easy realization of multi-channel imaging and economic efficiency. Organic fluorescent dyes have been widely used as biological imaging reagents due to their excellent photoelectric properties, functional modification, adjustable optical properties, and good biocompatibility. However, conventional organic fluorescent molecules cause aggregation-caused quenching (ACQ) due to π-π stacking in the aggregated state, limiting their bioimaging applications in aggregated or high concentrations. Since the discovery of the unique luminescence phenomenon of aggregation-induced emission (AIE), the ACQ phenomenon of traditional fluorescent materials has been eliminated. Stimulating responsive polymer nanoparticles have been widely used in the life sciences due to their combination of nanoparticle and polymer advantages and their ability to respond intelligently with environmental changes. Therefore, nanomaterials with excellent aggregation-induced emission (AIE) property, environmental stimuli responsiveness and biocompatibility based on AIE molecules and smart responsive polymers have shown attractive application prospects in the life sciences. A kind of multi-responsive AIE-active polymer nanospheres, which were composed of tetraphenylethylene (TPE) and stimuli-responsive poly[N]-2-(diethylamino)-ethyl]acrylamide (PDEAEAM), were constructed in this study. Firstly, a multi-stimulation responsive monomer N-[2-(diethylamino)ethyl]acrylamide (DEAEAM) and TPE derivative tetraphenylethene-4-(12-hydroxydodecyl-2-methylpropionyl) (TPE-BIB) with propionyl bromide were synthesized, respectively, and a multi-stimuli-responsive amphiphilic polymer of tetraphenylethene-graft-poly[N-[2-(diethylamino)ethyl]acrylamide] (TPE-g-PDEAEAM) was then successfully synthesized by atom transfer radical polymerization (ATRP) using TPE-BIB as initiator. Lastly, polymer nanospheres TPE-g-PDEAEAM of approximately 200 nm were formed by a self-assembling process. The results of the performed experiments showed that the LCST of TPE-g-PDEAEAM in aqueous solution is about 60℃. Meanwhile, the luminescence change of TPE-g-PDEAEAM at different temperatures from 20 to 66℃ was observed. The fluorescence intensity of TPE-g-PDEAEAM firstly decreased with increasing temperature from 20 to 58℃, and the fluorescence intensity increased with increasing temperature from 58 to 66℃. The phase transfer of PDEAEAM in TPE-g-PDEAEAM may be the reason of luminescence change which may lead to the fluorescent temperature response. Moreover, the fluorescence intensity of TPE-g-PDEAEAM nanospheres in aqueous solution increased with increasing temperature pH. Besides, the fluorescence intensity of TPE-g-PDEAEAM decreased dramatically when the volume of CO₂ increased from 0.0 to 1.2 mL. Therefore, TPE-g-PDEAEAM was a new temperature and pH/CO₂ responsive materials and might be used as multi-functional smart fluorescent sensors. More importantly, the fluorescent signals were significantly strong in HeLa cells after cells were incubated with TPE-g-PDEAEAM for 24 h based on the characteristic of AIE fluorescence and low cytotoxicity. The resultant nanospheres were able to be internalized by the cancer cells and effectively track the HeLa cells for as long as 11 passages. So, the polymer nanomaterial is an ideal living cell fluorescent tracer probe, which is expected to be applied as biosensors, long-term cell traces and medical biomaterials.
- AIE,
- multiple sensitive response,
- polymer nanospheres,
- cell tracing,
- fluorescence imaging
1. [1]
  Xia, Z. Q.; Shao, A. D.; Li, Q.; Zhu, S. Q.; Zhu, W. H. Acta Chim. Sinica 2016, 74, 351.
2. [2]
  Guo, S.; Zheng, F.; Zeng, F.; Wu, S. Z. Chinese J. Polym. Sci. 2016, 34, 830. doi: 10.1007/s10118-016-1793-5
3. [3]
  Chen, Y.; Qiu, T.; Zhao, W.; Fan, L. Polym. Chem. 2015, 6, 1576. doi: 10.1039/C4PY01615G
4. [4]
  Yu, C.; Li, X.; Zeng, F.; Zheng, F.; Wu, S. Z. Chem. Commun. 2013, 49, 403. doi: 10.1039/C2CC37329G
5. [5]
  Sun, J. B.; Zhang, G. H.; Jia, X. Y.; Xue, P. C.; Jia, J. H.; Lu, R. Acta Chim. Sinica 2016, 74, 165.
6. [6]
  Xu, S. Y.; Sun, X.; Ge, H.; Arrowsmith, R. L.; Fossey, J. S.; Pascu, S. I.; Jiang, Y. B.; James, T. D. Org. Biomol. Chem. 2015, 13, 4143. doi: 10.1039/C4OB02267J
7. [7]
  Mei, J.; Leung, N. L.; Kwok, R. T.; Lam, J. W.; Tang, B. Z. Chem. Rev. 2015, 115, 11718. doi: 10.1021/acs.chemrev.5b00263
8. [8]
  Gao, M.; Hu, Q.; Feng, G.; Tang, B. Z.; Liu, B. J. Mater. Chem. B 2014, 2, 3438. doi: 10.1039/C4TB00345D
9. [9]
  Liu, Z.; Xue, W.; Cai, Z.; Zhang, G.; Zhang, D. J. Mater. Chem. 2011, 21, 14487. doi: 10.1039/c1jm12400e
10. [10]
  Tang, X.; Bai, Q.; Peng, Q.; Gao, Y.; Li, J.; Liu, Y.; Yao, L.; Lu, P.; Yang, B.; Ma, Y. Chem. Mater. 2015, 27, 7050. doi: 10.1021/acs.chemmater.5b02685
11. [11]
  Zhang, Y.; Kong, L.; Shi, J.; Tong, B.; Zhi, J.; Feng, X.; Dong, Y. Chin. J. Chem. 2015, 33, 701. doi: 10.1002/cjoc.201500116
12. [12]
  Hu, F.; Zhang, G.; Zhan, C.; Zhang, W.; Yan, Y.; Zhao, Y.; Fu, H.; Zhang, D. Small 2015, 11, 1335. doi: 10.1002/smll.201402051
13. [13]
  Hu, R.; Xin, D. H.; Qin, A. J.; Tang, B. Z. Acta Polymerica Sinica 2018, 2, 132. doi: 10.11777/j.issn1000-3304.2018.17280
14. [14]
  Jiang, M. J.; Guo, Z. J.; Tang, B. Z. Sci. Technol. Rev. 2018, 36, 27.
15. [15]
  Gao, Y.; Qu, Y.; Jiang, T.; Zhang, H.; He, N.; Li, B.; Wu, J.; Hua, J. J. Mater. Chem. C 2014, 2, 6353.
16. [16]
  Li, S.; Langenegger, S. M.; Häner, R. Chem. Commun. 2013, 49, 5835. doi: 10.1039/c3cc42706d
17. [17]
  Singh, A.; Lim, C. K.; Lee, Y. D.; Maeng, J. H.; Lee, S.; Koh, J.; Kim, S. ACS Appl. Mater. Interfaces 2013, 5, 8881. doi: 10.1021/am4012066
18. [18]
  Ma, S. Q.; Ma, L.; Han, W. K.; Jiang, S.; Xu, B.; Tian, W. J. Sci. China Chem. 2018, 48, 683.
19. [19]
  Wang, Z. L.; Yang, J. L.; Yang, Y. Q.; Xu, X.; Li, M. X.; Zhang, Y.; Fang, H.; Xu, H. J.; Wang, S. F. Chin. J. Org. Chem. 2018, 38, 1401.
20. [20]
  Wang, Z.; Chen, S.; Lam, J. W. Y. J. Am. Chem. Soc. 2013, 135, 8238. doi: 10.1021/ja312581r
21. [21]
  Wang, D.; Su, H. F.; Tang, B. Z. Chem. Sci. 2018, 9, 3685. doi: 10.1039/C7SC04963C
22. [22]
  Wang, J.; Wu, Y. L.; Sun, L. H.; Zeng, F.; Wu, S. Z. Acta Chim. Sinica 2016, 74, 910.
23. [23]
  Chen, S.; Jiang, F. J.; Cao, Z. Q.; Wang, G. J.; Dang, Z. M. Chem. Commun. 2015, 51, 12633. doi: 10.1039/C5CC04087F
24. [24]
  Guo, J.; Wang, N. J.; Peng, L.; Wu, J. J.; Ye, Q. Q.; Yuan, J. Y. J. Mater. Chem. B 2016, 4, 4009.
25. [25]
  Yuan, T. T.; Dong, J.; Hana, G. X.; Wang, G. J. RSC Adv. 2016, 6, 10904. doi: 10.1039/C5RA26894J
26. [26]
  Karimi, M.; Ghasemi, A.; Zangabad, P. S.; Rahighi, R.; Beyzavi, J. A.; Vaseghi, K. A.; Haghani, M. L.; Bahramia, N. S.; Hamblin, M. R. Chem. Soc. Rev. 2016, 45, 1457. doi: 10.1039/C5CS00798D
27. [27]
  Guan, X. L; Meng, L.; Jin, Q. J.; Lu, B. C.; Chen, Y. B.; Li, Z. F.; Wang, L.; Lai, S. J.; Lei, Z. Q. Macromol. Mater. Eng. 2018, 303, 1700553. doi: 10.1002/mame.201700553
28. [28]
  Wang, Z.; Yong, T. Y.; Wan, J.; Li, Z. H.; Zhao, H.; Zhao, Y.; Gan, L.; Yang, X. L.; Xu, H. B.; Zhang, C. ACS Appl. Mater. Interfaces 2015, 7, 3420. doi: 10.1021/am509161y
29. [29]
  Yuan, Y.; Kwok, R. T. K.; Tang, B. Z.; Liu, B. Small 2015, 11, 4682. doi: 10.1002/smll.201501498
30. [30]
  Song, Z.; Wang, K.; Gao, C.; Wang, S.; Zhang, W. Q. Macromolecules 2016, 49, 162. doi: 10.1021/acs.macromol.5b02458
31. [31]
  Jiang, X.; Feng, C.; Lu, G.; Huang, X. ACS Macro Lett. 2014, 3, 1121. doi: 10.1021/mz5005822
32. [32]
  Zhang, G. Z.; Jiang, M.; Wu, Q. Chin. Polym. Bull. 2005, 4, 82.
33. [33]
  Anirudhan, T. S.; Nair, A. S. J. Mater. Chem. B 2018, 6, 428. doi: 10.1039/C7TB02292A
34. [34]
  Zhang, Y. F.; Wu, T.; Liu, S. Y. Macromol. Chem. Phys. 2007, 208, 2492. doi: 10.1002/macp.200700293
1. [1]
  Siyi ZHONG , Xiaowen LIN , Jiaxin LIU , Ruyi WANG , Tao LIANG , Zhengfeng DENG , Ao ZHONG , Cuiping HAN . Targeting imaging and detection of ovarian cancer cells based on fluorescent magnetic carbon dots. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1483-1490. doi: 10.11862/CJIC.20240093
2. [2]
  Xing Tian , Di Wu , Wanheng Wei , Guifu Dai , Zhanxian Li , Benhua Wang , Mingming Yu . A lipid droplets-targetable fluorescent probe for polarity detection in cells of iron death, inflammation and fatty liver tissue. Chinese Chemical Letters, 2024, 35(6): 108912-. doi: 10.1016/j.cclet.2023.108912
3. [3]
  Donghui PAN , Yuping XU , Xinyu WANG , Lizhen WANG , Junjie YAN , Dongjian SHI , Min YANG , Mingqing CHEN . Preparation and in vivo tracing of ⁶⁸Ga-labeled PM_2.5 mimetic particles for positron emission tomography imaging. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 669-676. doi: 10.11862/CJIC.20230468
4. [4]
  Di WU , Ruimeng SHI , Zhaoyang WANG , Yuehua SHI , Fan YANG , Leyong ZENG . Construction of pH/photothermal dual-responsive delivery nanosystem for combination therapy of drug-resistant bladder cancer cell. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1679-1688. doi: 10.11862/CJIC.20240135
5. [5]
  Yue WANG , Zhizhi GU , Jingyi DONG , Jie ZHU , Cunguang LIU , Guohan LI , Meichen LU , Jian HAN , Shengnan CAO , Wei WANG . Effects of kelp-derived carbon dots on embryonic development of zebrafish. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1209-1217. doi: 10.11862/CJIC.20230423
6. [6]
  Jinlong YAN , Weina WU , Yuan WANG . A simple Schiff base probe for the fluorescent turn-on detection of hypochlorite and its biological imaging application. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1653-1660. doi: 10.11862/CJIC.20240154
7. [7]
  Peiyan Zhu , Yanyan Yang , Hui Li , Jinhua Wang , Shiqing Li . Rh(Ⅲ)‐Catalyzed sequential ring‐retentive/‐opening [4 + 2] annulations of 2H‐imidazoles towards full‐color emissive imidazo[5,1‐a]isoquinolinium salts and AIE‐active non‐symmetric 1,1′‐biisoquinolines. Chinese Chemical Letters, 2024, 35(10): 109533-. doi: 10.1016/j.cclet.2024.109533
8. [8]
  Xin MA , Ya SUN , Na SUN , Qian KANG , Jiajia ZHANG , Ruitao ZHU , Xiaoli GAO . A Tb₂ complex based on polydentate Schiff base: Crystal structure, fluorescence properties, and biological activity. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1347-1356. doi: 10.11862/CJIC.20230357
9. [9]
  Zhaoyang WANG , Chun YANG , Yaoyao Song , Na HAN , Xiaomeng LIU , Qinglun WANG . Lanthanide(Ⅲ) complexes derived from 4′-(2-pyridyl)-2, 2′∶6′, 2″-terpyridine: Crystal structures, fluorescent and magnetic properties. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1442-1451. doi: 10.11862/CJIC.20240114
10. [10]
  Guimin ZHANG , Wenjuan MA , Wenqiang DING , Zhengyi FU . Synthesis and catalytic properties of hollow AgPd bimetallic nanospheres. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 963-971. doi: 10.11862/CJIC.20230293
11. [11]
  Xiutao Xu , Chunfeng Shao , Jinfeng Zhang , Zhongliao Wang , Kai Dai . Rational Design of S-Scheme CeO₂/Bi₂MoO₆ Microsphere Heterojunction for Efficient Photocatalytic CO₂ Reduction. Acta Physico-Chimica Sinica, 2024, 40(10): 2309031-. doi: 10.3866/PKU.WHXB202309031
12. [12]
  Qi Li , Pingan Li , Zetong Liu , Jiahui Zhang , Hao Zhang , Weilai Yu , Xianluo Hu . Fabricating Micro/Nanostructured Separators and Electrode Materials by Coaxial Electrospinning for Lithium-Ion Batteries: From Fundamentals to Applications. Acta Physico-Chimica Sinica, 2024, 40(10): 2311030-. doi: 10.3866/PKU.WHXB202311030
13. [13]
  Peiran ZHAO , Yuqian LIU , Cheng HE , Chunying DUAN . A functionalized Eu³⁺ metal-organic framework for selective fluorescent detection of pyrene. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 713-724. doi: 10.11862/CJIC.20230355
14. [14]
  Jiakun BAI , Ting XU , Lu ZHANG , Jiang PENG , Yuqiang LI , Junhui JIA . A red-emitting fluorescent probe with a large Stokes shift for selective detection of hypochlorous acid. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1095-1104. doi: 10.11862/CJIC.20240002
15. [15]
  Endong YANG , Haoze TIAN , Ke ZHANG , Yongbing LOU . Efficient oxygen evolution reaction of CuCo₂O₄/NiFe-layered bimetallic hydroxide core-shell nanoflower sphere arrays. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 930-940. doi: 10.11862/CJIC.20230369
16. [16]
  Qiangqiang SUN , Pengcheng ZHAO , Ruoyu WU , Baoyue CAO . Multistage microporous bifunctional catalyst constructed by P-doped nickel-based sulfide ultra-thin nanosheets for energy-efficient hydrogen production from water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1151-1161. doi: 10.11862/CJIC.20230454
17. [17]
  Yuanpei ZHANG , Jiahong WANG , Jinming HUANG , Zhi HU . Preparation of magnetic mesoporous carbon loaded nano zero-valent iron for removal of Cr(Ⅲ) organic complexes from high-salt wastewater. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1731-1742. doi: 10.11862/CJIC.20240077
18. [18]
  Xinyu ZENG , Guhua TANG , Jianming OUYANG . Inhibitory effect of Desmodium styracifolium polysaccharides with different content of carboxyl groups on the growth, aggregation and cell adhesion of calcium oxalate crystals. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1563-1576. doi: 10.11862/CJIC.20230374
19. [19]
  Yonghui ZHOU , Rujun HUANG , Dongchao YAO , Aiwei ZHANG , Yuhang SUN , Zhujun CHEN , Baisong ZHU , Youxuan ZHENG . Synthesis and photoelectric properties of fluorescence materials with electron donor-acceptor structures based on quinoxaline and pyridinopyrazine, carbazole, and diphenylamine derivatives. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 701-712. doi: 10.11862/CJIC.20230373
20. [20]
  Zongfei YANG , Xiaosen ZHAO , Jing LI , Wenchang ZHUANG . Research advances in heteropolyoxoniobates. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 465-480. doi: 10.11862/CJIC.20230306

Get Citation

PDF

XML

Metrics

PDF Downloads(27)
Abstract views(1876)
HTML views(377)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142