Acta Chimica Sinica ›› 2019, Vol. 77 ›› Issue (10): 1036-1044.DOI: 10.6023/A19060226 Previous Articles     Next Articles

Special Issue: 分子探针、纳米生物学与生命分析化学



关晓琳a*(), 王林a, 李志飞a, 刘美娜a, 王凯龙a, 林斌a, 杨学琴a, 来守军b, 雷自强a   

  1. a 西北师范大学 生态环境相关高分子材料教育部重点实验室 甘肃省高分子材料重点实验室 化学化工学院 兰州 730070
    b 兰州文理学院化工学院 兰州 730000
  • 投稿日期:2019-06-21 发布日期:2019-08-13
  • 通讯作者: 关晓琳
  • 基金资助:

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

Guan, Xiaolina*(), Wang, Lina, Li, Zhifeia, Liu, Meinaa, Wang, Kailonga, Lin, Bina, Yang, Xueqinga, Lai, Shoujunb, Lei, Ziqianga   

  1. 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
  • Received:2019-06-21 Published:2019-08-13
  • Contact: Guan, Xiaolin
  • Supported by:
    Project supported by the National Natural Science Foundation of China(21761032);Project supported by the National Natural Science Foundation of China(51363019);the Key Laboratory of Ecological Environment Related Polymer Materials, Ministry of Education Open Fund(KF-18-05)

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 pro-cess. 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.

Key words: AIE, multiple sensitive response, polymer nanospheres, cell tracing, fluorescence imaging