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

doi:10.6023/A19060226

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

Special Issue: 分子探针与纳米生物学

Article

基于AIE效应的多重刺激响应性聚合物纳米微球的制备及其细胞示踪应用

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

^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 E-mail:guanxiaolin@nwnu.edu.cn
基金资助:
项目受国家自然科学基金(21761032);项目受国家自然科学基金(51363019);生态环境相关高分子材料教育部重点实验室开放基金(KF-18-05)

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

Received:2019-06-21 Published:2019-08-13
Contact: Guan, Xiaolin E-mail:guanxiaolin@nwnu.edu.cn
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)

1. Preparation of Multi-stimulus Responsive Polymer Nanospheres Based on AIE Effect and Its Cell Tracing Application.PDF(632KB)

Abstract

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

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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.

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Fig. & Tab. 9

Figure 1. Synthetic route of the polymer TPE-g-PDEAEAM

Figure 2. (a) Hydrodynamic size with concentration of 2 mg/mL. Inset: Photograph of TPE-g-PDEAEAM solutions in water under irradiation of laser point. (b) SEM image of TPE-g-PDEAEAM polymer dots

Figure 3. (a) Fluorescence spectra of aqueous solutions of TPE-g-PDEAEAM at different concentrations (ex=337 nm). (b) Relative changes in fluorescence intensity of different concentrations of TPE-g-PDEAEAM aqueous solution and digital photographs under UV light (365 nm)

Figure 4. (a) Fluorescence spectra of TPE-g-PDEAEAM in a mixed solvent of water and THF (λex=337 nm). (b) The relative change in fluorescence intensity of TPE-g-PDEAEAMTPE in a water/THF mixed solvent and its digital photograph under UV light (365 nm)

Figure 5. TPE-g-PDEAEAM polymer quantum dots in a variable temperature ultraviolet (UV) concentration of 2 g/L. Inset: Photograph of visible light in TPE-PDEAEAM solution at 25 ℃ (left) and 65 ℃ (right)

Figure 6. (a) Fluorescent spectra of the TPE-g-PDEAEAM in aqueous solution with temperature increasing from 20 to 66 ℃. [TPE-g- PDEAEAM]=2.0 g/L. λex=337 nm. Inset: Photo of TPE-g-PDEAEAM solution under 25 ℃ (left) and 65 ℃ (right) under visible and UV light. (b) Change of relative fluorescent intensity (I/I0) of TPE-g-PDEAEAM in aqueous solution under different temperature

Figure 7. (a) Fluorescent spectra of the TPE-g-PDEAEAM in different pH solution. (b) Change of relative fluorescent intensity (I/I0) of TPE-g-PDEAEAM in aqueous solution under different pH. [TPE-g-PDEAEAM]=2.0 g/L

Figure 8. (a) Fluorescence spectra of TPE-g-PDEAEAM in different CO2 volume solutions. Inset: Digital photo of a 2 mg/mL TPE-g- PDEAEAM aqueous solution under UV light (365 nm) before and after carbon dioxide. (b) The relationship between the linearity of relative fluorescence intensity (I/I0) and the volume of CO2

Figure 9. (a) Cell viabilities of HeLa cells treated with different concentrations of TPE-g-PDEAEAM for 48 h by MTT assay. (b) Confocal microscopy images of HeLa cells TPE-g-PDEAEAM staining (100 μg/mL) in different algebras. The scale bar is 25 μm

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基于AIE效应的多重刺激响应性聚合物纳米微球的制备及其细胞示踪应用

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

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