Citation: Xiao-Lin GUAN, Yuan-Yuan DING, Shou-Jun LAI, Xue-Qin YANG, Jing-Yu WEI, Jia-Ming ZHANG, Li-Yuan ZHANG, Jin-Hui TONG, Zi-Qiang LEI. Ultra-small Size Rare Earth Complex Fluorescent Nanoprobe for Dual Color Imaging of Tumor Cells Constructed with PCL-b-PNIPAM Coordinated Eu(Ⅲ)[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(6): 1023-1036. doi: 10.11862/CJIC.2022.097 shu

Ultra-small Size Rare Earth Complex Fluorescent Nanoprobe for Dual Color Imaging of Tumor Cells Constructed with PCL-b-PNIPAM Coordinated Eu(Ⅲ)

1.
Key Laboratory of Eco-functional Polymer Materials of the Ministry of Education, Key Laboratory of Polymer Materials of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, China
2.
School of Chemical Engineering, Lanzhou University of Arts and Science, Lanzhou 730000, China

Corresponding author: Xiao-Lin GUAN, guanxiaolin@nwnu.edu.cn
Received Date: 30 August 2021
Revised Date: 24 February 2022

Figures(6)

Three amphiphilic block copolymers 1s-TPE-PCL-b-PNIPAM, 2s-TPE-PCL-b-PNIPAM, and 4s-TPE-PCL -b-PNIPAM (PCL=polycaprolactone, PNIPAM=poly(N - isopropylacrylamide)) were synthesized by in situ polymerization with tetraphenylethylene (TPE) fluorescent small molecules as the center. Then, the rare earth element Eu(Ⅲ) was coordinated with the hydrophilic fragment PNIPAM to synthesize block copolymer-Eu(Ⅲ) complexes (1s-TPE-PCL-b-PNIPAM-Eu(Ⅲ) for one-arm, 2s-TPE-PCL-b -PNIPAM-Eu(Ⅲ) for two-arm, and 4s-TPE-PCL-b-PNIPAM-Eu(Ⅲ) for four-arm). Finally, non-semiconductor polymer dots (Pdots) were prepared by self-assembly of the complexes in water. The three kinds of Pdots had excellent water solubility and ultra-small particle size below 5 nm (average particle sizes were 4.8, 4.3, and 2.7 nm, respectively). The optical test results showed that the single, double, and fourarm Pdots mainly emitted blue light at 430 nm under the excitation of 360 nm, and exhibited excellent aggregation-induced emission characteristics. At 395 nm, the red emission was mainly at 615 nm, and there had little mutual interference because of blue-red emission wavelength spacing was as high as 195 nm, showing excellent double fluorescence properties. The four-arm Pdots aqueous solution had a wider range of color changes and a better double fluorescence effect. In addition, the lower critical solution temperatures (LCSTs) of the three Pdots were 32, 36, and 37 ℃, respectively. While the LCSTs of the four -arm Pdots were closer to the normal body temperature. At the same time, the conformation of the PNIPAM chain in Pdots changed from expansion state to contraction state along with the increase of temperature. As a result, the aggregation degree of TPE on the chain was enhanced, which caused the temperature response of Pdots aqueous solution fluorescence. Ultimately, cytotoxicity and cell imaging studies showed that the three Pdots had low cytotoxicity and could enter HeLa, A549, and HepG2 tumor cells by endocytosis. Under different excitation wavelengths, strong blue or red fluorescence signals could be received in the cells, exhibiting blue/red dual-color fluorescence imaging ability and reversible dual-color fluorescence switching function. In addition, the comparison of the three Pdots found that the four-arm Pdots had the smallest particle size, the best dual fluorescence performance, and the best cell imaging effect.
- polymer dots,
- amphiphilic block copolymer,
- Eu(Ⅲ) complex,
- small size,
- dual fluorescence,
- cell imaging
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Ultra-small Size Rare Earth Complex Fluorescent Nanoprobe for Dual Color Imaging of Tumor Cells Constructed with PCL-b-PNIPAM Coordinated Eu(Ⅲ)

南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积

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通讯作者: 陈斌, bchen63@163.com