三元共聚法制备高亮度近红外二区荧光共轭聚合物纳米粒子及其二区光热治疗应用  

Enhanced Imaging Brightness of NIR-Ⅱ Fluorescent Conjugated Polymer Nanoparticles Prepared by Ternary Copolymerization Method and Its NIR-Ⅱ Photothermal Application

作　　者：张华[1] 孙鹏飞[1] 范曲立[1] 黄维[2] Hua Zhang;Peng-fei Sun;Qu-li Fan;Wei Huang(Key Laboratory for Organic Electronics and Information Displays&Institute of Advanced Materials(IAM),Jiangsu National Synergetic Innovation Center for Advanced Materials(SICAM),Nanjing University of Posts and Telecommunications,Nanjing 210023;Frontiers Science Center for Flexible Electronics&Shaanxi Institute of Flexible Electronics,Northwestern Polytechnical University,Xi’an 710072)

机构地区：[1]南京邮电大学有机电子与信息显示国家重点实验室培育基地信息材料与纳米技术研究院,江苏先进生物与化学制造协同创新中心,南京210023 [2]西北工业大学柔性电子前沿科学中心,陕西柔性电子研究所,西安710072

出　　处：《高分子学报》2021年第10期1343-1352,共10页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号21674048,21604042);江苏省自然科学基金(基金号BK20201380);有机电子协同创新中心资助项目。

摘　　要：为获得同时具有优异的溶解性,高亮度的近红外二区(NIR-Ⅱ,1000~1700 nm)荧光和强的NIR-Ⅱ光热转换能力的共轭聚合物,采用三元共聚策略构建了基于强电子受体和供体的NIR-Ⅱ发射共轭骨架.在此基础上,进一步通过调控电子给体BDT与2TC之间的比例,得到了一系列具有NIR-Ⅱ吸收和优异溶解性的共轭聚合物(BDT-2TC12,BDT-2TC11,BDT-2TC21).这些聚合物在700~1200 nm具有较强的NIR吸收,并在808 nm激光激发下表现出在1000~1400 nm区域内的优异NIR-Ⅱ荧光性能.利用纳米沉积的方法,将目标聚合物BDT-2TC12用两亲性的二硬脂酰磷脂酰乙酰胺-甲氧基聚乙二醇(DSPE-mPEG)进行包覆,制备得到水溶性良好的纳米粒子(BDT-2TC12NPs).该纳米粒子具有良好的稳定性,在808和1064 nm处均有较强的吸收.在1064 nm激光照射下,纳米粒子表现出优异的NIR-Ⅱ光热转换效果,可以实现对肿瘤细胞的光热治疗(PTT).在808 nm的激光激发下,纳米粒子还可以实现对小鼠血管和其他生物组织的高清晰度的NIR-Ⅱ荧光成像(FI).In order to simultaneously achieve excellent solubility, high brightness of second near-infrared(NIR-Ⅱ,1000-1700 nm) fluorescence, and strong NIR-Ⅱ photothermal transduction capability of conjugated polymers, we employed a ternary copolymerization strategy to construct the NIR-Ⅱ emissive conjugated polymers with strong electron acceptor and electron donor in our previous work. In this work, we further adjusted the ratio between the two electron donors, BDT and 2 TC, to obtain a series of conjugated polymers, named as BDT-2 TC12, BDT-2 TC11, and BDT-2 TC21. These polymers have strong absorption in the NIR-Ⅱ region and excellent solubility in organic phase. All of them show strong NIR absorption in the wavelength of 700-1200 nm extended to the NIR-Ⅱ region and exhibit strong NIR-Ⅱ fluorescence emission in the NIR-Ⅱ region of 1000-1400 nm, which was excited by an 808 nm laser. Thereafter, water-soluble and biocompatible nanoparticles(BDT-2 TC12 NPs) were facilely prepared by encapsulating the target conjugated polymer BDT-2 TC12 into the amphiphilic distearyl phosphatidylacetamide-methoxy polyethylene glycol(DSPE-mPEG) through nanoprecipitation method. These prepared nanoparticles have good size-stability and photostability, and exhibit strong absorption at both 808 nm and 1064 nm. Thus, under the irradiation of a 1064 nm laser, BDT-2 TC12 NPs showed an excellent NIR-Ⅱ photothermal conversion effect(the photothermal conversion efficiency of the BDT-2 TC12 NPs aqueous solution was calculated to be 56.3%), which could realize the photothermal therapy(PTT) of tumor cells. In addition,under the 808 nm laser excitation, the nanoparticles can also achieve high-resolution NIR-Ⅱ fluorescence imaging(FI) of the mouse blood vessels and other biological tissues.

关 键 词：高亮度 共轭聚合物 1064 nm激光 近红外二区光热治疗 近红外二区荧光成像 

分 类 号：R730.5[医药卫生—肿瘤] TQ317[医药卫生—临床医学]