自组装辅助聚合法制备纤维素基温度/pH双敏感性荧光纳米凝胶

doi:10.7503/cjcu20131103

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (7): 1608.doi: 10.7503/cjcu20131103

• 高分子化学 • 上一篇

自组装辅助聚合法制备纤维素基温度/pH双敏感性荧光纳米凝胶

李祯珍, 周淑彦, 窦红静(), 孙康

上海交通大学材料科学与工程学院, 金属基复合材料国家重点实验室, 上海 200240

收稿日期:2013-11-15 出版日期:2014-07-10 发布日期:2019-08-01
作者简介:联系人简介: 窦红静, 女, 博士, 副教授, 博士生导师, 主要从事生物医用材料研究. E-mail: hjdou@sjtu.edu.cn
基金资助:
国家自然科学基金(批准号: 20904032, 21174082, 21374061)、教育部新世纪优秀人才支持计划、上海交通大学SMC-晨星青年学者奖励计划和金属基复合材料国家重点实验室开放基金资助

Temperature/pH Dual-sensitive Fluorescence Nano-gel Based on Cellulose Through Self-assembly Assisted Polymerization^†

LI Zhenzhen, ZHOU Shuyan, DOU Hongjing^*(), SUN Kang

State Key Lab of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

Received:2013-11-15 Online:2014-07-10 Published:2019-08-01
Contact: DOU Hongjing E-mail:hjdou@sjtu.edu.cn
Supported by:
Supported by the National Natural Science Fundation of China(Nos20904032, 21174082, 21374061), the New Century Excellent Talents in University of China, the Shanghai Jiao Tong University SMC-Excellent Young Scholar Award and the Open Fund of State Key Laboratory of Metal Matrix Composite in Shanghai Jiao Tong University

摘要/Abstract

摘要：

通过自组装辅助的一步法制备了具有温度和pH双重响应性的荧光纳米凝胶(FNG). 首先设计制备了一种水溶性含双键的荧光单体5-丙烯酰胺荧光素(5-AAF), 在水溶性纤维素醚——羟丙基纤维素(HPC)主链上引发5-AAF的接枝共聚, 同时由于5-AAF的疏水作用力诱导共聚物发生自组装, 并通过双官能团交联剂亚甲基二丙烯酰胺(MBA)的加入使自组装纳米聚集体交联, 从而一步制得具有环境响应性的FNG, 该过程在水相中进行, 具有高效、 “绿色”的优点. 研究结果表明, 改变合成过程中HPC的分子量可调控所得FNG的环境响应性. 对FNG环境响应性的研究表明, FNG链段上的亲疏水基团及与水分子间的氢键作用是影响凝胶温度响应性的主要因素. 此外, FNG的荧光在中性及碱性溶液中显著加强, 在酸性溶液中迅速猝灭. 由于FNG的荧光信号对温度和pH的显著敏感性, 且具有较低的细胞毒性, 因此在荧光标记生物检测及生物微环境的温度/pH检测等领域具有广泛的应用前景.

关键词: 纳米凝胶, 自组装, 温度/pH敏感性, 荧光, 羟丙基纤维素

Abstract:

Temperature/pH dual-sensitive fluorescence nanogels(FNGs) were synthesized through a self-assembly assisted(SAA) “one-step” method. A hydrophilic fluorescence monomer 5-acrylamide fluorescein(5-AAF) has been fabricated, on this basis, graft copolymerization of 5-AAF from the backbone of hydroxypropyl cellulose(HPC) was initiated using ceric ammonium nitrate(CAN), the self-assembly of 5-AAF graft chains induced by both hydrogen bond and the hydrophobic interaction of fluorescence group proceeded with the polymerization of 5-AAF. Furthermore, N,N'-methylenebisacrylamide(MBA) was applied as crosslinker. As a result, FNGs were synthesized efficiently and environment-friendly with stable temperature/pH sensitivity properties. The environment-sensitivity of resultant FNGs can be tuned by changing molecular weight of HPC, the existence of hydrophobic/hydrophilic group on FNGs as well as the hydrogen bond contributed to FNGs’ temperature-sensitivity. Moreover, FNGs displayed impressive pH-sensitivity under various pH values, the fluorescence intensity can be rapidly enhanced at neutral and alkalic environment, while it quenches at acidic environment. The influence of pH on fluorescence intensity can be reversed without any other recovery process. The cytotoxicity of FNG was preliminarily studied, the results revealed good biocompatibility of FNGs. The temperature/pH responsivity of the FNGs’ fluorescence are of great potential in biomedical detection, such as fluorescence labeling, or temperature/pH sensor for micro-environment.

Key words: Nanogel, Self-assembly, Temperature/pH sensitivity, Fluorescence, Hydroxypropyl cellulose

中图分类号:

TrendMD:

李祯珍, 周淑彦, 窦红静, 孙康. 自组装辅助聚合法制备纤维素基温度/pH双敏感性荧光纳米凝胶. 高等学校化学学报, 2014, 35(7): 1608.

LI Zhenzhen, ZHOU Shuyan, DOU Hongjing, SUN Kang. Temperature/pH Dual-sensitive Fluorescence Nano-gel Based on Cellulose Through Self-assembly Assisted Polymerization^†. Chem. J. Chinese Universities, 2014, 35(7): 1608.

图/表 5

Scheme 1 Schematic illustration of the preparation of temperature/pH-sensitive FNG nanogel

Fig.1 Relationship between average size anda. pH=3.0; b. pH=6.0; c. pH=7.6.

Fig.2 Temperature-responsive property of FNG08 at pH=3.0

Fig.3 Fluorescence intensity of I520 from the emission spectra in various pH of FNG08 at concerntration of 0.75 mg/mL(A) and FNG08’s reversibility of fluorescence intensity under pH=3.0(down) and 10.0(up)(B) (A)λex=492 nm; excitation and emission slit: 3 nm; insets show the fluorescence microscope images of FNG08 at pH=3.0(a), pH=11.0(b), respectively.

Fig.4 Cytotoxicity profiles of incubated HeLa cells with various concentrations of FNG08 as determined via MTT assay experiments The data represent the mean±SD, n=5.

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自组装辅助聚合法制备纤维素基温度/pH双敏感性荧光纳米凝胶

Temperature/pH Dual-sensitive Fluorescence Nano-gel Based on Cellulose Through Self-assembly Assisted Polymerization^†

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自组装辅助聚合法制备纤维素基温度/pH双敏感性荧光纳米凝胶

Temperature/pH Dual-sensitive Fluorescence Nano-gel Based on Cellulose Through Self-assembly Assisted Polymerization†

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Temperature/pH Dual-sensitive Fluorescence Nano-gel Based on Cellulose Through Self-assembly Assisted Polymerization^†