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光和温度作为双重刺激导致超支化偶氮苯封端的聚（N-异丙基丙烯酰胺）的自组装。

Light and Temperature as Dual Stimuli Lead to Self-Assembly of Hyperbranched Azobenzene-Terminated Poly(N-isopropylacrylamide).

作者信息

Huang Wenyan, Yang Jing, Xia Yunqing, Wang Xuezi, Xue Xiaoqiang, Yang Hongjun, Wang Guifang, Jiang Bibiao, Li Fang, Komarneni Sridhar

机构信息

Jiangsu Key Laboratory of Material Surface Science and Technology, School of Material Science and Engineering, Changzhou University, Changzhou 213164, Jiangsu, China.

Materials Research Laboratory, Materials Research Institute, The Pennsylvania State University, University Park, PA 16802, USA.

出版信息

Polymers (Basel). 2016 May 7;8(5):183. doi: 10.3390/polym8050183.

DOI:10.3390/polym8050183
PMID:30979277
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6432090/
Abstract

Hyperbranched poly(-isopropylacrylamide)s (HBPNIPAMs) end-capped with different azobenzene chromophores (HBPNIPAM-Azo-OC₃H₇, HBPNIPAM-Azo-OCH₃, HBPNIPAM-Azo, and HBPNIPAM-Azo-COOH) were successfully synthesized by atom transfer radical polymerization (ATRP) of -isopropylacrylamide using different azobenzene-functional initiators. All HBPNIPAMs showed a similar highly branched structure, similar content of azobenzene chromophores, and similar absolute weight/average molecular weight. The different azobenzene structures at the end of the HBPNIPAMs exhibited reversible isomerization behavior under alternating UV and Vis irradiation, which lowered the critical solution temperature (LCST) due to different self-assembling behaviors. The spherical aggregates of HBPNIPAM-Azo-OC₃H₇ and HBPNIPAM-Azo-OCH₃ containing hydrophobic para substituents either changed to bigger nanorods or increased in number, leading to a change in LCST of -2.0 and -1.0 °C, respectively, after UV irradiation. However, the unimolecular aggregates of HBPNIPAM-Azo were unchanged, while the unstable multimolecular particles of HBPNIPAM-Azo-COOH end-capped with strongly polar carboxyl groups partly dissociated to form a greater number of unimolecular aggregates and led to an LCST increase of 1.0 °C.

摘要

通过使用不同的偶氮苯功能引发剂对异丙基丙烯酰胺进行原子转移自由基聚合（ATRP），成功合成了以不同偶氮苯发色团封端的超支化聚（N-异丙基丙烯酰胺）（HBPNIPAM-Azo-OC₃H₇、HBPNIPAM-Azo-OCH₃、HBPNIPAM-Azo和HBPNIPAM-Azo-COOH）。所有HBPNIPAM均呈现出相似的高度支化结构、相似的偶氮苯发色团含量以及相似的绝对重均分子量。HBPNIPAM末端不同的偶氮苯结构在交替的紫外光和可见光照射下表现出可逆的异构化行为，由于不同的自组装行为，这降低了临界溶解温度（LCST）。含有疏水对位取代基的HBPNIPAM-Azo-OC₃H₇和HBPNIPAM-Azo-OCH₃的球形聚集体在紫外光照射后，要么转变为更大的纳米棒，要么数量增加，导致LCST分别变化-2.0和-1.0℃。然而，HBPNIPAM-Azo的单分子聚集体未发生变化，而用强极性羧基封端的HBPNIPAM-Azo-COOH的不稳定多分子颗粒部分解离形成更多的单分子聚集体，并导致LCST升高1.0℃。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5c8/6432090/477f38ed2273/polymers-08-00183-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5c8/6432090/0f6ceaede094/polymers-08-00183-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5c8/6432090/335d0f827dde/polymers-08-00183-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5c8/6432090/b79883dca587/polymers-08-00183-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5c8/6432090/766b285d97b5/polymers-08-00183-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5c8/6432090/551f15ffd5db/polymers-08-00183-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5c8/6432090/1f422a1e596c/polymers-08-00183-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5c8/6432090/c261332e3c87/polymers-08-00183-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5c8/6432090/a20ef143115f/polymers-08-00183-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5c8/6432090/477f38ed2273/polymers-08-00183-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5c8/6432090/0f6ceaede094/polymers-08-00183-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5c8/6432090/335d0f827dde/polymers-08-00183-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5c8/6432090/b79883dca587/polymers-08-00183-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5c8/6432090/766b285d97b5/polymers-08-00183-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5c8/6432090/551f15ffd5db/polymers-08-00183-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5c8/6432090/1f422a1e596c/polymers-08-00183-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5c8/6432090/c261332e3c87/polymers-08-00183-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5c8/6432090/a20ef143115f/polymers-08-00183-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5c8/6432090/477f38ed2273/polymers-08-00183-g008.jpg

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