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Coordinate Bond Breaking Induced by Collapse of Poly(N-isopropyl acrylamide) as Ligands of a Rare Earth Complex
Tian-yu Song,Yan-yang Zhu,Shuo-feng Liang,Gang Zou*,Qi-jin Zhang*
Author NameAffiliationE-mail
Tian-yu Song CAS Key Laboratory of Soft Matter Chemistry, Key Laboratory of Optoelectronic Science and Technology, Innovation Centre of Chemistry for Energy Materials, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026, China  
Yan-yang Zhu CAS Key Laboratory of Soft Matter Chemistry, Key Laboratory of Optoelectronic Science and Technology, Innovation Centre of Chemistry for Energy Materials, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026, China  
Shuo-feng Liang CAS Key Laboratory of Soft Matter Chemistry, Key Laboratory of Optoelectronic Science and Technology, Innovation Centre of Chemistry for Energy Materials, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026, China  
Gang Zou* CAS Key Laboratory of Soft Matter Chemistry, Key Laboratory of Optoelectronic Science and Technology, Innovation Centre of Chemistry for Energy Materials, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026, China gangzou@ustc.edu.cn 
Qi-jin Zhang* CAS Key Laboratory of Soft Matter Chemistry, Key Laboratory of Optoelectronic Science and Technology, Innovation Centre of Chemistry for Energy Materials, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026, China zqjm@ustc.edu.cn 
Abstract:
A novel water-soluble luminescent complex consisting of Eu(ally-dbm)3-2Tppo and poly(N-isopropyl acrylamide) (PNIPAM) is synthesized through a series of chemical reactions. The structure of the complex is characterized by TGA, GPC, HNMR, and the thermal-responsive fluorescence of the complex in aqueous solution is investigated. It is found that PNIPAM collapse above the lower critical solution temperature causes the coordination bond breaking, leading to weakening of the fluorescence from Eu3+ and enhancing of the fluorescence from the ligands. When temperature decreases, the fluorescence from Eu3+ is found to boost up and the fluorescence from ligands weakens accordingly. It is deduced from this phenomenon that the ligands re-coordinate with europium ions again along with the temperature decreasing, which is further con rmed by IR measurements. This thermal-responsive fluorescence is of reversibility, which can be used as molecular probes for biological imaging and collapse studying of PNIPAM.
Key words:  Thermo-responsive polymer, Thermal quenching, Reversiblity
FundProject:
稀土配合物的配体PNIPAM塌缩诱导配位键断裂
宋田雨,朱晏阳,梁硕丰,邹 纲*,张其锦*
摘要:
通过一系列化学反应合成得到了Eu(ally-DBM)3-2TPPO和PNIPAM形成的大分子水溶性发光配合物. 本文通过TGA、GPC、HNMR表征复合物的结构,并研究了配合物在水溶液中的荧光热响应性. 研究发现,PNIPAM在低临界溶解温度以上塌缩引起配位键断裂,导致Eu3+的荧光减弱和配体荧光增强. 当温度降低时,发现Eu3+的荧光增强,配体荧光相应减弱. 推断当温度降低时配体再次与铕离子重新配位,并通过红外光谱进一步证实了. 这种配合物的荧光热响应性具有可逆性,可用作分子探针应用在生物成像方面和研究PNIPAM塌缩.
关键词:  热敏聚合物,热淬灭,可逆性
DOI:10.1063/1674-0068/31/cjcp1804059
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