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[资源] Acc. Chem. Res. 最新综述：水溶液中的刺激响应性超分子聚合物——田禾院士出品

Stimuli-Responsive Supramolecular Polymers in Aqueous Solution
Xiang Ma and He Tian*
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science & Technology, Shanghai 200237, P. R. China

CONSPECTUS
Aiming to construct various novel supramolecular polymeric structures in aqueous solution beyond small supramolecular
self-assembly molecules and develop functional supramolecular polymeric materials, research interest on functional supramolecular
polymers has been prevailing in recent years. Supramolecular polymers are formed by bridging monomers or components together via highly
directional noncovalent interactions such as hydrogen bonding, hydrophobic interaction, π−π interaction, metal − ligand coordination,
electrostatic interaction, and so forth. They can be easily functionalized by employing diverse building components with speci ﬁ c functions
besides the traditional polymeric properties, a number of which are responsive to such external stimuli as pH variance, photoirradiation,
chemically or electrochemically redox with the controllable conformation or construction switching, polymerization building and rebuilding, and function adjustment reversibly owing to the reversibility of noncovalent interactions. Supramolecular polymers are “ soft matters ” and can be functionalized with speci ﬁc properties such as morphology adjustment, controllable luminescence, shape memory, self-healing, and so forth. Supramolecular polymers constructed based on macrocycle recognition and interlocked structures represent one typical branch of the supramolecular polymer family. Cyclodextrin (CD), cucurbituril (CB), and hydrophilic calixarene derivatives are usually employed to construct hydrophilic supramolecular polymers in aqueous solution. Stimuli-responsive hydrophilic supramolecular polymers, constructed in aqueous solution particularly, can be promising candidates for mimicking biocompatible or vital functional materials.
This Account mainly focuses on the recent stimuli-responsive supramolecular polymers based on the host − guest interaction in
aqueous solution. We describe the hydrophilic supramolecular polymers constructed via hydrophobic e ﬀ ects, electrostatic
interaction, metal − ligand coordination, and multiple combinations of the above noncovalent interactions. The disparate ways to
engender stimuli-responsive supramolecular polymers via the hydrophobic e ﬀ ects of α -CD, β -CD, and γ -CD macrocycles are
illustrated and discussed. Some recent works on CD-based photoresponsive functional supramolecular polymers are summarized.
CB (especially CB[8]) based supramolecular polymers and their pH-responsive and photoresponsive properties are introduced.
Hydrophilic calixarene derivative (bis(p-sulfonatocalix[4]arene) typically) based supramolecular polymers via electrostatic
interactions are reviewed, and their redox-responsive association/disassociation elaborated in detail. More complicate
supramolecular polymers based on multiple noncovalent interactions are illustrated including hydrophobic e ﬀ ect, metal − ligand
coordination, and electrostatic interactions and their functional stimuli-responsiveness elaborated as well. Finally, we give
perspectives on the strength of these diverse noncovalent interactions to form supramolecular polymers in aqueous solution, on
the advantage, disadvantage, e ﬃ ciency, and reversibility of using certain stimuli in constructing supramolecular polymers and
prospect the future function improvement of these polymers as functional materials.

Biography
Xiang Ma was born in China in 1980. He obtained his B.S. degree from Tianjin University in 2003 and Ph.D. in applied chemistry in 2008 from East China University of Science and Technology (ECUST) under the supervision of Prof. He Tian. From January 2011 to July 2012, he worked as a research associate in Liquid Crystal Institute, Kent State University. He is now an associate professor at ECUST, and his current research interests focus on controllable functional supramolecular machines and polymers.
Biography
He Tian was born in China in 1962. In 1999, he was appointed Cheung Kong Distinguished Professor by the Education Ministry of China. In 2011, he was selected as a member of the Chinese Academy of Science. In 2013, he became a Fellow of the TWAS—the World Academy of Science—for the advancement of science in developing countries. His current research interests include the supramolecular machines and switches, the synthesis of novel functional organic dyes, and the development of interdisciplinary materials science that determines the electronic and optical properties of materials.

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