基于聚β-环糊精模板效应的可拉伸功能性超分子水凝胶
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摘要
以β-环糊精与环氧氯丙烷的线形共聚物为大分子主体,以亲水性短链修饰的含可聚合双键的二茂铁单体为客体分子,利用二者间的主-客体包结络合作用,制备了一种新型的"大分子超分子交联剂".进而借助聚β-环糊精的大分子超分子模版效应,通过简单自由基共聚合反应,实现了基于β-环糊精与二茂铁客体分子间包结络合作用的可超长拉伸、抗刺、黏附性超分子水凝胶的制备.
cyclodextrin-ferrocene host-guest inclusion complex has been widely used to construct various
functional supramolecular hydrogels,but all these reported hydrogels are often very weak and/or brittle.In this work,β-cyclodextrin(β-CD)based linear copolymer(polyβ-CD)was synthesized and used as the macromolecular host,hydrophilic and flexible spacer modified ferrocene(Fc)monomer acted as the guest.The polymerizable Fc monomer was preloaded on polyβ-CD to form a novel type of‘macromolecular supramolecular cross-linker’(MSCL)owing to the inclusion complexation betweenβ-CD and Fc.For the first time,stretchable,stab-resistant and adhesive supramolecular hydrogels were prepared via simple free-radical copolymerization of MSCL and acrylamide.Tensile-testing results showed that the obtained supramolecular hydrogel can be stretched up to more than 30 times of its original length without breaking.The gel can also be stabbed by sharp tips of scissors or pencil without fracture,indicating excellent stab resistance property.At the same time,the hydrogel also exhibited strong adhesion to the surfaces of human hand,hydrophilic glass or hydrophobic porcine skin.We attribute these distinguished behaviors to the successful use of polyβ-CD and the introduction of flexible hydrophilic spacer to the Fc monomer.Firstly,polyβ-CD acted as a macromolecular supramolecular imprint to form pre-organized Fcpolyβ-CD complexes,and thus resulted in relatively local high density of pendent Fc groups in the polymeric network.This is different from most of the reported host-guest interaction based supramolecular hydrogels,where the host and guest groups are randomly attached in the polymeric network.Secondly,after copolymerization,polyβ-CD was homogeneously immersed in the network by noncovalent interaction but not covalently conjugated in the network,which would greatly limit its mobility.Finally,the introduction of hydrophilic spacer on Fc not only can yield water soluble Fc-polyβ-CD macromolecular supramolecular complex,but also provide the released free Fc groups with more flexibility.Altogether,the local high density of both the guest and host groups in the network combined with their relatively high flexibility provided the present supramolecular hydrogels with excellent mechanical properties.
cyclodextrin-ferrocene host-guest inclusion complex has been widely used to construct various
functional supramolecular hydrogels,but all these reported hydrogels are often very weak and/or brittle.In this work,β-cyclodextrin(β-CD)based linear copolymer(polyβ-CD)was synthesized and used as the macromolecular host,hydrophilic and flexible spacer modified ferrocene(Fc)monomer acted as the guest.The polymerizable Fc monomer was preloaded on polyβ-CD to form a novel type of‘macromolecular supramolecular cross-linker’(MSCL)owing to the inclusion complexation betweenβ-CD and Fc.For the first time,stretchable,stab-resistant and adhesive supramolecular hydrogels were prepared via simple free-radical copolymerization of MSCL and acrylamide.Tensile-testing results showed that the obtained supramolecular hydrogel can be stretched up to more than 30 times of its original length without breaking.The gel can also be stabbed by sharp tips of scissors or pencil without fracture,indicating excellent stab resistance property.At the same time,the hydrogel also exhibited strong adhesion to the surfaces of human hand,hydrophilic glass or hydrophobic porcine skin.We attribute these distinguished behaviors to the successful use of polyβ-CD and the introduction of flexible hydrophilic spacer to the Fc monomer.Firstly,polyβ-CD acted as a macromolecular supramolecular imprint to form pre-organized Fcpolyβ-CD complexes,and thus resulted in relatively local high density of pendent Fc groups in the polymeric network.This is different from most of the reported host-guest interaction based supramolecular hydrogels,where the host and guest groups are randomly attached in the polymeric network.Secondly,after copolymerization,polyβ-CD was homogeneously immersed in the network by noncovalent interaction but not covalently conjugated in the network,which would greatly limit its mobility.Finally,the introduction of hydrophilic spacer on Fc not only can yield water soluble Fc-polyβ-CD macromolecular supramolecular complex,but also provide the released free Fc groups with more flexibility.Altogether,the local high density of both the guest and host groups in the network combined with their relatively high flexibility provided the present supramolecular hydrogels with excellent mechanical properties.
引文
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2Calvert P.Adv Mater,2009,21(7):743-756
3Thiele J,Ma Y,Bruekers S M C,Ma S,Huck W T S.Adv Mater,2014,26(1):125-148
4Doering A,Birnbaum W,Kuckling D.Chem Soc Rev,2013,42(17):7391-7420
5Du X W,Zhou J,Shi J F,Xu B.Chem Rev,2015,115(24):13165-13307
6Jungst T,Smolan W,Schacht K,Scheibel T,Groll J.Chem Rev,2016,116(3):1496-1539
7Okumura Y,Ito K.Adv Mater,2001,13(7):485-487
8Gong J P,Katsuyama Y,Kurokawa T,Osada Y.Adv Mater,2003,15(14):1155-1158
9Haraguchi K,Takehisa T.Adv Mater,2002,14(16):1120-1124
10Huang T,Xu H,Jiao K,Zhu L,Brown H R,Wang H.Adv Mater,2007,19(12):1622-1626
11Sakai T,Matsunaga T,Yamamoto Y,Ito C,Yoshida R,Suzuki S,Sasaki N,Shibayama M,Chung U.Macromolecules,2008,41(14):5379-5384
12Lin P,Ma S,Wang X,Zhou F.Adv Mater,2015,27(12):2054-2059
13Bai T,Zhang P,Han Y,Liu Y,Liu W,Zhao X,Lu W.Soft Matter,2011,7(6):2825-2831
14Abdurrahmanoglu S,Can V,Okay O.Polymer,2009,50(23):5449-5455
15Jiang G,Liu C,Liu X,Zhang G,Yang M,Liu F.Macromol Mater Eng,2009,294(12):815-820
16Chen Q,Zhu L,Zhao C,Wang Q,Zheng J.Adv Mater,2013,25(30):4171-4176
17Sun T L,Kurokawa T,Kuroda S,Bin Ihsan A,Akasaki T,Sato K,Haque M A,Nakajima T,Gong J P.Nat Mater,2013,12(10):932-937
18Dai X,Zhang Y,Gao L,Bai T,Wang W,Cui Y,Liu W.Adv Mater,2015,27(23):3566-3571
19Guo M,Pitet L M,Wyss H M,Vos M,Dankers P Y W,Meijer E W.J Am Chem Soc,2014,136(19):6969-6977
20Cui Y,Tan M,Zhu A,Guo M.J Mater Chem B,2014,2(20):2978-2982
21Cui Y,Tan M,Zhu A,Guo M.J Mater Chem B,2015,3(14):2834-2841
22Yang N,Yang H,Shao Z,Guo M.Macromol Rapid Commun,2017,38(17):1700275
23Guo M,Jiang M.Macromol Rapid Commum,2010,31(19):1736-1739
24Guo M,Jiang M,Pispas S,Yu W,Zhou C.Macromolecules,2008,41(24):9744-9749
25Liu J,Chen G,Guo M,Jiang M.Macromolecules,2010,43(19):8086-8093
26Tan M,Cui Y,Zhu A,Han H,Guo M,Jiang M.Polym Chem,2015,6(43):7543-7549
27Dong Z Q,Cao Y,Yuan Q J,Wang Y F,Li J H,Li B J,Zhang S.Macromol Rapid Commun,2013,34(10):867-872
28Tomatsu I,Hashidzume A,Harada A.Macromol Rapid Commun,2006,27(4):238-241
29Nakahata M,Takashima Y,Yamaguchi H,Harada A.Nat Commun,2011,2:511
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