基于动态硼酸酯键的水凝胶的模块化组装和智能形变
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摘要
将苯硼酸基团引入水凝胶网络中,以聚乙烯醇(PVA)为胶水,在碱性条件下通过水凝胶表面与PVA形成动态硼酸酯键,实现了含有苯硼酸基团的水凝胶的模块化组装.通过显微红外表征,证明了在2块水凝胶界面形成了硼酸酯键,并且组装后的水凝胶黏合强度大于水凝胶本体.随后引入聚阳离子单体甲基丙烯酰氧乙基三甲基氯化铵(METAC)以及N-异丙基丙烯酰胺(NIPAm)实现了双层水凝胶的离子与温度双重刺激响应,并且通过胶水黏合位置的选择,实现了二维与三维复杂形变.最后通过刺激响应的双重正向叠加制备了抓取力可调的软机械夹具.
The reversible mechanical deformations of smart hydrogel actuators, such as swelling/shrinking and bending, under various external stimuli have earned them mounting attention in the application arenas of biomimetic actuators, soft robots, etc. Hydrogel actuators were initailly designed with isotropic structures for a simple swelling/shrinking triggered by external stimuli, while the research progress afterwards focuses more on the design of anisotropic structures that aims at complex shape deformation. However, the determined structure of traditional anisotropic hydrogel actuators typically led to fixed shape deformation direction and degree, which limited them from meeting the actual needs. To this end, we got inspired by the assembly of building blocks and integrated boronic acid groups into the hydrogel bulks. Poly(vinyl alcohol)(PVA) promoted the binding process of newly introduced groups by forming PBA-diol ester bonds with them under alkaline conditions, which was further confirmed by microscopic infrared spectroscopy. The dynamic covalent bonds between two hydrogel sheets were so strong that they were adhered firmly with each other without breaking during the tensile test. Then,two kinds of cationic monomers, methacryloxyethyltrimethyl ammonium chloride(METAC) and N-isopropyl acrylamide(NIPAM), were introduced into the hydrogel system, respectively, to afford two types of stimuliresponsive hydrogels, and the smart hydrogel actuators that dually responded to temeperature and ionic strength were successfully fabricated by the sheet combination via PBA-diol ester bonds. Both 2 D and 3 D architectures could be achieved at elaborate selection of bonding positions. For instance, bonding of a 2 D octopus-shaped hydrogel to another planar hydrogel could transfrom the 2 D structure into a 3 D type along with the swelling of octopus-shaped hydrogel. Finally, integration of METAC and NIPAM into one system could afford a soft gripper with tunable grasping force and dual responsiveness to ion strength and temperature. Our research has provided a new perspective for the design and fabrication of novel hydrogel actuators with complex deformations.
The reversible mechanical deformations of smart hydrogel actuators, such as swelling/shrinking and bending, under various external stimuli have earned them mounting attention in the application arenas of biomimetic actuators, soft robots, etc. Hydrogel actuators were initailly designed with isotropic structures for a simple swelling/shrinking triggered by external stimuli, while the research progress afterwards focuses more on the design of anisotropic structures that aims at complex shape deformation. However, the determined structure of traditional anisotropic hydrogel actuators typically led to fixed shape deformation direction and degree, which limited them from meeting the actual needs. To this end, we got inspired by the assembly of building blocks and integrated boronic acid groups into the hydrogel bulks. Poly(vinyl alcohol)(PVA) promoted the binding process of newly introduced groups by forming PBA-diol ester bonds with them under alkaline conditions, which was further confirmed by microscopic infrared spectroscopy. The dynamic covalent bonds between two hydrogel sheets were so strong that they were adhered firmly with each other without breaking during the tensile test. Then,two kinds of cationic monomers, methacryloxyethyltrimethyl ammonium chloride(METAC) and N-isopropyl acrylamide(NIPAM), were introduced into the hydrogel system, respectively, to afford two types of stimuliresponsive hydrogels, and the smart hydrogel actuators that dually responded to temeperature and ionic strength were successfully fabricated by the sheet combination via PBA-diol ester bonds. Both 2 D and 3 D architectures could be achieved at elaborate selection of bonding positions. For instance, bonding of a 2 D octopus-shaped hydrogel to another planar hydrogel could transfrom the 2 D structure into a 3 D type along with the swelling of octopus-shaped hydrogel. Finally, integration of METAC and NIPAM into one system could afford a soft gripper with tunable grasping force and dual responsiveness to ion strength and temperature. Our research has provided a new perspective for the design and fabrication of novel hydrogel actuators with complex deformations.
引文
1Yao C,Liu Z,Yang C,Wang W,Ju X J,Xie R,Chu L Y.Adv Funct Mater,2015,25:2980-2991
2 Yao C,Liu Z,Yang C,Wang W,Ju X J,Xie R,Chu L Y.ACS Appl Mater Interfaces,2016,8:21721-21730
3 Zeng Jinfeng(曾金凤),Yang Wendi(杨雯迪),Shi Dongjian(施冬健),Li Xiaojie(李小杰),Chen Mingqing(陈明清).Acta Polymerica Sinica(高分子学报),2018,(10):1297-1306
4 Xiao S W,Zhang M Z,He X M,Huang L,Zhang Y X,Ren B P,Zhong M Q,Chang Y,Yang J T,Zheng J.ACS Appl Mater Interfaces,2018,10:21642-21653
5 Xiao S W,Yang Y,Zhong M Q,Chen H,Zhang Y X,Yang J T.ACS Appl Mater Interfaces,2017,9:20843-20851
6 Gong X L,Xiao Y Y,Pan M,Kang Y,Li B J,Zhang S.ACS Appl Mater Interfaces,2016,8:27432-27437
7 Ma C X,Le X X,Tang X L,He J,Xiao P,Zheng J,Xiao H,Lu W,Zhang J W,Huang Y J,Chen T.Adv Funct Mater,2016,26:8670-8676
8 Zhang Ying(张滢),Liu Liang(刘梁),Wang Tinghong(王庭宏),Tian Huayu(田华雨),Chen Xuesi(陈学思).Acta Polymerica Sinica(高分子学报),2017,(7):1150-1158
9 Yan X Z,Wang F,Zheng B,Huang F H.Chem Soc Rev,2012,41:6042-6065
10 Ionov L.Mater Today,2014,17:494-503
11 Zheng J,Xiao P,Le X X,Lu W,Théato P,Ma C X,Du B Y,Zhang J W,Huang Y J,Chen T.J Mater Chem C,2018,6:1320-1327
12 Ma C X,Lu W,Yang X X,He J,Le X X,Wang L,Zhang J W,Serpe M J,Huang Y J,Chen T.Adv Funct Mater,2018,28:1704568-1704575
13 Wang L,JianY K,Le X X,Lu W,Ma C X,Zhang J W,Huang Y J,Huang C F,Chen T.Chem Commun,2018,54:1229-1232
14 Yuk H,Lin S,Ma C,Takaffoli M,Fang N X,Zhao X.Nat Commun,2017,8:14230-14242
15 Lee Y,Cha S H,Kim Y W,Choi D,Sun J Y.Nat Commun,2018,9:1804-1812
16 Han D,Farino C,Yang C,Scott T,Browe D,Choi W,Freeman J W,Lee H.ACS Appl Mater Interfaces,2018,10:17512-17518
17 Oh M S,Song Y S,Kim C,Kim J,You J B,Kim T S,Lee C S,Im S G.ACS Appl Mater Interfaces,2016,8:8782-8788
18 Liu Y,Zhang K H,Ma J H,Vancso G J.ACS Appl Mater Interfaces,2017,9:901-908
19 Ionov L.Adv Funct Mater,2013,23:4555-4570
20 Kim S J,Kim M S,Kim S I,Spinks G M,Kim B C,Wallace G G.Chem Mater,2006,18:5805-5809
21 Lou R C,Wu J,Dinh N D,Chen C H.Adv Funct Mater,2015,25:7272-7279
22Asoh T,Matsusaki M,Kaneko T,Akashi M.Adv Mater,2008,20:2080-2083
23Kim Y S,Liu M J,Ishida Y,Ebina Y,Osada M,Sasaki T,Hikima T,Takata M,Aida T.Nat Commun,2015,14:1002-1007
24Liu M J,Ishida Y,Ebina Y,Sasaki T,Takara M,Aida T.Nat Mater,2015,517:68-72
25Cheng M J,Zhu G Q,Li L,Zhang S,Zhang D Q,Kuehne A J C,Shi F.Angew Chem Int Ed,2018,57:14106-14110
26Ju G N,Guo F L,Zhang Q,Kuehne A J C,Cui S X,Cheng M J,Shi F.Adv Mater,2017,29:1702444-1702450
27Ju G N,Cheng M J,Guo F L,Zhang Q,Shi F.Angew Chem Int Ed,2018,130:9101-9105
28Zhao Q,Yang X X,Ma C X,Chen D,Bai H,Li T F,Yang W,Xie T.Mater Horiz,2016,3:422-428
29Tamesue S,Yasuda K,Endo T.ACS Appl Mater Interfaces,2018,10:29925-29932
30Gladman A S,Matsumoto E A,Nuzzo R G,Mahadevan L,Lewis J A.Nat Mater,2016,15:413-418
31Ge Q,Qi H J,Dunn M L.Appl Phys Lett,2013,103:131901-13906
32Wang X J,Guo X G,Ye J L,Zheng N,Kogli P,Choi D,Zhang Y,Xie Z Q,Zhang Q H,Luan H W,Nan K,Kim B H,Xu Y M,Shan X W,Bai W.B,Sun R J,Wang Z Z,Jang H,Zhang F,Ma Y J,Xu Z,Feng X,Xie T,Huang Y H,Zhang Y H,Rogers J A.Adv Mater,2018,31(2):1805615-1805624
33Ma C X,Li T F,Zhao Q,Yang X X,Wu J J,Luo Y W,Xie T.Adv Mater,2014,26:5665-5669
34Cromwell O R,Chung J,Guan Z B.J Am Chem Soc,2015,137:6492-6495
35Hong S H,Kim S,Park J P,Shin M,Kim K,Ryu J H,Lee H.Biomacromolecules,2018,19:2053-2061
36Brewer S H,Allen A M,Lappi S E,Chasse T L,Briggman K A,Gorman C B,Franzen S.Langmuir,2004,20:5512-5520
37Chen Y,Tang Z,Zhang X,Liu Y,Wu S,Guo B.ACS Appl Mater Interfaces,2018,10:24224-24231
2 Yao C,Liu Z,Yang C,Wang W,Ju X J,Xie R,Chu L Y.ACS Appl Mater Interfaces,2016,8:21721-21730
3 Zeng Jinfeng(曾金凤),Yang Wendi(杨雯迪),Shi Dongjian(施冬健),Li Xiaojie(李小杰),Chen Mingqing(陈明清).Acta Polymerica Sinica(高分子学报),2018,(10):1297-1306
4 Xiao S W,Zhang M Z,He X M,Huang L,Zhang Y X,Ren B P,Zhong M Q,Chang Y,Yang J T,Zheng J.ACS Appl Mater Interfaces,2018,10:21642-21653
5 Xiao S W,Yang Y,Zhong M Q,Chen H,Zhang Y X,Yang J T.ACS Appl Mater Interfaces,2017,9:20843-20851
6 Gong X L,Xiao Y Y,Pan M,Kang Y,Li B J,Zhang S.ACS Appl Mater Interfaces,2016,8:27432-27437
7 Ma C X,Le X X,Tang X L,He J,Xiao P,Zheng J,Xiao H,Lu W,Zhang J W,Huang Y J,Chen T.Adv Funct Mater,2016,26:8670-8676
8 Zhang Ying(张滢),Liu Liang(刘梁),Wang Tinghong(王庭宏),Tian Huayu(田华雨),Chen Xuesi(陈学思).Acta Polymerica Sinica(高分子学报),2017,(7):1150-1158
9 Yan X Z,Wang F,Zheng B,Huang F H.Chem Soc Rev,2012,41:6042-6065
10 Ionov L.Mater Today,2014,17:494-503
11 Zheng J,Xiao P,Le X X,Lu W,Théato P,Ma C X,Du B Y,Zhang J W,Huang Y J,Chen T.J Mater Chem C,2018,6:1320-1327
12 Ma C X,Lu W,Yang X X,He J,Le X X,Wang L,Zhang J W,Serpe M J,Huang Y J,Chen T.Adv Funct Mater,2018,28:1704568-1704575
13 Wang L,JianY K,Le X X,Lu W,Ma C X,Zhang J W,Huang Y J,Huang C F,Chen T.Chem Commun,2018,54:1229-1232
14 Yuk H,Lin S,Ma C,Takaffoli M,Fang N X,Zhao X.Nat Commun,2017,8:14230-14242
15 Lee Y,Cha S H,Kim Y W,Choi D,Sun J Y.Nat Commun,2018,9:1804-1812
16 Han D,Farino C,Yang C,Scott T,Browe D,Choi W,Freeman J W,Lee H.ACS Appl Mater Interfaces,2018,10:17512-17518
17 Oh M S,Song Y S,Kim C,Kim J,You J B,Kim T S,Lee C S,Im S G.ACS Appl Mater Interfaces,2016,8:8782-8788
18 Liu Y,Zhang K H,Ma J H,Vancso G J.ACS Appl Mater Interfaces,2017,9:901-908
19 Ionov L.Adv Funct Mater,2013,23:4555-4570
20 Kim S J,Kim M S,Kim S I,Spinks G M,Kim B C,Wallace G G.Chem Mater,2006,18:5805-5809
21 Lou R C,Wu J,Dinh N D,Chen C H.Adv Funct Mater,2015,25:7272-7279
22Asoh T,Matsusaki M,Kaneko T,Akashi M.Adv Mater,2008,20:2080-2083
23Kim Y S,Liu M J,Ishida Y,Ebina Y,Osada M,Sasaki T,Hikima T,Takata M,Aida T.Nat Commun,2015,14:1002-1007
24Liu M J,Ishida Y,Ebina Y,Sasaki T,Takara M,Aida T.Nat Mater,2015,517:68-72
25Cheng M J,Zhu G Q,Li L,Zhang S,Zhang D Q,Kuehne A J C,Shi F.Angew Chem Int Ed,2018,57:14106-14110
26Ju G N,Guo F L,Zhang Q,Kuehne A J C,Cui S X,Cheng M J,Shi F.Adv Mater,2017,29:1702444-1702450
27Ju G N,Cheng M J,Guo F L,Zhang Q,Shi F.Angew Chem Int Ed,2018,130:9101-9105
28Zhao Q,Yang X X,Ma C X,Chen D,Bai H,Li T F,Yang W,Xie T.Mater Horiz,2016,3:422-428
29Tamesue S,Yasuda K,Endo T.ACS Appl Mater Interfaces,2018,10:29925-29932
30Gladman A S,Matsumoto E A,Nuzzo R G,Mahadevan L,Lewis J A.Nat Mater,2016,15:413-418
31Ge Q,Qi H J,Dunn M L.Appl Phys Lett,2013,103:131901-13906
32Wang X J,Guo X G,Ye J L,Zheng N,Kogli P,Choi D,Zhang Y,Xie Z Q,Zhang Q H,Luan H W,Nan K,Kim B H,Xu Y M,Shan X W,Bai W.B,Sun R J,Wang Z Z,Jang H,Zhang F,Ma Y J,Xu Z,Feng X,Xie T,Huang Y H,Zhang Y H,Rogers J A.Adv Mater,2018,31(2):1805615-1805624
33Ma C X,Li T F,Zhao Q,Yang X X,Wu J J,Luo Y W,Xie T.Adv Mater,2014,26:5665-5669
34Cromwell O R,Chung J,Guan Z B.J Am Chem Soc,2015,137:6492-6495
35Hong S H,Kim S,Park J P,Shin M,Kim K,Ryu J H,Lee H.Biomacromolecules,2018,19:2053-2061
36Brewer S H,Allen A M,Lappi S E,Chasse T L,Briggman K A,Gorman C B,Franzen S.Langmuir,2004,20:5512-5520
37Chen Y,Tang Z,Zhang X,Liu Y,Wu S,Guo B.ACS Appl Mater Interfaces,2018,10:24224-24231