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1.南开大学,化学学院,天津 300071
2.南开大学,功能高分子材料教育部重点实验室,天津 300071
3.南开大学,元素有机化学国家重点实验室,天津 300071
Kang Cai, E-mail: kangcai@nankai.edu.cn
Dong-sheng Guo, E-mail: dshguo@nankai.edu.cn
Published:20 October 2022,
Published Online:11 August 2022,
Received:25 May 2022,
Accepted:14 June 2022
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姚顺雨,蔡康,郭东升.基于深穴偶氮杯[4]芳烃构筑的乏氧响应超分子水凝胶[J].高分子学报,2022,53(10):1271-1278.
Yao Shun-yu,Cai Kang,Guo Dong-sheng.A Hypoxia-responsive Supramolecular Hydrogel Based on a Deep-cavity Azocalix[4]arene[J].ACTA POLYMERICA SINICA,2022,53(10):1271-1278.
姚顺雨,蔡康,郭东升.基于深穴偶氮杯[4]芳烃构筑的乏氧响应超分子水凝胶[J].高分子学报,2022,53(10):1271-1278. DOI: 10.11777/j.issn1000-3304.2022.22201.
Yao Shun-yu,Cai Kang,Guo Dong-sheng.A Hypoxia-responsive Supramolecular Hydrogel Based on a Deep-cavity Azocalix[4]arene[J].ACTA POLYMERICA SINICA,2022,53(10):1271-1278. DOI: 10.11777/j.issn1000-3304.2022.22201.
以
N
-乙胺基-4-氮杂环丁基-1
8-萘酰亚胺(EANA)染料客体接枝的透明质酸(HA)为水凝胶骨架,以乏氧响应的深穴偶氮杯[4
]
芳烃(CSAC4A)为交联剂
利用CSAC4A和EANA形成1:2主客体复合物的识别作用,制备了一种新型超分子水凝胶(HA-CA),并对其形貌、力学性能和刺激响应性进行了表征和分析. 实验表明,当处于乏氧环境时,HA-CA中的CSAC4A能够发生响应断裂,物理交联点被破坏,释放出其中包裹的EANA染料,进而导致荧光信号恢复.
Stimulus-responsive hydrogels based on host-guest interactions have attractive tremendous attentions in recent years
and have been applied successfully in a variety of research areas. Currently
a lot of macrocyclic hosts—such as cyclodextrin
crown ether
calixarenes
cucurbiturils
and pillararenes
etc
.—have been widely investigated in the preparation of stimulus-responsive supramolecular hydrogels. The major approach to introduce stimulus-responsive properties into these supramolecular hydrogels is exploiting specially designed guests which can response to external stimuli. However
most of functional guests—such as organic dyes—are fail to manifest stimulus-responsive properties
which is a big limitation for the development of functional host-guest supramolecular hydrogels. Introducing stimulus-responsive hosts with excellent guest-binding abilities as the building blocks of supramolecular hydrogels may be an efficient way to address this problem. Herein
hyaluronic acid (HA) was modified with
N
-ethylamino-4-azetidinyl-1
8-naphthalene anhydride (EANA) dyes and used as the polymeric backbone of the hydrogel
and a hypoxia-responsive
deep-cavity azocalix[4
]
arene (CSAC4A) was exploited as the noncovalent cross-linking agent. By utilizing the strong 1:2 recognition interactions between CSAC4A and the EANA moieties on the HA backbones
a new supramolecular hydrogel with hypoxia-responsiveness was prepared
and its morphology
mechanical properties
and hypoxia-responsive behavior were fully characterized. It has been showed that
the pore sizes of HA-CA are mainly distributed in the range of 40-70 μm
which indicates HA-CA is a typical microporous supramolecular hydrogel. Besides
the storage modulus (
G
') of HA-CA is stable at around 100 Pa
under the evaluation conditions of 0.5% strain
1 Hz. When HA-CA was put under a hypoxia environment
the azo bonds of CSAC4A were reduced and cleaved
leading to the release of the encapsulated EANA dyes
along with the recovery of their fluorescent emission. At the same time
due to the destruction of the physical cross-linking points
the cross-linked structure of the supramolecular hydrogel was destroyed
and its mechanical strength was significantly reduced. Therefore
HA-CA represents a novel type of hypoxia-responsive supramolecular hydrogel which might be potentially useful for biomedical applications.
超分子水凝胶主客体相互作用乏氧响应大环主体偶氮杯芳烃
Supramolecular hydrogelHost-guest interactionHypoxia responseMacrocyclic hostAzocalix[4]arene
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