Citation: Li-yuan Wang, Ping-zhang Cheng, Ming-yu Guo. Stretchable and Functional Supramolecular Hydrogels Based on the Template Effect of Poly(β-cyclodextrin)[J]. Acta Polymerica Sinica, ;2018, 0(8): 1097-1106. doi: 10.11777/j.issn1000-3304.2018.18041 shu

Stretchable and Functional Supramolecular Hydrogels Based on the Template Effect of Poly(β-cyclodextrin)

College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123

Corresponding author: Ming-yu Guo, guomingyu@suda.edu.cn
Received Date: 2 February 2018
Revised Date: 8 March 2018
Available Online: 1 March 2018

β-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 between β-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 Fc-polyβ-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.
- Host-guest,
- Hydrogel,
- Template effect,
- Stab-resistant,
- Adhesive
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