School of Materials Engineering, Shanghai University of Engineering Science, Shanghai 201620, China.
Division of Physical Biology, CAS Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201800, China and Shanghai Synchrotron Radiation Facility, Zhangjiang Laboratory, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201210, China and University of Chinese Academy of Sciences, Beijing 100049, China.
Nanoscale. 2020 Feb 27;12(8):5186-5195. doi: 10.1039/c9nr10779g.
Supramolecular hydrogels with stimuli-responsive behaviors under aqueous environments are attractive for their potential applications in controlled drug delivery, clinical diagnostics, and tissue engineering. However, there still remain challenges in developing multicomponent hydrogels as a new generation of "smart" soft materials with multiple intelligent functions toward complex biochemical stimuli. In this work, a three dimensional (3D)-nanostructured supramolecular hydrogel was fabricated using a simple and facile strategy via the self-assembly of graphene oxide (GO) nanosheets, poly(vinyl alcohol) (PVA) chains, and G-quartet/hemin (G4/H) motifs. The as-prepared GO/PVA/G4/H hydrogel exhibited a honeycomb-like 3D GO network architecture as well as excellent mechanical properties. Importantly, the hydrogel demonstrated pH-inducing reversible and cyclic phase transitions between solution and hydrogel states, which could be used as "ink" for injectable 3D printing of different shaped patterns. Also, binary AND and OR logic gates were successfully built by encapsulating enzymes into the hydrogels, which responded to a variety of biochemicals. In addition, the hydrogels showed excellent peroxidase-like activity, achieving the ultrasensitive detection of H2O2 at a concentration as low as 100 nM by their deposition on an electrochemical electrode. The design of multicomponent hydrogels opens up an avenue to fabricate novel "smart" soft matter for biological and medical applications.
在水相环境下具有刺激响应行为的超分子水凝胶因其在控制药物释放、临床诊断和组织工程等方面的潜在应用而受到关注。然而，在开发具有多种智能功能的多组分水凝胶作为新一代“智能”软材料以应对复杂的生化刺激方面仍然存在挑战。在这项工作中，通过氧化石墨烯（GO）纳米片、聚乙烯醇（PVA）链和 G-四聚体/血红素（G4/H）基序的自组装，采用简单易行的策略制备了三维（3D）纳米结构超分子水凝胶。所制备的 GO/PVA/G4/H 水凝胶具有蜂窝状 3D GO 网络结构和优异的机械性能。重要的是，该水凝胶表现出 pH 诱导的可逆和循环相转变，可在溶液和水凝胶状态之间转换，可用作不同形状图案的可注射 3D 打印“墨水”。此外，通过将酶封装在水凝胶中成功构建了二进制 AND 和 OR 逻辑门，它们可以响应多种生化物质。此外，水凝胶表现出优异的过氧化物酶样活性，通过将其沉积在电化学电极上，可实现低至 100 nM 的 H2O2 的超灵敏检测。多组分水凝胶的设计为生物和医学应用中制造新型“智能”软物质开辟了一条途径。
