Institute of Organic Chemistry, Johannes Gutenberg-University Mainz, Duesbergweg 10-14, 55128, Mainz, Germany.
Institute of Physics, Johannes Gutenberg-University Mainz, Max Planck Institute for Polymer Research, Ackermannweg 10, 55128, Mainz, Germany.
Angew Chem Int Ed Engl. 2017 Nov 27;56(48):15461-15465. doi: 10.1002/anie.201708857. Epub 2017 Nov 3.
A multistimuli-responsive transient supramolecular polymerization of β-sheet-encoded dendritic peptide monomers in water is presented. The amphiphiles, which contain glutamic acid and methionine, undergo a glucose oxidase catalyzed, glucose-fueled transient hydrogelation in response to an interplay of pH and oxidation stimuli, promoted by the production of reactive oxygen species (ROS). Adjusting the enzyme and glucose concentration allows tuning of the assembly and the disassembly rates of the supramolecular polymers, which dictate the stiffness and transient stability of the hydrogels. The incorporation of triethylene glycol chains introduces thermoresponsive properties to the materials. We further show that repair enzymes are able to reverse the oxidative damage in the methionine-based thioether side chains. Since ROS play an important role in signal transduction cascades, our strategy offers great potential for applications of these dynamic biomaterials in redox microenvironments.
本文报道了一种在水中由β-折叠编码树枝状肽单体引发的多刺激响应瞬态超分子聚合。这些两亲分子含有谷氨酸和蛋氨酸，在葡萄糖氧化酶的催化作用下，在 pH 值和氧化刺激的共同作用下，通过产生活性氧物种（ROS），响应葡萄糖进行瞬态水凝胶化。通过调节酶和葡萄糖的浓度，可以调节超分子聚合物的组装和解组装速率，从而控制水凝胶的硬度和瞬态稳定性。三甘醇链的引入为材料带来了温敏性。我们进一步表明，修复酶能够逆转蛋氨酸硫醚侧链的氧化损伤。由于 ROS 在信号转导级联中起着重要作用，我们的策略为这些动态生物材料在氧化还原微环境中的应用提供了很大的潜力。
