Xue Teng, Peng Bo, Xue Min, Zhong Xing, Chiu Chin-Yi, Yang Si, Qu Yongquan, Ruan Lingyan, Jiang Shan, Dubin Sergey, Kaner Richard B, Zink Jeffrey I, Meyerhoff Mark E, Duan Xiangfeng, Huang Yu
1] Department of Materials Science and Engineering, University of California, Los Angeles, California 90095, USA [2].
1] Department of Chemistry, The University of Michigan, 930 N. University, Ann Arbor, Michigan 48109, USA [2].
Nat Commun. 2014;5:3200. doi: 10.1038/ncomms4200.
The integration of multiple synergistic catalytic systems can enable the creation of biocompatible enzymatic mimics for cascading reactions under physiologically relevant conditions. Here we report the design of a graphene-haemin-glucose oxidase conjugate as a tandem catalyst, in which graphene functions as a unique support to integrate molecular catalyst haemin and enzymatic catalyst glucose oxidase for biomimetic generation of antithrombotic species. Monomeric haemin can be conjugated with graphene through π-π interactions to function as an effective catalyst for the oxidation of endogenous L-arginine by hydrogen peroxide. Furthermore, glucose oxidase can be covalently linked onto graphene for local generation of hydrogen peroxide through the oxidation of blood glucose. Thus, the integrated graphene-haemin-glucose oxidase catalysts can readily enable the continuous generation of nitroxyl, an antithrombotic species, from physiologically abundant glucose and L-arginine. Finally, we demonstrate that the conjugates can be embedded within polyurethane to create a long-lasting antithrombotic coating for blood-contacting biomedical devices.
多种协同催化体系的整合能够在生理相关条件下创建用于级联反应的生物相容性酶模拟物。在此，我们报道了一种石墨烯-血红素-葡萄糖氧化酶共轭物作为串联催化剂的设计，其中石墨烯作为独特的载体，将分子催化剂血红素和酶催化剂葡萄糖氧化酶整合起来，用于仿生生成抗血栓物质。单体血红素可通过π-π相互作用与石墨烯共轭，作为过氧化氢氧化内源性L-精氨酸的有效催化剂。此外，葡萄糖氧化酶可共价连接到石墨烯上，通过血液葡萄糖的氧化在局部产生过氧化氢。因此，整合后的石墨烯-血红素-葡萄糖氧化酶催化剂能够轻易地从生理上丰富的葡萄糖和L-精氨酸中持续生成抗血栓物质硝酰。最后，我们证明该共轭物可嵌入聚氨酯中，为与血液接触的生物医学装置创建持久的抗血栓涂层。
