Chitosan confinement enhances hydrogen photogeneration from a mimic of the diiron subsite of [FeFe]-hydrogenase
Chitosan confinement enhances hydrogen photogeneration from a mimic of the diiron subsite of [FeFe]-hydrogenase
复制标题
壳聚糖限制增强了 [FeFe]-氢化酶二铁亚位点模拟物的氢光生作用
DOI：
10.1038/ncomms3695
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发表时间：
2013-10-01
影响因子：
16.6
通讯作者：
Wu, Li-Zhu
中科院分区：
文献类型：
--
作者：
Jian, Jing-Xin;Liu, Qiang;Wu, Li-Zhu
大自然创造了[FeFe]-氢化酶作为具有高周转率的氢形成催化剂。然而，由于其有限的稳定性以及其生产和纯化的成本，它不能满足经济上可用的催化剂的需求。合成化学允许制备非常接近的模拟[FeFe]-氢化酶，但迄今未能重现其催化活性。活性位点的大多数模型仅代表无机辅因子的模拟物，并且在受限环境中进行的酶样反应不太清楚。在这里，我们报告，壳聚糖，一种天然多糖，提高了效率和耐久性的典型模拟的二铁亚位点的[FeFe]-氢化酶的光催化析氢。与不存在壳聚糖的相同系统相比，自组装系统的周转数增加约4，000倍。据我们所知，这种显着的改善人工[FeFe]-氢化酶样系统的活性和稳定性，迄今尚未报道。
Nature has created [FeFe]-hydrogenase enzyme as a hydrogen-forming catalyst with a high turnover rate. However, it does not meet the demands of economically usable catalytic agents because of its limited stability and the cost of its production and purification. Synthetic chemistry has allowed the preparation of remarkably close mimics of [FeFe]-hydrogenase but so far failed to reproduce its catalytic activity. Most models of the active site represent mimics of the inorganic cofactor only, and the enzyme-like reaction that proceeds within restricted environments is less well understood. Here we report that chitosan, a natural polysaccharide, improves the efficiency and durability of a typical mimic of the diiron subsite of [FeFe]-hydrogenase for photocatalytic hydrogen evolution. The turnover number of the self-assembling system increases ~4,000-fold compared with the same system in the absence of chitosan. Such significant improvements to the activity and stability of artificial [FeFe]-hydrogenase-like systems have, to our knowledge, not been reported to date.