Co-localization of catalysts within a protein cage leads to efficient photochemical NADH and/or hydrogen production
Co-localization of catalysts within a protein cage leads to efficient photochemical NADH and/or hydrogen production
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DOI：
10.1039/c6tb01175f
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发表时间：
2016-01-01
影响因子：
7
通讯作者：
Douglas, Trevor
中科院分区：
文献类型：
--
作者：
Edwards, Ethan;Roychoudhury, Rajarshi;Douglas, Trevor
利用 P22 病毒样颗粒 (VLP) 的内部，我们共定位并约束了光敏剂 (Eosin-Y) 和 NADH/氢催化剂 (钴肟) 的多个副本。这些小分子与通过原子转移自由基聚合 (ATRP) 在 P22 衣壳范围内合成的带有胺的聚合物框架缀合。使用甲基丙烯酸氨乙酯 (AEMA) 和双丙烯酰胺作为单体，我们引入了具有可寻址胺的交联聚合物框架，并通过异硫氰酸酯部分缀合每个小分子。通过精确控制平均标记化学计量，我们将曙红-Y 和钴肟催化剂与聚合物共轭，使它们共定位在 P22 VLP 的内部。这种共定位促进了在水性条件下从NAD+光化学产生NADH，最大周转率为11.40 x 10 (-3) s(-1)。通过增加钴肟标记的相对化学计量，可以将反应产物从 NADH 转变为 H-2 生产。 VLP P22 内这种耦合催化系统的共同限制产生了一种纳米材料，其周转活性与本体浓度无关。这些结构是仿生材料设计和合成方法的一个例子，其中可以通过病毒样颗粒内的共定位催化剂来控制 NADH 和氢气的有效光化学生产。
Using the interior of the P22 virus-like particle (VLP) we have co-localized and constrained multiple copies of a photosensitizer (Eosin-Y) and a NADH/hydrogen catalyst (cobaloxime). These small molecules were conjugated to an amine bearing polymer framework synthesized within the confines of the P22 capsid by atom transfer radical polymerization (ATRP). Using aminoethyl methacrylate (AEMA) and bisacrylamide as the monomers we introduced a crosslinked polymer framework with addressable amines and conjugated each of the small molecules through an isothiocyanate moiety. With precise control over the average labeling stoichiometry, we conjugated the Eosin-Y and cobaloxime catalysts to the polymer such that they were co-localized on the interior of the P22 VLP. This co-localization facilitated the photochemical production of NADH from NAD+ under aqueous conditions with a maximum turnover of 11.40 x 10 (-3) s(-1). The reaction products could be switched from NADH to H-2 production by increasing the relative stoichiometry of the cobaloxime labeling. The co-confinement of this coupled catalytic system within the VLP P22 creates a nano-material whose turnover activity is independent of the bulk concentration. These constructs are an example of a biomimetic materials design and synthesis approach in which efficient photochemical production of both NADH and hydrogen can be controlled by co-localizing catalysts within a virus-like particle.