Shewanella oneidensis as a living electrode for controlled radical polymerization
Shewanella oneidensis as a living electrode for controlled radical polymerization
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DOI：
10.1073/pnas.1800869115
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发表时间：
2018-05-01
影响因子：
11.1
通讯作者：
Keitz, Benjamin K.
中科院分区：
文献类型：
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作者：
Fan, Gang;Dundas, Christopher M.;Keitz, Benjamin K.
代谢工程促进了药物，燃料和软材料的生产，但通常限于优化明确的代谢途径。我们假设，可用于代谢工程的反应空间可以通过将细胞外电子转移耦合到外源性氧化还原活性金属催化剂的性能来扩展。在这里，我们证明了电活性细菌希瓦氏菌oneidensis可以控制原子转移自由基聚合（ATRP）通过细胞外电子转移的铜催化剂的活性。利用S. oneidensis，我们实现了对生物正交聚合物的分子量和多分散性的精确控制，而类似的生物体，如大肠杆菌，没有显示出显著的活性。我们发现，催化剂的性能是细菌代谢和特定的电子传递蛋白的一个强大的功能，这两者都为未来的应用提供了潜在的生物靶标。总的来说，我们的研究结果表明，操纵细胞外电子传递途径可能是一个通用的策略，将有机金属催化到剧目的代谢控制的转换。
Metabolic engineering has facilitated the production of pharmaceuticals, fuels, and soft materials but is generally limited to optimizing well-defined metabolic pathways. We hypothesized that the reaction space available to metabolic engineering could be expanded by coupling extracellular electron transfer to the performance of an exogenous redox-active metal catalyst. Here we demonstrate that the electroactive bacterium Shewanella oneidensis can control the activity of a copper catalyst in atom-transfer radical polymerization (ATRP) via extracellular electron transfer. Using S. oneidensis, we achieved precise control over the molecular weight and polydispersity of a bioorthogonal polymer while similar organisms, such as Escherichia coli, showed no significant activity. We found that catalyst performance was a strong function of bacterial metabolism and specific electron transport proteins, both of which offer potential biological targets for future applications. Overall, our results suggest that manipulating extracellular electron transport pathways may be a general strategy for incorporating organometallic catalysis into the repertoire of metabolically controlled transformations.