Rational Design of Covalent Multiheme Cytochrome-Carbon Dot Biohybrids for Photoinduced Electron Transfer
Rational Design of Covalent Multiheme Cytochrome-Carbon Dot Biohybrids for Photoinduced Electron Transfer
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DOI：
10.1002/adfm.202302204
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发表时间：
2023-07-13
影响因子：
19
通讯作者：
Jeuken，Lars J. C.
中科院分区：
文献类型：
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作者：
Zhang，Huijie;Casadevall，Carla;Jeuken，Lars J. C.
生物混合系统可以将无机捕光材料和全细胞生物催化剂结合起来，利用太阳能生产化学品和燃料。全细胞生物催化剂具有内在的自我修复能力，能够通过代谢工程以可持续的方式生产各种多碳化合物。目前的全细胞生物杂交系统在吸光体和代谢酶之间的电子传递途径尚不明确，限制了合理的设计。为了能够设计有效的电子转移途径，开发了由石墨氮掺杂碳点(g-N-CDS)和来自圆球希瓦氏菌MR-1的外膜十血红素蛋白MtrC组成的共价生物杂化。MtrC是MtrCAB蛋白复合体的一个亚单位，它为细菌外膜上的双向电子交换提供了直接管道。通过碳二亚胺化学或酰氯活化，g-N-CDs用马来酰亚胺部分官能化，并与Y657C MtrC突变体表面暴露的半胱氨酸偶联。MtrC∼g-N-CD生物杂交种通过天然和变性凝胶电泳、层析、显微镜和荧光寿命光谱进行了表征。在牺牲电子供体的存在下，mtrC∼g-N-CD生物杂化材料的可见光照射导致mtrC降低。这些生物杂化材料可能在光诱导跨膜电子转移INS中得到应用。单株MR-1用于未来的化学合成。
Biohybrid systems can combine inorganic light‐harvesting materials and whole‐cell biocatalysts to utilize solar energy for the production of chemicals and fuels. Whole‐cell biocatalysts have an intrinsic self‐repair ability and are able to produce a wide variety of multicarbon chemicals in a sustainable way with metabolic engineering. Current whole‐cell biohybrid systems have a yet undefined electron transfer pathway between the light‐absorber and metabolic enzymes, limiting rational design. To enable engineering of efficient electron transfer pathways, covalent biohybrids consisting of graphitic nitrogen doped carbon dots (g‐N‐CDs) and the outer‐membrane decaheme protein, MtrC fromShewanella oneidensisMR‐1 are developed. MtrC is a subunit of the MtrCAB protein complex, which provides a direct conduit for bidirectional electron exchange across the bacterial outer membrane. The g‐N‐CDs are functionalized with a maleimide moiety by either carbodiimide chemistry or acyl chloride activation and coupled to a surface‐exposed cysteine of a Y657C MtrC mutant. MtrC∼g‐N‐CD biohybrids are characterized by native and denaturing gel electrophoresis, chromatography, microscopy, and fluorescence lifetime spectroscopy. In the presence of a sacrificial electron donor, visible light irradiation of the MtrC∼g‐N‐CD biohybrids results in reduced MtrC. The biohybrids may find application in photoinduced transmembrane electron transfer inS. oneidensisMR‐1 for chemical synthesis in the future.