对于有氧CODH的Mo/Cu辅因子的W/Cu合成模型表明,生物化学CO氧化需要一个丧的易斯酸/基对
Dibbendu Ghosh1, Soumen Sinhababu1, Bernard D Santarsiero2
1Department of Chemistry, University of Illinois at Chicago, 845 W. Taylor Street, Chicago, Illinois 60607, United States.
Journal of the American Chemical Society
|June 30, 2020
概括
研究人员创建了一个W/Cu复合体,一种合成模仿一氧化碳脱酶 (CODH). 这一突破为CO氧化机制提供了洞察力,并可以指导新能源储存催化剂的开发.
科学领域:
- 生物有机化学 生物有机化学
- 有机金属化学 有机金属化学
- 生物化学 生物化学
背景情况:
- 有氧一氧化碳脱酶 (CODH) 的活性位点对于调节大气中的CO和CO2至关重要.
- 在CODH中合成Mo/Cu活性部位的准确模型是一个重大挑战.
- 了解CODH的功能对于全球碳循环至关重要,它涉及化学性自性细菌和古生物.
研究的目的:
- 构建一个模仿空气性一氧化碳脱酶 (CODH) 的Mo/Cu活性位点的合成模型.
- 为了获得对生物化学CO氧化过程的机械洞察力.
- 为未来储能多金属催化剂的设计提供信息.
主要方法:
- 为了合成复合物,采用了一种silyl保护/脱保护策略.
- 在 (bdt) ((O) WVI和CuI ((NHC) 位点之间构建了一个具有混合O2-/S2-结合的W/Cu复合体.
- 对合成复合物的结构和电子特征进行了分析,并与原生CODH辅因子进行了比较.
主要成果:
- 合成了一种W/Cu复合物,代表了迄今为止最接近CODH活性部位的合成模仿物之一.
- 合成复合体和本地CODH辅因子之间的结构和电子特征的差异被确定.
- 这些发现表明,本地CODH活性部位需要紧张的几何和易斯酸/基丧,由蛋白质二次结构强制执行,用于生物化学CO氧化.
结论:
- 这项研究提出了一种新的W/Cu复合物,该复合物密切模仿CODH活性部位.
- 机械学的见解表明,紧张的活性部位和蛋白质诱导的丧对本地酶的功能的重要性.
- 这项研究可以指导用于储能应用的先进合成催化剂的开发.
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