氧化原子转移氧化物化学;NO的机制 (g) 到化物转化利用μ-oxoHeme-Fe (III) -O-Cu (II) (L) 构造物
Shabnam Hematian1, Isabell Kenkel2, Tatyana E Shubina2
1†Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21211, United States.
Journal of the American Chemical Society
|May 15, 2015
概括
合成的血铜复合物有效地将氧化氧化 (NO) 氧化为酸盐,模仿生物过程. 这项研究详细介绍了NO调节所涉及的机制和中间体.
科学领域:
- 生物有机化学 生物有机化学
- 生物物理化学 生物物理化学
- 协调化学 协调化学
背景情况:
- 氧化 (NO) 是一种重要的生物信号分子,需要严格控制细胞度.
- 氧化转化NO到酸盐 (NO2(-)) 是一个关键的调节机制,部分由细胞染色体c氧化酶介导.
- 了解NO代谢对于各种生理和病理过程至关重要.
研究的目的:
- 通过使用合成μ-oxo海姆-Fe (III) -O-Cu (II) -L) 结构,研究气态氧化物 (NO) 到化物 (NO2 ((-)) 的高效氧化.
- 为了阐明机械路径,并确定参与这种NO氧化过程的中间物种.
- 将新型μ-oxo复合物的结构和反应性与现有的类似物进行比较.
主要方法:
- 新的μ-oxo血铜复合物的合成和特征与不同的配体 (L).
- 谱学研究 (UV-Vis,EPR) 和动力学研究 (低温停止流) 来探测反应机制.
- 用于结构确定和密度功能理论 (DFT) 计算的X射线晶体学,以获得机械洞察力.
主要成果:
- 合成的μ-oxo复合物有效地催化NO ((g) 氧化为酸盐 (NO2 ((-)).
- 反应是通过NO的连续添加进行的,形成一个铁-酸盐和一个铜-酸盐复合体.
- 一个关键的中间体,一个bis-NO添加物[(NO) ((酸) Fe ((II) - ((NO2 (((-)) - Cu ((II) (((L) ](+),被识别并通过光谱学表征.
结论:
- 合成的μ-oxo血铜复合体有效地模仿了在生物系统中观察到的NO-to-nitrite转化.
- 通过实验和计算数据获得了对NO氧化和储存的详细机制见解,得到了支持.
- 这些发现有助于理解NO在生物信号传递中的作用以及潜在的治疗策略.
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