从合成和/M (M = Fe, Cu) 复合物中有效光解氧化物
H Christopher Fry1, Paul G Hoertz, Ian M Wasser
1Department of Chemistry, Johns Hopkins University, 3400 North Charles Street, Baltimore, MD 21218, USA.
Journal of the American Chemical Society
|December 23, 2004
概括
合成的血氧复合物在光激发时释放出氧气. 最简单的复合体显示了较高的二氧化物解离的量子产量,与其他和氧-肌球蛋白相比.
科学领域:
- 生物化学 生物化学
- 摄影化学的使用.
- 频谱学是一种光谱学.
背景情况:
- 血红二氧化物复合体在生物氧气运输和储存中至关重要.
- 了解这些复合物的光化学,可以了解它们的功能和潜在应用.
- 合成类似物允许对血红二氧化物相互作用进行受控研究.
研究的目的:
- 研究二氧化碳从合成血氧-二氧化碳和血氧-二氧化碳/M复合物的光解离.
- 为了比较不同复合体中二氧化物释放的量子产量.
- 为了确定二氧化碳与这些复合物重新结合的速率常数.
主要方法:
- 合成血红二氧化物和血红二氧化物/M复合物的低温稳定 (M = Cu, Fe).
- 使用激光 (355或532 nm) 进行单波长激发.
- 过渡吸收光谱检测频谱变化 (索雷特波段转移),这些变化表明了二氧化物解离和铁生成.
主要成果:
- 激发诱导的二氧化物解离,由铁 (Soret带在427nm) 的出现和铁超氧化物 (FeIII(O2-)) Soret带 (410nm) 的漂白证明.
- 对于所有四种研究的海姆复合体,二氧化物重新结合发生在类似的速率常数 (大约6-9 x 10^5 M^-1 s^-1) 上.
- 与其他复合物 (phi ≈ 0.2-0.3) 和氧-肌球蛋白 (phi = 0.3) 相比,最简单的血-O2复合物 (F8)FeIII(O2-) (phi = 0.60) 的O2离散量子产量最高.
结论:
- 合成的血-二氧化物复合物可以经历光诱导的二氧化物释放.
- 光解离的效率取决于特定的海姆复合体结构.
- 最简单的合成heme-O2复合体表现出结合的二氧化碳的优越光可变性.
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