Raman detection of a peroxy intermediate in the hydroquinone-oxidizing cytochrome aa3 of Bacillus subtilis.

Raman detection of a peroxy intermediate in the hydroquinone-oxidizing cytochrome aa3 of Bacillus subtilis.
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枯草芽孢杆菌氢醌氧化细胞色素 aa3 中过氧中间体的拉曼检测。

DOI:
10.1016/0005-2728(95)00076-u
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发表时间:
1995
期刊:
Biochimica et biophysica acta
影响因子:
--
通讯作者:
Wikström,M
Wikström,M
中科院分区:
--
文献类型:
--
作者:
Varotsis,C;Babcock,GT;Lauraeus,M;Wikström,M

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当枯草芽孢杆菌的氢醌氧化细胞色素aa 3 - 600的混合价、一氧化碳结合形式在O2存在下被照射时,它形成对应于“化合物C”的物质,该物质首先由Chance、Saronio和Leigh(J. Biol. Chem. 250(1975)9226-9237)描述为线粒体细胞色素c氧化酶。该物种的共振拉曼光谱显示出在366 cm− 1处的模式,当用18 O2重复实验时,该模式移动到342 cm− 1。在分辨率范围内,这种模式的出现对氘交换不敏感。高频(1200-1700 cm−1)和低频(200-500 cm−1)数据使我们能够将366 cm− 1模式归属于过氧化物加合物的Fe 3 +-O伸缩振动,其中铁是低或中等自旋。据我们所知,这是第一次报道了“化合物C”的18 O2敏感的铁-氧伸缩模式,为该物种是过氧化物加合物的概念提供了强有力的支持。观察到的366 cm−1ν(Fe 3 +-O−-O−)频率比之前在完全还原的线粒体酶和O2之间的反应中发现的瞬时过氧中间体高8 cm− 1。我们的观察表明,虽然相似,亚稳态过氧血红素a3物种在这里报道的几何形状,质子化状态,和/或氢键状态的细节不同。
When the mixed valence, carbon monoxide-bound form of the hydroquinone-oxidizing cytochrome aa3−600 of Bacillus subtilis is illuminated in the presence of O2, it forms a species that corresponds to ‘Compound C’, first described for the mitochondria) cytochrome c oxidase by Chance, Saronio and Leigh (J. Biol. Chem. 250 (1975) 9226–9237). Resonance Raman spectra of the this species show a mode at 366 cm−1that shifts to 342 cm−1when the experiment is repeated with18O2. The appearance of this mode is insensitive to deuteration exchange within the limits of resolution. High- (1200–1700 cm−1) and low-frequency (200–500 cm−1) data, allow us to assign the 366 cm−1mode to the Fe3+-O stretching vibration of a peroxide adduct where the iron is either low or intermediate spin. This is to our knowledge the first time an18O2-sensitive iron-oxygen stretching mode has been reported for ‘Compound C’, providing strong support for the notion that this species is a peroxide adduct. The observed 366 cm−1ν(Fe3+-O−-O−) frequency is 8 cm−1higher than that previously found for a transient peroxy intermediate in the reaction between the fully reduced mitochondria) enzyme and 02. Our observation indicates that, while similar, the metastable peroxyheme a3 species reported here differs in the fine details of geometry, protonation state, and/or hydrogen bond status.
通过共振拉曼光谱法对细胞色素 c 氧化酶的双氧中间体进行室温表征。
DOI: 10.1021/bi00495a018
发表时间: 1990
期刊: Biochemistry
影响因子: 2.9
作者:
Larsen,RW;Li,W;Copeland,RA;Witt,SN;Lou,BS;Chan,SI;Ondrias,MR
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细胞色素 c 氧化酶中存在氢氧化物中间体的证据。
DOI: --
发表时间: 1989
期刊: The Journal of biological chemistry
影响因子: --
作者:
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通讯作者: Rousseau,DL
DOI: 10.1021/bi00156a027
发表时间: 1992-10
期刊: Biochemistry
影响因子: 2.9
作者:
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DOI: 10.1021/ja00182a001
发表时间: 1990
影响因子: 15
作者:
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通讯作者: D. Rousseau
在细胞色素氧化酶/双氧反应中,ferr1-oxo 中间体出现 v(FeIV = O) 振动。
DOI: 10.1021/bi00484a001
发表时间: 1990
期刊: Biochemistry
影响因子: 2.9
作者:
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通讯作者: Babcock,GT