Resonance Raman spectroscopic studies of hydroperoxo derivatives of cobalt-substituted myoglobin.

Resonance Raman spectroscopic studies of hydroperoxo derivatives of cobalt-substituted myoglobin.
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钴取代肌红蛋白的氢过氧衍生物的共振拉曼光谱研究。

DOI:
10.1016/j.jinorgbio.2008.07.005
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发表时间:
2008
影响因子:
3.9
通讯作者:
Kincaid,JamesR
Kincaid,JamesR
中科院分区:
生物学2区
文献类型:
--
作者:
Mak,PiotrJ;Kincaid,JamesR

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最近的进展,在产生和稳定的反应性血红素蛋白酶的中间体,通过cryorradiolytic还原,促使应用一系列的光谱方法,以有效地询问这些物种。共振拉曼光谱表征这些样品的令人印象深刻的潜力,最近已被证明在一些过氧和氢过氧中间体的研究。虽然预期这种方法可以有效地应用于其反应循环天然涉及这些过氧和氢过氧中间体的广泛的血红素蛋白,但有时会出现的一个限制是缺乏天然系统中关键配体内ν(0 - 0)拉伸模式的增强。本工作进行探索钴取代的效用,以增强具有跨轴组氨酸连接的氢过氧形式的血红素蛋白的CoOOH片段的ν(Co-O)和ν(O-O)模式。因此,最近完成了氢过氧肌红蛋白的RR研究,现在注意力转向其钴取代的类似物。用16 O2和18 O2制备的样品获得光谱,以揭示ν(M-O)和ν(O-O)模式,后者实际上只在钴取代的蛋白质中观察到。此外,还获得了在氘代溶剂中制备的样品的光谱,为氢过氧物种的存在提供了明确的证据。
Recent progress in generating and stabilizing reactive heme protein enzymatic intermediates by cryoradiolytic reduction has prompted application of a range of spectroscopic approaches to effectively interrogate these species. The impressive potential of resonance Raman spectroscopy for characterizing such samples has been recently demonstrated in a number of studies of peroxo- and hydroperoxo-intermediates. While it is anticipated that this approach can be productively applied to the wide range of heme proteins whose reaction cycles naturally involve these peroxo- and hydroperoxo-intermediates, one limitation that sometimes arises is the lack of enhancement of the key intraligand ν(O–O) stretching mode in the native systems. The present work was undertaken to explore the utility of cobalt substitution to enhance both the ν(Co–O) and ν(O–O) modes of the CoOOH fragments of hydroperoxo forms of heme proteins bearing a trans–axial histidine linkage. Thus, having recently completed RR studies of hydroperoxo myoglobin, attention is now turned to its cobalt-substituted analogue. Spectra are acquired for samples prepared with16O2and18O2to reveal the ν(M–O) and ν(O–O) modes, the latter indeed being observed only for the cobalt-substituted proteins. In addition, spectra of samples prepared in deuterated solvents were also acquired, providing definitive evidence for the presence of the hydroperoxo-species.
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发表时间: 1979
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DOI: --
发表时间: 1986
期刊: The Journal of biological chemistry
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