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一氧化碳血红蛋白和氧合血红蛋白的亚皮秒共振拉曼光谱

Subpicosecond resonance Raman spectroscopy of carbonmonoxy- and oxyhemoglobin.

作者信息

van den Berg R, el-Sayed M A

机构信息

Department of Chemistry and Biochemistry, University of California, Los Angeles 90024.

出版信息

Biophys J. 1990 Oct;58(4):931-7. doi: 10.1016/S0006-3495(90)82437-1.

Abstract

In this paper we present the resonance Raman spectrum of the carbonmonoxy- (HbCO) and oxyhemoglobin (HbO2) photointermediates on a 800-900 fs timescale. In the case of HbCO, the frequencies of the so-called core-size markers (1500-1650 cm-1) are characteristic of a deoxylike photoproduct in a high spin state (S = 2) with a partially domed heme. The spectrum of the HbO2 photointermediate, on the other hand, is different, and may be characteristic of an excited-state species. These results are discussed in terms of a reaction scheme previously presented by Petrich, J. W., C. Poyart, and J. L. Martin (1988. Biochemistry. 27:4049-4060) and compared with those obtained in the literature on a 30-40 ps timescale. In both molecules a distinct downshift of the v4 mode was observed with respect to the equilibrium value, which is indicative of an elevated temperature of the heme after photodissociation.

摘要

在本文中,我们展示了碳氧血红蛋白(HbCO)和氧合血红蛋白(HbO₂)光中间体在800 - 900飞秒时间尺度上的共振拉曼光谱。对于HbCO,所谓的核心尺寸标记(1500 - 1650厘米⁻¹)的频率是处于高自旋态(S = 2)且具有部分穹顶状血红素的脱氧样光产物的特征。另一方面,HbO₂光中间体的光谱不同,可能是激发态物种的特征。这些结果根据Petrich、J. W.、C. Poyart和J. L. Martin(1988年,《生物化学》,27:4049 - 4060)之前提出的反应方案进行了讨论,并与在30 - 40皮秒时间尺度上文献中获得的结果进行了比较。在这两种分子中,相对于平衡值都观察到v4模式有明显的下移,这表明光解离后血红素的温度升高。

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本文引用的文献

2
Transient Raman study of CO-haemoprotein photolysis: origin of the quantum yield.
Nature. 1980 Apr 10;284(5756):570-2. doi: 10.1038/284570a0.
4
Resonance Raman spectroscopy of hemoglobin.血红蛋白的共振拉曼光谱
Methods Enzymol. 1981;76:371-413. doi: 10.1016/0076-6879(81)76132-9.
5
Geminate recombination of O2 and hemoglobin.氧气与血红蛋白的双分子复合。
Proc Natl Acad Sci U S A. 1980 Oct;77(10):5606-10. doi: 10.1073/pnas.77.10.5606.
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Hemoglobin: resonance Raman spectra.血红蛋白:共振拉曼光谱
Biochim Biophys Acta. 1972 May 18;263(3):830-3. doi: 10.1016/0005-2795(72)90072-4.
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Picosecond time-resolved resonance Raman studies of hemoglobin: implications for reactivity.
Science. 1985 Aug 16;229(4714):661-5. doi: 10.1126/science.4023704.

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