van den Berg R, el-Sayed M A
Department of Chemistry and Biochemistry, University of California, Los Angeles 90024.
Biophys J. 1990 Oct;58(4):931-7. doi: 10.1016/S0006-3495(90)82437-1.
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.
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。