FLUORESCENCE, RESONANCE RAMAN, AND RADIATIONLESS DECAY IN SEVERAL HEMOPROTEINS
FLUORESCENCE, RESONANCE RAMAN, AND RADIATIONLESS DECAY IN SEVERAL HEMOPROTEINS
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DOI：
10.1021/j100561a010
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发表时间：
1976-01-01
影响因子：
--
通讯作者：
ARONOWITZ, S
中科院分区：
文献类型：
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作者：
ADAR, F;GOUTERMAN, M;ARONOWITZ, S
共振拉曼（RR）光谱报告的五个血红素：（a）铁细胞色素b5;（B）氧合血红蛋白;（c）铁细胞色素65;（d）脱氧血红蛋白;和（e）高铁血红蛋白。化合物a显示背景荧光带，其给出不完全振动弛豫的证据。（a）：钯中卟啉：锌中卟啉的相对荧光产率为1：2.5 × 102：10 ~ 4.化合物（B）至（e）不显示荧光，但RR强度降低。（a）中荧光的出现和（a）~（e）的RR强度的降低是由于电子无辐射衰变时间re从100 fs减小到3 fs，其顺序为（a）>（B）>（c）~（d）>（e）。根据可见吸收带的分辨率估计时间re。因此，对于（a）可见带是^（，*），并且在较低能量下，相同自旋的唯一状态是1（d，d）;对于（B）在低于4 Q（ir，ir*）的能量下，不仅存在可能的1（d，d）状态，而且存在涉及O2配体上的跃迁的单线态和电荷转移单线态环->>氧;对于（c），可见激发态是2 Q（tt，t*），并且在较低能量下存在2（d，d）、2（ir，d）和2（，*）个激发态;类似地，对于（d），在比可见态5 Q（t，t*）低的能量下存在5（d，d）和5（，*）个激发态;最后，（e）在可见光能量区具有λ和6（Tr，d）电子态，它们之间具有重振动混合。探讨了光子相干时间rp和振动相对论rv在确定散射过程性质中的作用。
Resonance Raman (RR) spectra are reported for five hemoproteins:(a) ferrocytochrome b5;(b) oxyhemoglobin;(c) ferricytochrome 65;(d) deoxyhemoglobin; and (e) methemoglobin. Compound a shows background fluorescence bands which give evidence for incomplete vibrational relaxation. Relative fluorescence yields for (a): palladium mesoporphyrimzinc mesoporphyrin are 1: 2.5 X 102: 104. Compounds (b) through (e) show no fluorescence but decreasing RR intensity. The presence of fluorescence in (a) and the decreasing RR in-tensity of (a) through (e) are attributed to decreasing electronic radiationless decay times, re, from 100 to 3 fs across the series (a)>(b)>(c)~(d)>(e). The times re are estimated from the resolution of the visible ab-sorption bands. Iterative extended Hückel calculations are used to rationalize re: Thus for (a) the visible band is^(,*) and at lower energy the only state of the same spin is 1 (d, d); for (b) at lower energy than 4Q (ir, ir*) there is not only a possible 1 (d, d) state but singlets involving transitions on the O2 ligand and charge transfer singlets ring-» oxygen; for (c) the visible excited state is 2Q (tt, t*) and there are 2 (d, d), 2 (ir, d), and 2 (,*) excited states at lower energy; similarly for (d) there are 5 (d, d) and 5 (,*) at lower energy than the visible state 5Q (t, t*); finally (e) has both ánd 6 (Tr, d) electronic states in the visible energy region with heavy vibronic mixing between them. The roles of photon coherence time, rp, and vibrational re-laxation, rv, in determining the nature of the scattering process are explored.