Low frequency resonance Raman spectra of isolated alpha and beta subunits of hemoglobin and their deuterated analogues.
Low frequency resonance Raman spectra of isolated alpha and beta subunits of hemoglobin and their deuterated analogues.
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血红蛋白及其氘代类似物的分离 α 和 β 亚基的低频共振拉曼光谱。
DOI：
10.1002/bip.20573
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发表时间：
2006
期刊：
影响因子：
2.9
通讯作者：
Proniewicz,LeonardM
中科院分区：
文献类型：
--
作者：
Podstawka,Edyta;Mak,PiotrJ;Kincaid,JamesR;Proniewicz,LeonardM
为了进一步了解血红蛋白及其分离亚基的低频振动模式的本质，对几种不同同位素标记的类似物进行了全面研究，并在本文中进行了报道。具体来说，报告了包含天然丰度或各种氘代原血红素类似物的分离α和β亚基的脱氧和连接（CO和O2）形式的共振拉曼光谱，在200和500 cm−1之间。研究的氘化原血红素类似物包括1,3,5,8-C2H3-原血红素（d12-原血红素）、1,3-C2H3-原血红素（1,3-d6-原血红素）、5,8-C2H3-原血红素（5,8-d6-原血红素）和内消旋-C2H4-原血红素（d4-原血红素）。使用反卷积程序对整组采集的光谱进行了分析，以帮助将移位模式与原始形式光谱中的对应模式相关联。有趣的是，先前与所谓的乙烯基弯曲模式或丙酸变形模式相关的模式被证明对大环外围甲基的氘化非常敏感，移动高达 12-15 cm−1，揭示了它们的复杂性质。特别有趣的是，观察到的 1,3-d6- 和 5,8-d6-原血红素类似物的变化证实了某些模式与大环的给定部分相关的事实；即，只有某些模式在 1 和 3 甲基的氘化时发生转变，而其他模式在 5 和 8 甲基的氘化时发生转变。与之前报告的相应肌红蛋白衍生物的光谱相比，这里报告的数据揭示了几个附加特征的出现，这些特征意味着与丙酸酯基团相关的模式的分裂或表明血红素辅基的更大变形。 © 2006 Wiley periodicals, Inc. Biopolymers 83: 455–466, 2006本文最初作为已接受的预印本在线发表。 “在线发布”日期对应于预印本版本。您可以通过发送电子邮件至 Biopolymers 编辑部索取预印本副本：biopolymers@wiley.com
In an attempt to gain further insight into the nature of the low frequency vibrational modes of hemoglobin and its isolated subunits, a comprehensive study of several different isotopically labeled analogues has been undertaken and is reported herein. Specifically, the resonance Raman spectra, between 200 and 500 cm−1, are reported for the deoxy and ligated (CO and O2) forms of the isolated α and β subunits containing the natural abundance or various deuterated analogues of protoheme. The deuterated protoheme analogues studied include the 1,3,5,8‐C2H3‐protoheme (d12‐ protoheme), the 1,3‐C2H3‐protoheme (1,3‐d6‐protoheme), the 5,8‐C2H3‐protoheme (5,8‐d6‐protoheme), and the meso‐C2H4‐protoheme (d4‐protoheme). The entire set of acquired spectra has been analyzed using a deconvolution procedure to help correlate the shifted modes with their counterparts in the spectra of the native forms. Interestingly, modes previously associated with so‐called vinyl bending modes or propionate deformation modes are shown to be quite sensitive to deuteration of the peripheral methyl groups of the macrocycle, shifting by up to 12–15 cm−1, revealing their complex nature. Of special interest is the fact that shifts observed for the 1,3‐d6‐ and 5,8‐d6‐protoheme analogues confirm the fact that certain modes are associated with a given portion of the macrocycle; i.e., only certain modes shift upon deuteration of the 1 and 3 methyl groups, while others shift upon deuteration of the 5 and 8 methyl groups. Compared with the spectra previously reported for the corresponding myoglobin derivatives, the data reported here reveal the appearance of several additional features that imply splitting of modes associated with the propionate groups or that are indicative of greater distortion of the heme prosthetic groups. © 2006 Wiley Periodicals, Inc. Biopolymers 83: 455–466, 2006This article was originally published online as an accepted preprint. The “Published Online” date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com