Resonance Raman evidence for protein-induced out-of-plane distortion of the heme prosthetic group of mammalian lactoperoxidase.
Resonance Raman evidence for protein-induced out-of-plane distortion of the heme prosthetic group of mammalian lactoperoxidase.
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蛋白质诱导的哺乳动物乳过氧化物酶血红素辅基平面外变形的共振拉曼证据。
DOI：
10.1021/ja012578u
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发表时间：
2002
影响因子：
15
通讯作者：
Kincaid,JamesR
中科院分区：
文献类型：
--
作者：
Zbylut,StevenD;Kincaid,JamesR
已经获得了静止状态哺乳动物乳过氧化物酶LPO(N)及其六坐标低自旋（6CLS）氰化物配合物LPO（CN）的共振拉曼光谱，以及由部分或完全蛋白水解消化产生的各种含血红素1的片段。这些蛋白水解片段为LPO(N)和LPO（CN）酶的分析提供了一组有用的参考化合物，利用各种配体生成明确的五坐标和六坐标高自旋（5CHS和6CHS）物质。此外，这些模型化合物在多肽链上含有零、一个或两个共价连接的酯键，对于确定血红素周围酯键的存在对血红素共振拉曼标记带的影响程度非常有用。光谱结果不仅为静息状态酶作为6CHS物种的形成提供了强有力的证据，而且还证实了先前记录的几个低频共振拉曼带的异常强度，这是最合理的解释，这是由蛋白质诱导的血红素1大环的面外畸变引起的，这种畸变是由与完整蛋白质的相关多肽残基的共价酯连接介导的。
Resonance Raman spectra have been acquired for resting state mammalian lactoperoxidase, LPO(N), and its six-coordinate, low-spin (6CLS) cyanide complex, LPO(CN), as well as for various heme l containing fragments resulting from partial or complete proteolytic digestion. These proteolytic fragments provide a useful set of reference compounds for analysis of the LPO(N) and LPO(CN) enzymes, using various ligands to generate well-defined five-coordinate and six-coordinate high-spin (5CHS and 6CHS) species. In addition, these model compounds, which contain zero, one, or two covalently attached ester linkages to polypeptide chains, are quite useful for determining the extent to which the presence of the ester linkages at the heme periphery affects the characteristic heme resonance Raman marker bands. The spectral results not only provide strong evidence for the formulation of the resting state enzyme as a 6CHS species, but also confirm the previously documented anomalous intensities of several low-frequency resonance Raman bands, which are most reasonably interpreted to arise from a protein-induced out-of-plane distortion of the heme l macrocycle mediated by the covalent ester linkages to the associated polypeptide residues of the intact protein.