Andersson L A, Loehr T M, Wu W S, Chang C K, Timkovich R
Department of Chemical and Biological Sciences, Oregon Graduate Institute, Beaverton 97006-1999.
FEBS Lett. 1990 Jul 16;267(2):285-8. doi: 10.1016/0014-5793(90)80946-g.
The heme d1 macrocycle of Ps. aeruginosa dissimilatory nitrite reductase is an iron porphyrin-3,8-dione with a 17-acrylate substituent. We have compared the RR properties of Cu-d1, the copper(II) TME of extracted heme d1, with those of models that differ only with respect to the acrylate: Cu-17-acrylate mesoporphyrin-3,8-dione (2) and Cu-mesoporphyrin-3,8-dione (3). The RR spectrum of Cu-d1 is very similar to that of 2, including v(C = O) at approximately 1720 cm-1. Replacement of the acrylate with propionate changes the spectrum markedly. For example, the v(C = O) mode of 3 shifts to 1712 cm-1, and peaks of Cu-d1 and 2 at approximately 1400 and approximately 1535 cm-1 are shifted or absent from the spectrum of 3. FTIR spectra of 2 and 3 also differ in their voxo(C = O) frequencies. The acrylate thus has a surprisingly strong influence on the electronic structural and spectral properties of heme d1. These data provide a foundation for studies of the novel biological porphyrindione macrocycles.
铜绿假单胞菌异化亚硝酸盐还原酶的血红素d1大环是一种带有17-丙烯酸酯取代基的铁卟啉-3,8-二酮。我们已将提取的血红素d1的铜（II）TME即Cu-d1的拉曼光谱性质与仅在丙烯酸酯方面存在差异的模型的拉曼光谱性质进行了比较：Cu-17-丙烯酸酯中卟啉-3,8-二酮（2）和Cu-中卟啉-3,8-二酮（3）。Cu-d1的拉曼光谱与2的拉曼光谱非常相似，包括在约1720 cm⁻¹处的v（C = O）。用丙酸酯取代丙烯酸酯会使光谱发生显著变化。例如，3的v（C = O）模式移至1712 cm⁻¹，并且在约1400和约1535 cm⁻¹处的Cu-d1和2的峰在3的光谱中发生了位移或消失。2和3的傅里叶变换红外光谱在其voxo（C = O）频率上也存在差异。因此，丙烯酸酯对血红素d1的电子结构和光谱性质具有惊人的强烈影响。这些数据为新型生物卟啉二酮大环的研究奠定了基础。
