Fiallo M M, Tayeb H, Suarato A, Garnier-Suillerot A
Laboratoire de Chimie Bioinorganique, LPBC CNRS ESA7033, Université Paris Nord, 74, rue Marcel Cachin, 93017 Bobigny Cedex, France.
J Pharm Sci. 1998 Aug;87(8):967-75. doi: 10.1021/js970436l.
The band assignment of the circular dichroism (CD) spectra of anthracyclines can provide us with the tools to study the interaction of these molecules with biomolecules, such as DNA and membranes, and also with metal ions. This paper reports the CD spectra of 17 anthracycline derivatives and the tentative assignment of the bands to specific electronic transitions. The deprotonation of some anthracyclines, such as doxorubicin, daunorubicin, and idarubicin, have been also studied in order to characterize the electronic transitions involved in the acid-base process. Our evidence suggests the following assignment. The position of the band assigned to pi-->pi transition, polarized along the short axis of the molecule ( approximately 290 nm), does not depend on the hydroxyl group at C(11) (presence and/or ionization state), whereas the position of the band assigned to the pi-->pi transition ( approximately 480 nm), polarized along the long axis, is strongly dependent on it. Concerning the n-->pi transitions, the bands at approximately 320 and approximately 350 nm have a strong contribution of the n-->pi C(12)=O transition and the n-->pi C(5)=O transition, respectively.
蒽环类药物圆二色性（CD）光谱的谱带归属能够为我们提供工具，用以研究这些分子与生物分子（如DNA和细胞膜）以及金属离子之间的相互作用。本文报道了17种蒽环类衍生物的CD光谱，并对谱带归属到特定电子跃迁进行了初步分析。为了表征酸碱过程中涉及的电子跃迁，还对一些蒽环类药物（如多柔比星、柔红霉素和伊达比星）的去质子化进行了研究。我们的证据表明以下归属情况。归属到沿分子短轴极化的π→π跃迁的谱带位置（约290nm）不依赖于C(11)位的羟基（存在和/或电离状态），而归属到沿长轴极化的π→π跃迁的谱带位置（约480nm）则强烈依赖于该羟基。关于n→π跃迁，约320nm和约350nm处的谱带分别对n→π C(12)=O跃迁和n→π C(5)=O跃迁有很大贡献。
