Schmid Wolfgang F, John Roland O, Mühlgassner Gerhard, Heffeter Petra, Jakupec Michael A, Galanski Mathea Sophia, Berger Walter, Arion Vladimir B, Keppler Bernhard K
Institute of Inorganic Chemistry, University of Vienna, Währingerstr. 42, A-1090 Vienna, Austria.
J Med Chem. 2007 Dec 13;50(25):6343-55. doi: 10.1021/jm701042w. Epub 2007 Nov 13.
Paullones constitute a class of potent cyclin-dependent kinase inhibitors. To overcome the insufficient solubility and bioavailability, which hamper their potential medical application, we aim at the development of metal-based derivatives. Two types of paullone ligands, L (1) - L (3) and L (4) , with different locations of metal-binding sites, were prepared. They were found to form organometallic complexes of the general formula [M (II)Cl(eta (6)- p-cymene)L]Cl ( 1- 4, L = L (1) - L (4) ; a, M = Ru; b, M = Os). The complexes were characterized by X-ray crystallography, one- and two-dimensional NMR spectroscopy and other physical methods. Complexes 1- 3, with a coordinated amidine unit, were found to undergo E/ Z isomerization in solution. The reaction was studied by NMR spectroscopy, and activation parameters Delta H (double dagger) and Delta S (double dagger) were determined. Antiproliferative activity in the low micromolar range was observed in vitro in three human cancer cell lines by means of MTT assays. (3)H-Thymidine incorporation assays revealed the compounds to lower the rate of DNA synthesis, and flow cytometric analyses showed cell cycle arrest mainly in G 0/ G 1 phase.
泡林酮是一类有效的细胞周期蛋白依赖性激酶抑制剂。为克服其溶解度和生物利用度不足这一阻碍其潜在医学应用的问题,我们致力于开发金属基衍生物。制备了两种具有不同金属结合位点位置的泡林酮配体,即L(1)-L(3)和L(4)。发现它们能形成通式为[M(II)Cl(η(6)-对异丙基苯)L]Cl的有机金属配合物(1-4,L = L(1)-L(4);a,M = Ru;b,M = Os)。通过X射线晶体学、一维和二维核磁共振光谱及其他物理方法对这些配合物进行了表征。发现具有配位脒单元的配合物1-3在溶液中会发生E/Z异构化。通过核磁共振光谱研究了该反应,并测定了活化参数ΔH(‡)和ΔS(‡)。通过MTT试验在三种人类癌细胞系中观察到了低微摩尔浓度范围内的抗增殖活性。(3)H-胸腺嘧啶核苷掺入试验表明这些化合物可降低DNA合成速率,流式细胞术分析显示细胞周期主要阻滞在G0/G1期。