2,2′-联吡啶类似物的面羰基铼(I)配合物的结构和溶液配位研究

IF 3.7 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY ACS Omega Pub Date : 2024-10-26 DOI:10.1021/acsomega.4c0711710.1021/acsomega.4c07117
Tamás Pivarcsik, Jakob Kljun, Sergio Clemente Rodriguez, David Cortéz Alcaraz, Uroš Rapuš, Márta Nové, Egon F Várkonyi, József Nyári, Anita Bogdanov, Gabriella Spengler, Iztok Turel* and Éva A. Enyedy*, 
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引用次数: 0

摘要

在本研究中,我们报告了 12 种新型铼(I)配合物的合成和表征,这些配合物的通式为 fac-[Re(CO)3(NN)X]n+,其中 (NN) 是 2,2′-联吡啶类似配体,X = Cl-、Br- 或 H2O,n = 0 或 1,我们重点研究了它们在水溶液中的形态。所制备的有机铼配合物在水溶液中的 pH 值范围很宽,而且没有观察到双齿配体或羰基配体的释放。复合物在各种生物相关基质(细胞培养基和真实血清)中的稳定性也得到了证实。但同时观察到水取代了卤代配体,配体中的酯键水解缓慢,影响了化合物的溶解度和亲油性。在氯离子存在的情况下,水配合物变得更加亲脂,而由于酯键的水解,亲水性随着时间的推移显著增加,这可能是导致其药理活性较弱的原因。研究结果还显示,卤代配合物的水溶性受到动力学阻碍,而水生配合物的氯离子亲和力较低。络合物中配位的水配体在 pH = 7-10 范围内发生去质子化,导致在 pH = 7.4 时形成大量(18-30%)羟基物种。卤代配合物对人结肠腺癌癌细胞(Colo205 和 Colo320)的细胞毒性(IC50 = 60-99 μM)略高于相应的含水配合物(IC50 > 100 μM)。在所有情况下,均未观察到抗菌效果(MIC > 100 μM),但其中一些复合物对单纯疱疹病毒 2 显示出中等程度的抗病毒活性(IC50 ∼ 50 μM)。
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Structural and Solution Speciation Studies on fac-Tricarbonylrhenium(I) Complexes of 2,2′-Bipyridine Analogues

In this study, we report the synthesis and characterization of 12 novel rhenium(I) complexes with the general formula fac-[Re(CO)3(NN)X]n+ where (NN) is a 2,2′-bipyridine analogue ligand, X = Cl, Br, or H2O, and n = 0 or 1, focusing on their speciation in an aqueous solution. The prepared organorhenium complexes are stable in a wide pH range in an aqueous solution, and no release of the bidentate ligands or the carbonyl ligands was observed. The stability of the complexes in various biologically relevant matrices (cell culture medium and real blood serum) was also demonstrated. However, the simultaneous substitution of the halido ligand by water and slow hydrolysis of the ester bonds in the ligands were observed, affecting both the solubility and the lipophilicity of the compounds. The aqua complexes became more lipophilic in the presence of chloride ions, while the hydrophilicity increased significantly with time due to the hydrolysis of the ester bonds, which probably contributed to their weak pharmacological activity. The results also showed kinetically hindered aqueous solvation of the halido complexes and low chloride ion affinity of the aqua complexes. The deprotonation of the coordinated aqua ligand in the complexes occurs in the pH = 7–10 range, leading to significant formation (18–30%) of hydroxido species at pH = 7.4. The halido complexes showed somewhat higher cytotoxicity (IC50 = 60–99 μM) on human colon adenocarcinoma cancer cells (Colo205 and Colo320) than the corresponding aqua complexes (IC50 > 100 μM). In all cases, no antibacterial effect was observed (MIC > 100 μM), but some of the complexes showed moderate antiviral activity (IC50 ∼ 50 μM) on Herpes simplex virus 2.

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ACS Omega
ACS Omega Chemical Engineering-General Chemical Engineering
CiteScore
6.60
自引率
4.90%
发文量
3945
审稿时长
2.4 months
期刊介绍: ACS Omega is an open-access global publication for scientific articles that describe new findings in chemistry and interfacing areas of science, without any perceived evaluation of immediate impact.
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