Department of Chemistry, Physics and Environment, Faculty of Sciences and Environment, "Dunarea de Jos" University of Galati, 111 Domneasca Street, 800201 Galati, Romania.
Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia.
Molecules. 2020 Nov 13;25(22):5298. doi: 10.3390/molecules25225298.
Seeking to enrich the yet less explored field of scorpionate complexes bearing antioxidant properties, we, here, report on the synthesis, characterization and assessment of the antioxidant activity of new complexes derived from three scorpionate ligands. The interaction between the scorpionate ligands thallium(I) hydrotris(5-methyl-indazolyl)borate (TlTp), thallium(I) hydrotris(4,5-dihydro-2H-benzo[g]indazolyl)borate (TlTp) and potassium hydrotris(3--butyl- pyrazolyl)borate (KTp), and metal(II) chlorides, in dichloromethane at room temperature, produced a new family of complexes having the stoichiometric formula [M(Tp)] (M = Cu, ; Zn, ; Cd, ), [M(Tp)] (M = Cu, ; Zn, ; Cd, ), [Cu(Hpz)Cl] (), [Zn(Tp)Cl] () and [Cd(Bp)(Hpz)Cl] (). The obtained metal complexes were characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance and elemental analysis, highlighting the total and partial hydrolysis of the scorpionate ligand Tp during the synthesis of the Cu(II) complex and the Cd(II) complex , respectively. An assessment of the antioxidant activity of the obtained metal complexes was performed through both enzymatic and non-enzymatic assays against 1,1-diphenyl-2-picryl- hydrazyl (DPPH), 2,2'-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), hydroxyl (HO), nitric oxide (NO), superoxide (O) and peroxide (OOH) radicals. In particular, the complex [Cu(Tp)]⋅0.5HO () exhibited significant antioxidant activity, as good and specific activity against superoxide (O), (IC50 values equal to 5.6 ± 0.2 μM) and might be identified as auspicious SOD-mimics (SOD = superoxide dismutase).
为了丰富具有抗氧化性质的冠醚配合物这一研究较少的领域，我们在此报告了三种冠醚配体衍生的新型配合物的合成、表征和抗氧化活性评估。在室温下，将铊（I）氢三（5-甲基-吲唑基）硼酸盐（TlTp）、铊（I）氢三（4,5-二氢-2H-苯并[g]吲唑基）硼酸盐（TlTp）和钾氢三（3-丁基-吡唑基）硼酸盐（KTp）与金属（II）氯化物在二氯甲烷中相互作用，生成了具有通式[M（Tp）]（M = Cu， ；Zn， ；Cd， ）的新型配合物家族[M（Tp）]（M = Cu， ；Zn， ；Cd， ）、[Cu（Hpz）Cl]（）、[Zn（Tp）Cl]（）和[Cd（Bp）（Hpz）Cl]（）。通过傅里叶变换红外光谱、质子核磁共振和元素分析对所得到的金属配合物进行了表征，分别强调了在 Cu（II）配合物[Cu（Tp）]（）和 Cd（II）配合物[Cd（Bp）（Hpz）Cl]（）的合成过程中，Tp 冠醚配体的完全和部分水解。通过 1,1-二苯基-2-苦基肼基（DPPH）、2,2'-联氮-双（3-乙基苯并噻唑啉-6-磺酸）（ABTS）、羟基（HO）、一氧化氮（NO）、超氧自由基（O）和过氧自由基（OOH）自由基的酶促和非酶促测定评估了所得到的金属配合物的抗氧化活性。特别是配合物[Cu（Tp）]⋅0.5HO（）表现出显著的抗氧化活性，对超氧自由基（O）具有良好和特异的活性（IC50 值等于 5.6 ± 0.2 μM），并可能被鉴定为有希望的 SOD 模拟物（SOD = 超氧化物歧化酶）。
