Yasui Hiroyuki, Adachi Yusuke, Katoh Akira, Sakurai Hiromu
Department of Analytical and Bioinorganic Chemistry, Kyoto Pharmaceutical University, 5 Nakauchi-cho, Misasagi, Yamashina-ku, Kyoto 607-8414, Japan.
J Biol Inorg Chem. 2007 Aug;12(6):843-53. doi: 10.1007/s00775-007-0239-5. Epub 2007 May 15.
The antidiabetic effect of vanadium is a widely accepted phenomenon; some oxovanadium(IV) complexes have been found to normalize high blood glucose levels in both type 1 and type 2 diabetic animals. In light of the future clinical use of these complexes, the relationship among their chemical structures, physicochemical properties, metallokinetics, and antidiabetic activities must be closely investigated. Recently, we found that among bis(3-hydroxypyronato)oxovanadium(IV) [VO(3hp)(2)] related complexes, bis(allixinato)oxovanadium(IV) [VO(alx)(2)] exhibits a relatively strong hypoglycemic effect in diabetic animals. Next, we examined its metallokinetics in the blood of rats that received five VO(3hp)(2)-related complexes by the blood circulation monitoring-electron paramagnetic resonance method. The metallokinetic parameters were obtained from the blood clearance curves based on a two-compartment model; most parameters, such as area under the concentration curve and mean residence time, correlated significantly with the in vitro insulinomimetic activity in terms of 1/IC(50) (IC(50) is the 50% inhibitory concentration of the complex required for the release of free fatty acids in adipocytes) and the lipophilicity of the complex (log P (com)). The oxovanadium(IV) concentration was significantly higher and the species resided longer in the blood of rats that received VO(alx)(2) than in the blood of rats that received VO(3hp)(2) or bis(kojato)oxovanadium(IV); VO(alx)(2) also exhibited higher log P (com) and 1/IC(50) values. On the basis of these results, we propose that the introduction of lipophilic groups at the C2 and C6 positions of the 3hp ligand is an effective method to enhance the hypoglycemic effect of the complexes, as supported by the observed in vivo exposure and residence in the blood.
钒的抗糖尿病作用是一个被广泛认可的现象;已发现一些氧钒(IV)配合物可使1型和2型糖尿病动物的高血糖水平恢复正常。鉴于这些配合物未来的临床应用,必须密切研究它们的化学结构、物理化学性质、金属动力学和抗糖尿病活性之间的关系。最近,我们发现,在双(3-羟基吡喃酮基)氧钒(IV)[VO(3hp)(2)]相关配合物中,双(蒜藜芦素基)氧钒(IV)[VO(alx)(2)]在糖尿病动物中表现出相对较强的降血糖作用。接下来,我们通过血液循环监测-电子顺磁共振方法,研究了其在接受5种VO(3hp)(2)相关配合物的大鼠血液中的金属动力学。金属动力学参数是基于二室模型从血药清除曲线中获得的;大多数参数,如浓度曲线下面积和平均驻留时间,在1/IC(50)(IC(50)是配合物在脂肪细胞中释放游离脂肪酸所需的50%抑制浓度)和配合物的亲脂性(log P (com))方面与体外胰岛素模拟活性显著相关。接受VO(alx)(2)的大鼠血液中的氧钒(IV)浓度显著高于接受VO(3hp)(2)或双(曲酸基)氧钒(IV)的大鼠血液中的浓度,且该物种在血液中的驻留时间更长;VO(alx)(2)还表现出更高的log P (com)和1/IC(50)值。基于这些结果,我们提出在3hp配体的C2和C6位置引入亲脂性基团是增强配合物降血糖作用的有效方法,体内暴露和血液驻留情况也证实了这一点。