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羧酸盐与过渡金属或稀土元素及其配体新配合物的高效薄层层析和磁色谱法——亲脂性研究

HPTLC and magnetochromatography of new complexes of carboxylates with transition metals or rare earth elements and their ligands - study of lipophilicity.

作者信息

Malinowska Irena, Wronka Agnieszka, Ferenc Wiesława

机构信息

Department of Planar Chromatography, Chair of Physical Chemistry, Faculty of Chemistry, Maria Curie-Skłodowska University, Lublin, Poland.

Department of General and Coordination Chemistry, Maria Curie-Skłodowska University, Lublin, Poland.

出版信息

Biomed Chromatogr. 2017 May;31(5). doi: 10.1002/bmc.3872. Epub 2016 Dec 5.

Abstract

Nineteen new complexes of carboxylates with transition and rare elements as central ions and their ligands were characterized by chromatographic analyses. The parameter of relative lipophilicity (R ) of the tested compounds was determined experimentally by the reversed-phase high-performance thin layer chromatography method with mixtures of various organic modifiers (acetonitrile, acetone, dioxane) and water as a mobile phase. The extrapolated R values were compared with the logP values calculated from the molecular structures of tested solutes. Similarities between the lipophilicity indices were analysed by principal component analysis and linear regression. Thin-layer chromatography combined with a magnetic field has been proposed as a complementary method for determination of lipophilicity of the investigated compounds. The chromatograms in the field and outside it were developed simultaneously in two identical chromatographic chambers. One of them was placed in the external magnetic field of 0.4 T inductivity. We proved that chelation causes a drastic change in compound lipophilicity, but all complexes did not exhibit enhanced activity as compared with the parent ligand. Also in the magnetic field the retention of some complexes changed, which means that the presence of the field influences the physicochemical properties of the compounds and their interactions with the stationary phase.

摘要

通过色谱分析对19种以过渡元素和稀土元素为中心离子及其配体的新型羧酸盐配合物进行了表征。采用反相高效薄层色谱法,以各种有机改性剂(乙腈、丙酮、二氧六环)和水的混合物作为流动相,通过实验测定了受试化合物的相对亲脂性参数(R)。将外推的R值与根据受试溶质分子结构计算得到的logP值进行比较。通过主成分分析和线性回归分析亲脂性指数之间的相似性。提出了薄层色谱结合磁场作为测定所研究化合物亲脂性的补充方法。在两个相同的色谱室中同时展开磁场内和磁场外的色谱图。其中一个置于感应强度为0.4 T的外部磁场中。我们证明螯合作用会导致化合物亲脂性发生剧烈变化,但与母体配体相比,所有配合物均未表现出增强的活性。在磁场中,一些配合物的保留情况也发生了变化,这意味着磁场的存在会影响化合物的物理化学性质及其与固定相的相互作用。

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