SYNTHESIS AND BIOLOGICAL ACTIVITY OF 3d-­METAL COMPLEXES WITH BIS(PHOSPHONOMETHYL)AMINOSUNRIC ACID

E. Trunova, M. Rusakova, T. Makotryk
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Abstract

New complexes of 3d-metals (Co2+, Ni2+, Zn2+) with bis(phosphonomethyl)aminosuccinic acid (H6BPMAS) have been synthesized. The complexes were studied in aqueous solutions at ratios M2+:H6BPMAS = 1:1 in a wide pH range (1÷10). Regardless of the nature of the metal, the formation of complexes of the general composition [M(HnBPMAS)(OH)m] (n= 4÷0, m=1÷0) is shown. The stability constants of the formed differently protonated complexes are calculated and diagrams of their distribution are plotted. It is shown that the process of complexation takes place most completely in the region of pH>4. For all bis(phosphonomethyl)aminosuccinates of 3d metals, the dominance of the complex with one form of the ligand occurs in approximately the same pH ranges. A close order of change in the values of lgKst. complexes testifies to the same type of structure of their internal coordination sphere. Solid complexes of the composition Na4[MBPMAS]⋅4H2O were synthesized. Their composition, structure, and thermal characteristics were determined by the set of me­thods such as diffuse reflectance spectroscopy, IR spectroscopy, DTA and non-quantitative mass spectrometry. It is proved that the complexes have the structure of a distorted octahedron, in which the 3-d metal ions are bound to the oxygen atoms of the carboxyl and phosphonic groups and the tertiary nitrogen atom of the ligand. At the same time, two 5-membered (aminomethylenephosphonic and glycine) and one 6-membered (β-alanine) metallocycles are formed in bis(phosphonomethyl)aminosuccinates. The biological activity of H6BPMAS and its complexes with Ni(II) and Co(II) against non-pathogenic bacterial species of microorganisms Pseudomonas fluorescens and Pseudomonas aureofaciens was studied. The study of the activity of substances was carried out in a liquid sterile Hiss medium. The maxi­mum stimulating effect on the growth of bacterial cultures for the studied compounds was recorded at a concentration of 1 µM in 24 hours after the start of cultivation of mic­ro­organisms. The highest growth of microorganisms was recorded for metal complexes (50% Na4[CoBPMAS]·4H2O and 35% Na4[NiBPMAS]·4H2O). The maximum stimulating effect on the growth of bacterial cultures is shown by the Co(II) complex, which is able to initiate the synthesis of one of the most important growth hormones - heteroauxin.
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与双(磷甲乙基)氨基酸配合物的合成及生物活性
合成了新的三维金属(Co2+, Ni2+, Zn2+)与双(磷甲乙基)氨基琥珀酸(H6BPMAS)配合物。在较宽的pH范围内,以M2+:H6BPMAS = 1:1的比例在水溶液中研究了配合物(1÷10)。无论金属的性质如何,都显示出一般组成[M(HnBPMAS)(OH) M] (n= 4÷0, M =1÷0)的配合物的形成。计算了形成的不同质子化配合物的稳定常数,并绘制了它们的分布图。结果表明,在pH>4的区域,络合反应最完全。对于所有的三维金属的二(磷甲乙基)氨基琥珀酸盐,与一种形式的配体的配合物的优势发生在大约相同的pH范围。lgKst值变化的紧密顺序。配合物的内部配位球具有相同的结构类型。合成了Na4[MBPMAS]⋅4H2O组成的固体配合物。通过漫反射光谱、红外光谱、差热分析和非定量质谱等方法测定了它们的组成、结构和热特性。证明了配合物具有畸变八面体的结构,其中三维金属离子与配体的羧基和膦基的氧原子以及叔氮原子结合。同时,在二(磷甲乙基)氨基琥珀酸酯中形成了两个5元(氨基膦和甘氨酸)和一个6元(β-丙氨酸)金属环。研究了H6BPMAS及其与Ni(II)和Co(II)配合物对非致病性荧光假单胞菌和金黄色假单胞菌的生物活性。在无菌Hiss液体培养基中进行了物质活性的研究。在微生物培养开始后的24小时内,以1µM的浓度记录了所研究化合物对细菌培养物生长的最大刺激作用。金属配合物(50% Na4[CoBPMAS]·4H2O和35% Na4[NiBPMAS]·4H2O)的微生物生长最高。对细菌培养物生长的最大刺激作用是Co(II)复合物,它能够启动最重要的生长激素之一-异生长素的合成。
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