Peculiarities of manganese(II) interaction with hydroxyethylidene diphosphonic acid and aminomethylated calix[4]resorcinol in organized media

E.A. Burilova ^a*, L.I. Vagapova ^b**, Z.A. Nasirova ^a***, T.V. Nikitina ^a****, A.N. Solodov ^a*****, J.R. Shaiymova ^a******, R.R. Amirov ^a*******

^aKazan Federal University, Kazan, 420008 Russia

^bArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Kazan, 420088 Russia

E-mail: ^*burilovajen07@mail.ru, ^**vagapoval@iopc.ru, ^***nasirovaz89@mail.ru, ^****vlalinik2012@yandex.ru, ^*****sanya.solodoff@yandex.ru, ^******julia_shayimova@mail.ru, ^*******ramirov@kpfu.ru

Received April 9, 2019

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DOI: 10.26907/2542-064X.2019.2.199-210

For citation: Burilova E.A., Vagapova L.I., Nasirova Z.A., Nikitina T.V., Solodov A.N., Shaiymova J.R., Amirov R.R. Peculiarities of manganese(II) interaction with hydroxyethylidene diphosphonic acid and aminomethylated calix[4]resorcinol in organized media. Uchenye Zapiski Kazanskogo Universiteta. Seriya Estestvennye Nauki, 2019, vol. 161, no. 2, pp. 199–210. doi: 10.26907/2542-064X.2019.2.199-210. (In Russian)

Abstract

The hydration state of the first coordination sphere of manganese complexes with hydroxyethylidene diphosphonic acid (HEDP, H4L) as well as for Mn(II) systems with salt compositions of aminomethylated calix[4]resorcinol (AMC) of different lipophilicity in micellar solutions, was evaluated by the nuclear magnetic relaxation method using manganese(II) as a paramagnetic probe. In acidic (pH 2–4) solutions of the Mn(II) –HEDP – AMC system for AMC with pentyl radicals, a bell-like rise in the relaxation efficiency values (up to 2 times) was observed. In the remaining pH areas and with a low ligand content, the calix[4]resorcinol do not affect the relaxation efficiency of Mn (II) complexes with HEDP.

Keywords: manganese(II), hydroxyethylidene diphosphonic acid, aminomethylated calix[4]resor­cinol, complexation, NMR relaxation

Acknowledgments. The study was supported by the Russian Foundation for Basic Research (project no. № 18-33-00441-mol_a).

Figure Captions

Scheme 1. Ca(II)-activated complex hexylaminobis (methylenephosphonate) –Gd(III) – DOTA and a schematic representation of possible metal ion detection using MRI [7].

Fig. 1. Changes in the spin-spin relaxation efficiency R₂ (a) and the R₂/R₁ ratio (b) depending on pH of the medium of the Mn(II) –HEDP system. С_Mn(II) 0.2 mM, С_HEDP 0.21 (1), 0.84 (2), 4 (3), 8 (4) mM.

Fig. 2. Changes in the spin-lattice R₁ (a), spin-spin (b) relaxation efficiency and the R₂/R₁ ratio (c) depending on pH of the medium of the Mn(II) –HEDP system. С_Mn(II) 0.2 mM, С_АМКЕО 0.21 (1), 1 (2), 2 mM (3).

Fig. 3. Changes in the spin-lattice R₁ (a) and spin-spin R₂ (b) relaxation efficiency depending on pH of the medium of the following systems: Mn(II) – HEDP (1), Mn(II) – AMCEO (2), Mn(II) – AMCPO – TritonХ100 (3), Mn(II) – AMCPO – Bridge35 (4). С_Mn(II) 0.2 mM, С_HEDP 8 mM (1), С_AMCEO 2 mM (2), С_AMCPO 2 mM (3, 4), С_TritonХ100 10 mM (3), С_Bridge35 10 mM (4).

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