«Green-Ligand» in Metallodrugs Design—Cu(II) Complex with Phytic Acid: Synthetic Approach, EPR-Spectroscopy, and Antimycobacterial Activity
The interaction of sodium phytate hydrate C<sub>6</sub>H<sub>18</sub>O<sub>24</sub>P<sub>6</sub>·xNa·yH<sub>2</sub>O (phytNa) with Cu(OAc)<sub>2</sub>·H<sub>2</sub>O and 1,10-phenanthroline (phen) led to the anionic...
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2025-01-01
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| author | Kseniya A. Koshenskova Natalia V. Makarenko Fedor M. Dolgushin Dmitriy S. Yambulatov Olga B. Bekker Matvey V. Fedin Sergei A. Dementev Olesya A. Krumkacheva Igor L. Eremenko Irina A. Lutsenko |
| author_facet | Kseniya A. Koshenskova Natalia V. Makarenko Fedor M. Dolgushin Dmitriy S. Yambulatov Olga B. Bekker Matvey V. Fedin Sergei A. Dementev Olesya A. Krumkacheva Igor L. Eremenko Irina A. Lutsenko |
| author_sort | Kseniya A. Koshenskova |
| collection | DOAJ |
| description | The interaction of sodium phytate hydrate C<sub>6</sub>H<sub>18</sub>O<sub>24</sub>P<sub>6</sub>·xNa·yH<sub>2</sub>O (phytNa) with Cu(OAc)<sub>2</sub>·H<sub>2</sub>O and 1,10-phenanthroline (phen) led to the anionic tetranuclear complex [Cu<sub>4</sub>(H<sub>2</sub>O)<sub>4</sub>(phen)<sub>4</sub>(phyt)]·2Na<sup>+</sup>·2NH<sub>4</sub><sup>+</sup>·32H<sub>2</sub>O (<b>1</b>), the structure of the latter was determined by X-ray diffraction analysis. The phytate <b>1</b> is completely deprotonated; six phosphate<sup>−</sup> fragments (with atoms P1–P6) are characterized by different spatial arrangements relative to the cyclohexane ring (1a5e conformation), which determines two different types of coordination to the complexing agents—P1 and P3, P4, and P6 have monodentate, while P2 and P5 are bidentately bound to Cu<sup>2+</sup> cations. The molecular structure of the anion complex is stabilized by a set of strong intramolecular hydrogen bonds involving coordinated water molecules. Aromatic systems of phen ligands chelating copper ions participate in strong intramolecular and intermolecular π-π interactions, further contributing to their association. At the supramolecular level, endless stacks are formed, in the voids of which sodium and ammonium cations and water molecules are present. The stability of <b>1</b> in the presence of human serum albumin (HSA) was investigated using Electron Paramagnetic Resonance (EPR) spectroscopy. Continuous wave (CW) EPR spectra in water/glycerol frozen solution clearly indicate a presence of an exchange-coupled Cu(II)-Cu(II) dimeric unit, as well as a Cu(II) monomer-like signal arising from spins sufficiently distant from each other, with comparable contributions of two types of signals. In the presence of albumin at a 1:1 ratio (<b>1</b> to albumin), the EPR spectrum changes significantly, primarily due to the reduced contribution of the S = 1 fraction showing dipole–dipole splitting. The biological activity of <b>1</b> in vitro against the non-pathogenic (model for <i>Mycobacterium tuberculosis</i>) strain of <i>Mycolicibacterium smegmatis</i> is comparable to the first-line drug for tuberculosis treatment, rifampicin. |
| format | Article |
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| institution | Kabale University |
| issn | 1420-3049 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | MDPI AG |
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| series | Molecules |
| spelling | doaj-art-a35eeedceccf44b4812bba209983bdce2025-01-24T13:43:33ZengMDPI AGMolecules1420-30492025-01-0130231310.3390/molecules30020313«Green-Ligand» in Metallodrugs Design—Cu(II) Complex with Phytic Acid: Synthetic Approach, EPR-Spectroscopy, and Antimycobacterial ActivityKseniya A. Koshenskova0Natalia V. Makarenko1Fedor M. Dolgushin2Dmitriy S. Yambulatov3Olga B. Bekker4Matvey V. Fedin5Sergei A. Dementev6Olesya A. Krumkacheva7Igor L. Eremenko8Irina A. Lutsenko9N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 31, 119991 Moscow, RussiaInstitute of Chemistry of the Far Eastern Branch, Russian Academy of Sciences, Prosp. 100-Letiya Vladivostoka, 159, 690022 Vladivostok, RussiaN. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 31, 119991 Moscow, RussiaN. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 31, 119991 Moscow, RussiaN. I. Vavilov Institute of General Genetics, Russian Academy of Sciences, Gubkina, 3, 119333 Moscow, RussiaInternational Tomography Center SB RAS, Institutskaya 3a, 630090 Novosibirsk, RussiaInternational Tomography Center SB RAS, Institutskaya 3a, 630090 Novosibirsk, RussiaInternational Tomography Center SB RAS, Institutskaya 3a, 630090 Novosibirsk, RussiaN. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 31, 119991 Moscow, RussiaN. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 31, 119991 Moscow, RussiaThe interaction of sodium phytate hydrate C<sub>6</sub>H<sub>18</sub>O<sub>24</sub>P<sub>6</sub>·xNa·yH<sub>2</sub>O (phytNa) with Cu(OAc)<sub>2</sub>·H<sub>2</sub>O and 1,10-phenanthroline (phen) led to the anionic tetranuclear complex [Cu<sub>4</sub>(H<sub>2</sub>O)<sub>4</sub>(phen)<sub>4</sub>(phyt)]·2Na<sup>+</sup>·2NH<sub>4</sub><sup>+</sup>·32H<sub>2</sub>O (<b>1</b>), the structure of the latter was determined by X-ray diffraction analysis. The phytate <b>1</b> is completely deprotonated; six phosphate<sup>−</sup> fragments (with atoms P1–P6) are characterized by different spatial arrangements relative to the cyclohexane ring (1a5e conformation), which determines two different types of coordination to the complexing agents—P1 and P3, P4, and P6 have monodentate, while P2 and P5 are bidentately bound to Cu<sup>2+</sup> cations. The molecular structure of the anion complex is stabilized by a set of strong intramolecular hydrogen bonds involving coordinated water molecules. Aromatic systems of phen ligands chelating copper ions participate in strong intramolecular and intermolecular π-π interactions, further contributing to their association. At the supramolecular level, endless stacks are formed, in the voids of which sodium and ammonium cations and water molecules are present. The stability of <b>1</b> in the presence of human serum albumin (HSA) was investigated using Electron Paramagnetic Resonance (EPR) spectroscopy. Continuous wave (CW) EPR spectra in water/glycerol frozen solution clearly indicate a presence of an exchange-coupled Cu(II)-Cu(II) dimeric unit, as well as a Cu(II) monomer-like signal arising from spins sufficiently distant from each other, with comparable contributions of two types of signals. In the presence of albumin at a 1:1 ratio (<b>1</b> to albumin), the EPR spectrum changes significantly, primarily due to the reduced contribution of the S = 1 fraction showing dipole–dipole splitting. The biological activity of <b>1</b> in vitro against the non-pathogenic (model for <i>Mycobacterium tuberculosis</i>) strain of <i>Mycolicibacterium smegmatis</i> is comparable to the first-line drug for tuberculosis treatment, rifampicin.https://www.mdpi.com/1420-3049/30/2/313copper(II) compoundsphytic acidcrystal structureEPR spectraantimycobacterial activity |
| spellingShingle | Kseniya A. Koshenskova Natalia V. Makarenko Fedor M. Dolgushin Dmitriy S. Yambulatov Olga B. Bekker Matvey V. Fedin Sergei A. Dementev Olesya A. Krumkacheva Igor L. Eremenko Irina A. Lutsenko «Green-Ligand» in Metallodrugs Design—Cu(II) Complex with Phytic Acid: Synthetic Approach, EPR-Spectroscopy, and Antimycobacterial Activity Molecules copper(II) compounds phytic acid crystal structure EPR spectra antimycobacterial activity |
| title | «Green-Ligand» in Metallodrugs Design—Cu(II) Complex with Phytic Acid: Synthetic Approach, EPR-Spectroscopy, and Antimycobacterial Activity |
| title_full | «Green-Ligand» in Metallodrugs Design—Cu(II) Complex with Phytic Acid: Synthetic Approach, EPR-Spectroscopy, and Antimycobacterial Activity |
| title_fullStr | «Green-Ligand» in Metallodrugs Design—Cu(II) Complex with Phytic Acid: Synthetic Approach, EPR-Spectroscopy, and Antimycobacterial Activity |
| title_full_unstemmed | «Green-Ligand» in Metallodrugs Design—Cu(II) Complex with Phytic Acid: Synthetic Approach, EPR-Spectroscopy, and Antimycobacterial Activity |
| title_short | «Green-Ligand» in Metallodrugs Design—Cu(II) Complex with Phytic Acid: Synthetic Approach, EPR-Spectroscopy, and Antimycobacterial Activity |
| title_sort | green ligand in metallodrugs design cu ii complex with phytic acid synthetic approach epr spectroscopy and antimycobacterial activity |
| topic | copper(II) compounds phytic acid crystal structure EPR spectra antimycobacterial activity |
| url | https://www.mdpi.com/1420-3049/30/2/313 |
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