Eduardo Sánchez-Lara, Roberto Favela, Kitze Tzian, Brian Monroy-Torres, Adriana Romo-Pérez, María Teresa Ramírez-Apan, Marcos Flores-Alamo, Antonio Rodríguez-Diéguez, Javier Cepeda, Ivan Castillo
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The [V<sub>4</sub>O<sub>12</sub>]<sup>4−</sup> anion is functionalized with mixed copper(II) units in <b>1</b> and <b>2</b>; while in <b>3</b>, it acts as a counterion of two [Cu(dmp)]<sup>2+</sup> units. Compound <b>4</b> crystallized as a unit that did not incorporate the vanadium cluster. All compounds present magnetic couplings arising from Cu⋯O/Cu⋯Cu bridges. Stability studies of water-soluble <b>3</b> and <b>4</b> by UV–Vis spectroscopy in cell culture medium confirmed the robustness of <b>3</b>, while <b>4</b> appears to undergo ligand scrambling over time, resulting partially in the stable species [Cu(dmp)<sub>2</sub>]<sup>+</sup> that was also identified by electrospray ionization mass spectrometry at <i>m</i>/<i>z</i> = 479. The in vitro cytotoxicity activity of <b>3</b> and <b>4</b> was determined in six cancer cell lines; the healthy cell line COS-7 was also included for comparative purposes. MCF-7 cells were more sensitive to compound <b>3</b> with an IC<sub>50</sub> value of 12 ± 1.2 nmol. The tested compounds did not show lipid peroxidation in the TBARS assay, ruling out a mechanism of action via reactive oxygen species formation. Both compounds inhibited cell migration at 5 µM in wound-healing assays using MCF-7, PC-3, and SKLU-1 cell lines, opening a new window to study the anti-metastatic effect of mixed vanadium–copper(II) systems.</p><h3>Graphical abstract</h3>\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":603,"journal":{"name":"Journal of Biological Inorganic Chemistry","volume":"29 1","pages":"139 - 158"},"PeriodicalIF":2.7000,"publicationDate":"2024-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11001746/pdf/","citationCount":"0","resultStr":"{\"title\":\"Effects of the tetravanadate [V4O12]4− anion on the structural, magnetic, and biological properties of copper/phenanthroline complexes\",\"authors\":\"Eduardo Sánchez-Lara, Roberto Favela, Kitze Tzian, Brian Monroy-Torres, Adriana Romo-Pérez, María Teresa Ramírez-Apan, Marcos Flores-Alamo, Antonio Rodríguez-Diéguez, Javier Cepeda, Ivan Castillo\",\"doi\":\"10.1007/s00775-023-02035-9\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The aim to access linked tetravanadate [V<sub>4</sub>O<sub>12</sub>]<sup>4−</sup> anion with mixed copper(II) complexes, using <i>α</i>-amino acids and phenanthroline-derived ligands, resulted in the formation of four copper(II) complexes [Cu(dmb)(Gly)(OH<sub>2</sub>)]<sub>2</sub>[Cu(dmb)(Gly)]<sub>2</sub>[V<sub>4</sub>O<sub>12</sub>]·9H<sub>2</sub>O (<b>1</b>) [Cu(dmb)(Lys)]<sub>2</sub>[V<sub>4</sub>O<sub>12</sub>]·8H<sub>2</sub>O (<b>2</b>), [Cu(dmp)<sub>2</sub>][V<sub>4</sub>O<sub>12</sub>]·C<sub>2</sub>H<sub>5</sub>OH·11H<sub>2</sub>O (<b>3</b>), and [Cu(dmp)(Gly)Cl]·2H<sub>2</sub>O (<b>4</b>), where dmb = 4,4′-dimethioxy-2,2′-bipyridine; Gly = glycine; Lys = lysine; and dmp = 2,9-dimethyl-1,10-phenanthroline. The [V<sub>4</sub>O<sub>12</sub>]<sup>4−</sup> anion is functionalized with mixed copper(II) units in <b>1</b> and <b>2</b>; while in <b>3</b>, it acts as a counterion of two [Cu(dmp)]<sup>2+</sup> units. Compound <b>4</b> crystallized as a unit that did not incorporate the vanadium cluster. All compounds present magnetic couplings arising from Cu⋯O/Cu⋯Cu bridges. Stability studies of water-soluble <b>3</b> and <b>4</b> by UV–Vis spectroscopy in cell culture medium confirmed the robustness of <b>3</b>, while <b>4</b> appears to undergo ligand scrambling over time, resulting partially in the stable species [Cu(dmp)<sub>2</sub>]<sup>+</sup> that was also identified by electrospray ionization mass spectrometry at <i>m</i>/<i>z</i> = 479. The in vitro cytotoxicity activity of <b>3</b> and <b>4</b> was determined in six cancer cell lines; the healthy cell line COS-7 was also included for comparative purposes. 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Effects of the tetravanadate [V4O12]4− anion on the structural, magnetic, and biological properties of copper/phenanthroline complexes
The aim to access linked tetravanadate [V4O12]4− anion with mixed copper(II) complexes, using α-amino acids and phenanthroline-derived ligands, resulted in the formation of four copper(II) complexes [Cu(dmb)(Gly)(OH2)]2[Cu(dmb)(Gly)]2[V4O12]·9H2O (1) [Cu(dmb)(Lys)]2[V4O12]·8H2O (2), [Cu(dmp)2][V4O12]·C2H5OH·11H2O (3), and [Cu(dmp)(Gly)Cl]·2H2O (4), where dmb = 4,4′-dimethioxy-2,2′-bipyridine; Gly = glycine; Lys = lysine; and dmp = 2,9-dimethyl-1,10-phenanthroline. The [V4O12]4− anion is functionalized with mixed copper(II) units in 1 and 2; while in 3, it acts as a counterion of two [Cu(dmp)]2+ units. Compound 4 crystallized as a unit that did not incorporate the vanadium cluster. All compounds present magnetic couplings arising from Cu⋯O/Cu⋯Cu bridges. Stability studies of water-soluble 3 and 4 by UV–Vis spectroscopy in cell culture medium confirmed the robustness of 3, while 4 appears to undergo ligand scrambling over time, resulting partially in the stable species [Cu(dmp)2]+ that was also identified by electrospray ionization mass spectrometry at m/z = 479. The in vitro cytotoxicity activity of 3 and 4 was determined in six cancer cell lines; the healthy cell line COS-7 was also included for comparative purposes. MCF-7 cells were more sensitive to compound 3 with an IC50 value of 12 ± 1.2 nmol. The tested compounds did not show lipid peroxidation in the TBARS assay, ruling out a mechanism of action via reactive oxygen species formation. Both compounds inhibited cell migration at 5 µM in wound-healing assays using MCF-7, PC-3, and SKLU-1 cell lines, opening a new window to study the anti-metastatic effect of mixed vanadium–copper(II) systems.
期刊介绍：
Biological inorganic chemistry is a growing field of science that embraces the principles of biology and inorganic chemistry and impacts other fields ranging from medicine to the environment. JBIC (Journal of Biological Inorganic Chemistry) seeks to promote this field internationally. The Journal is primarily concerned with advances in understanding the role of metal ions within a biological matrix—be it a protein, DNA/RNA, or a cell, as well as appropriate model studies. Manuscripts describing high-quality original research on the above topics in English are invited for submission to this Journal. The Journal publishes original articles, minireviews, and commentaries on debated issues.
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