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A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Bioinorganic Chemistry".

Deadline for manuscript submissions: closed (31 March 2022) | Viewed by 32772

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Prof. Dr. Dinorah Gambino

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Área Química Inorgánica, Facultad de Química, Universidad de la República, Montevideo, Uruguay
Interests: vanadium chemistry and biological inorganic chemistry; metal-based drugs; bioorganometallic chemistry; medicinal inorganic chemistry
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Dear Colleagues,

The recognition of the exceptional chemical and biological properties of vanadium compounds has led, in recent decades, to extensive research in order to explore their chemistry, biochemistry, and medicinal chemistry. Due to prospective application of vanadium compounds as therapeutic agents against diseases like diabetes, cancer and those provoked by parasites and bacteria, vanadium coordination chemistry and biochemistry has been an area of extensive research. Currently, the most promising potential uses of vanadium compounds are as nutritional supplements and as anticancer agent potentiated by immunotherapy. Nevertheless, researchers from all over the world are dedicating their efforts to vanadium research related with other potential therapeutic applications of vanadium compounds and to get insight into their beneficial effects on health and their mode of action. This Special Issue aims to collect research contributions focused on recent advances in vanadium chemistry, biochemistry, and medicinal chemistry. I expect that this issue will have a great impact on the future direction of vanadium research. Therefore, I invite you to contribute to it with your more recent work.

Prof. Dr. Dinorah Gambino
Guest Editor

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Keywords

vanadium chemistry
vanadium biological inorganic chemistry
vanadium-based drugs
vanadium biochemistry

Published Papers (11 papers)

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Editorial

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3 pages, 181 KiB

Open AccessEditorial

New Trends on Vanadium Chemistry, Biochemistry, and Medicinal Chemistry

by Dinorah Gambino

Inorganics 2022, 10(5), 68; https://doi.org/10.3390/inorganics10050068 - 22 May 2022

Viewed by 1580

Abstract

Vanadium was discovered twice [...] Full article

(This article belongs to the Special Issue New Trends on Vanadium Chemistry, Biochemistry, and Medicinal Chemistry)

Research

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19 pages, 3156 KiB

Open AccessArticle

Antioxidant and Anticancer Activities and Protein Interaction of the Oxidovanadium(IV) Naringin Complex

by Andrés Gonzalo Restrepo-Guerrero, Helen Goitia-Semenco, Luciana G. Naso, Marilin Rey, Pablo J. Gonzalez, Evelina G. Ferrer and Patricia A. M. Williams

Inorganics 2022, 10(1), 13; https://doi.org/10.3390/inorganics10010013 - 15 Jan 2022

Cited by 6 | Viewed by 2506

Abstract

The complex of oxidovanadium(IV) with naringin (Narg) [VO(Narg)₂] 8H₂O (VONarg) was prepared according to the literature improving the synthetic procedure and physicochemical characterization. In addition, biological activities (cytotoxic, antioxidant, and BSA interaction) were determined. The metal coordinated through the 5-hydroxy and 4-carbonyl groups of rings A and C of naringin, respectively. The antioxidant activity of VONarg, determined in vitro, was higher than those of the flavonoid against superoxide and peroxyl reactive oxygen species (ROS) and DPPH radical. The cytotoxic properties were determined by a MTT assay on adenocarcinoma human alveolar basal epithelial cells (A549). VONarg exerted a 20% decrease in cancer cells viability at 24 h incubation, while naringin and oxidovanadium(IV) cation did not show cytotoxicity. Measurements with the normal HEK293 cell line showed that the inhibitory action of the complex is selective. VONarg generated intracellular reactive oxygen species (ROS), depletion of reduced glutathione and depolarization of mitochondrial membrane potential, typical for apoptotic pathway, producing cell death by oxidative stress mechanism. Moreover, naringin interacted with bovine serum albumin (BSA) through hydrophobic interactions in a spontaneous process, and VONarg showed greater affinity for the protein but can still be transported and delivered by it (K_a 10⁴ L·mol⁻¹ order). Full article

(This article belongs to the Special Issue New Trends on Vanadium Chemistry, Biochemistry, and Medicinal Chemistry)

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16 pages, 1984 KiB

Open AccessArticle

Phenanthroline Complexation Enhances the Cytotoxic Activity of the VO-Chrysin System

by Agustin Actis Dato, Luciana G. Naso, Marilin Rey, Pablo J. Gonzalez, Evelina G. Ferrer and Patricia A. M. Williams

Inorganics 2022, 10(1), 4; https://doi.org/10.3390/inorganics10010004 - 28 Dec 2021

Cited by 2 | Viewed by 2226

Abstract

Metal complexation in general improves the biological properties of ligands. We have previously measured the anticancer effects of the oxidovanadium(IV) cation with chrysin complex, VO(chrys)₂. In the present study, we synthesized and characterized a new complex generated by the replacement of one chrysin ligand by phenanthroline (phen), VO(chrys)phenCl, to confer high planarity for DNA chain intercalation and more lipophilicity, giving rise to a better cellular uptake. In effect, the uptake of vanadium has been increased in the complex with phen and the cytotoxic effect of this complex proved higher in the human lung cancer A549 cell line, being involved in its mechanisms of action, the production of cellular reactive oxygen species (ROS), the decrease of the natural antioxidant compound glutathione (GSH) and the ratio GSH/GSSG (GSSG, oxidized GSH), and mitochondrial membrane damage. Cytotoxic activity studies using the non-tumorigenic HEK293 cell line showed that [VO(chrys)phenCl] exhibits selectivity action towards A549 cells after 24 h incubation. The interaction with bovine serum albumin (BSA) by fluorometric determinations showed that the complex could be carried by the protein and that the binding of the complex to BSA occurs through H-bond and van der Waals interactions. Full article

(This article belongs to the Special Issue New Trends on Vanadium Chemistry, Biochemistry, and Medicinal Chemistry)

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12 pages, 5918 KiB

Open AccessArticle

The Effect of Vanadium Inhalation on the Tumor Progression of Urethane-Induced Lung Adenomas in a Mice Model

by Nelly López-Valdez, Marcela Rojas-Lemus and Teresa I. Fortoul

Inorganics 2021, 9(11), 78; https://doi.org/10.3390/inorganics9110078 - 29 Oct 2021

Cited by 1 | Viewed by 2197

Abstract

Lung cancer has the highest death rates. Aerosol drug delivery has been used for other lung diseases. The use of inhaled vanadium (V) as an option for lung cancer treatment is explored. Four groups of mice were studied: (1) Saline inhalation alone, (2) Single intraperitoneal (i.p.) dose of urethane, (3) V nebulization twice a week (Wk) for 8 Wk, and (4) A single dose of urethane and V nebulization for 8 Wk. Mice were sacrificed at the end of the experiment. Number and size of tumors, PCNA (proliferating cell nuclear antigen) and TUNEL (terminal deoxynucleotidyl tranferase dUTP nick-end labeling) immunohistochemistry were evaluated and compared within groups. Results: The size and number of tumors decreased in mice exposed to V-urethane and the TUNEL increased in this group; differences in the PCNA were not observed. Conclusions: Aerosol V delivery increased apoptosis and possibly the growth arrest of the tumors with no respiratory clinical changes in the mice. Full article

(This article belongs to the Special Issue New Trends on Vanadium Chemistry, Biochemistry, and Medicinal Chemistry)

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20 pages, 6748 KiB

Open AccessArticle

Vanadium(V) Complexes with Siderophore Vitamin E-Hydroxylamino-Triazine Ligands

by Maria Loizou, Ioanna Hadjiadamou, Chryssoula Drouza, Anastasios D. Keramidas, Yannis V. Simos and Dimitrios Peschos

Inorganics 2021, 9(10), 73; https://doi.org/10.3390/inorganics9100073 - 29 Sep 2021

Cited by 5 | Viewed by 2602

Abstract

Novel vitamin E chelate siderophore derivatives and their V^V and Fe^III complexes have been synthesised and the chemical and biological properties have been evaluated. In particular, the α- and δ-tocopherol derivatives with bis-methyldroxylamino triazine (α-tocTHMA) and (δ-tocDPA) as well their V^V complexes, [V₂^VO₃(α-tocTHMA)₂] and [V₂^IVO₃(δ-tocTHMA)₂], have been synthesised and characterised by infrared (IR), nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR) and ultra violet-visible (UV-Vis) spectroscopies. The dimeric vanadium complexes in solution are in equilibrium with their respefrctive monomers, H₂O + [V₂^VO₂(μ-O)]⁴⁺ = 2 [V^VO(OH)]²⁺. The two amphiphilic vanadium complexes exhibit enhanced hydrolytic stability. EPR shows that the complexes in lipophilic matrix are mild radical initiators. Evaluation of their biological activity shows that the compounds do not exhibit any significant cytotoxicity to cells. Full article

(This article belongs to the Special Issue New Trends on Vanadium Chemistry, Biochemistry, and Medicinal Chemistry)

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21 pages, 5938 KiB

Open AccessArticle

2-Aminopyrimidinium Decavanadate: Experimental and Theoretical Characterization, Molecular Docking, and Potential Antineoplastic Activity

by Amalia García-García, Lisset Noriega, Francisco J. Meléndez-Bustamante, María Eugenia Castro, Brenda L. Sánchez-Gaytán, Duane Choquesillo-Lazarte, Enrique González-Vergara and Antonio Rodríguez-Diéguez

Inorganics 2021, 9(9), 67; https://doi.org/10.3390/inorganics9090067 - 30 Aug 2021

Cited by 11 | Viewed by 3108

Abstract

The interest in decavanadate anions has increased in recent decades, since these clusters show interesting applications as varied as sensors, batteries, catalysts, or new drugs in medicine. Due to the capacity of the interaction of decavanadate with a variety of biological molecules because of its high negative charge and oxygen-rich surface, this cluster is being widely studied both in vitro and in vivo as a treatment for several global health problems such as diabetes mellitus, cancer, and Alzheimer’s disease. Here, we report a new decavanadate compound with organic molecules synthesized in an aqueous solution and structurally characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. The decavanadate anion was combined with 2-aminopyrimidine to form the compound [2-ampymH]6[V10O28]·5H2O (1). In the crystal lattice, organic molecules are stacked by π–π interactions, with a centroid-to-centroid distance similar to that shown in DNA or RNA molecules. Furthermore, computational DFT calculations of Compound 1 corroborate the hydrogen bond interaction between pyrimidine molecules and decavanadate anions, as well as the π–π stacking interactions between the central pyrimidine molecules. Finally, docking studies with test RNA molecules indicate that they could serve as other potential targets for the anticancer activity of decavanadate anion. Full article

(This article belongs to the Special Issue New Trends on Vanadium Chemistry, Biochemistry, and Medicinal Chemistry)

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16 pages, 1993 KiB

Open AccessArticle

Study of DNA Interaction and Cytotoxicity Activity of Oxidovanadium(V) Complexes with ONO Donor Schiff Base Ligands

by Gurunath Sahu, Edward R. T. Tiekink and Rupam Dinda

Inorganics 2021, 9(9), 66; https://doi.org/10.3390/inorganics9090066 - 27 Aug 2021

Cited by 14 | Viewed by 2527

Abstract

Two new oxidovanadium(V) complexes, (HNEt₃)[V^VO₂L] (1) and [(V^VOL)₂μ-O] (2), have been synthesized using a tridentate Schiff base ligand H₂L [where H₂L = 4-((E)-(2-hydroxy-5-nitrophenylimino)methyl)benzene-1,3-diol] and VO(acac)₂ as starting metal precursor. The ligand and corresponding metal complexes are characterized by physicochemical (elemental analysis), spectroscopic (FT-IR, UV–Vis, and NMR), and spectrometric (ESI–MS) methods. X-ray crystallographic analysis indicates the anion in salt 1 features a distorted square-pyramidal geometry for the vanadium(V) center defined by imine-N, two phenoxide-O, and two oxido-O atoms. The interaction of the compounds with CT–DNA was studied through UV–Vis absorption titration and circular dichroism methods. The results indicated that complexes showed enhanced binding affinity towards DNA compared to the ligand molecule. Finally, the in vitro cytotoxicity studies of H₂L, 1, and 2 were evaluated against colon cancer (HT-29) and mouse embryonic fibroblast (NIH-3T3) cell lines by MTT assay. The results demonstrated that the compounds manifested a cytotoxic potential comparable with clinically referred drugs and caused cell death by apoptosis. Full article

(This article belongs to the Special Issue New Trends on Vanadium Chemistry, Biochemistry, and Medicinal Chemistry)

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17 pages, 2809 KiB

Open AccessArticle

Acute Toxicity Evaluation of Non-Innocent Oxidovanadium(V) Schiff Base Complex

by Lidiane M. A. Lima, Heide Murakami, D. Jackson Gaebler, Wagner E. Silva, Mônica F. Belian, Eduardo C. Lira and Debbie C. Crans

Inorganics 2021, 9(6), 42; https://doi.org/10.3390/inorganics9060042 - 24 May 2021

Cited by 20 | Viewed by 3928

Abstract

The vanadium(V) complexes have been investigated as potential anticancer agents which makes it essential to evaluate their toxicity for safe use in the clinic. The large-scale synthesis and the acute oral toxicity in mice of the oxidovanadium(V) Schiff base catecholate complex, abbreviated as [VO(HSHED)dtb] containing a redox-active ligand with tridentate Schiff base (HSHED = N-(salicylideneaminato)-N’-(2-hydroxyethyl)-1,2-ethylenediamine) and dtb = 3,5-di-(t-butyl)catechol ligands were carried out. The body weight, food consumption, water intake as well biomarkers of liver and kidney toxicity of the [VO(HSHED)dtb] were compared to the precursors, sodium orthovanadate, and free ligand. The 10-fold scale-up synthesis of the oxidovanadium(V) complex resulting in the preparation of material in improved yield leading to 2–3 g (79%) material suitable for investigating the toxicity of vanadium complex. No evidence of toxicity was observed in animals when acutely exposed to a single dose of 300 mg/kg for 14 days. The toxicological results obtained with biochemical and hematological analyses did not show significant changes in kidney and liver parameters when compared with reference values. The low oral acute toxicity of the [VO(HSHED)dtb] is attributed to redox chemistry taking place under biological conditions combined with the hydrolytic stability of the oxidovanadium(V) complex. These results document the design of oxidovanadium(V) complexes that have low toxicity but still are antioxidant and anticancer agents. Full article

(This article belongs to the Special Issue New Trends on Vanadium Chemistry, Biochemistry, and Medicinal Chemistry)

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20 pages, 3535 KiB

Open AccessArticle

Kinetic Studies of Sodium and Metforminium Decavanadates Decomposition and In Vitro Cytotoxicity and Insulin- Like Activity

by Aniela M. Silva-Nolasco, Luz Camacho, Rafael Omar Saavedra-Díaz, Oswaldo Hernández-Abreu, Ignacio E. León and Irma Sánchez-Lombardo

Inorganics 2020, 8(12), 67; https://doi.org/10.3390/inorganics8120067 - 8 Dec 2020

Cited by 14 | Viewed by 3095

Abstract

The kinetics of the decomposition of 0.5 and 1.0 mM sodium decavanadate (NaDeca) and metforminium decavanadate (MetfDeca) solutions were studied by ⁵¹V NMR in Dulbecco’s modified Eagle’s medium (DMEM) medium (pH 7.4) at 25 °C. The results showed that decomposition products are orthovanadate [H₂VO₄]⁻ (V₁) and metavanadate species like [H₂V₂O₇]²⁻ (V₂), [V₄O₁₂]⁴⁻ (V₄) and [V₅O₁₅]⁵⁻ (V₅) for both compounds. The calculated half-life times of the decomposition reaction were 9 and 11 h for NaDeca and MetfDeca, respectively, at 1 mM concentration. The hydrolysis products that presented the highest rate constants were V₁ and V₄ for both compounds. Cytotoxic activity studies using non-tumorigenic HEK293 cell line and human liver cancer HEPG2 cells showed that decavanadates compounds exhibit selectivity action toward HEPG2 cells after 24 h. The effect of vanadium compounds (8–30 μM concentration) on the protein expression of AKT and AMPK were investigated in HEPG2 cell lines, showing that NaDeca and MetfDeca compounds exhibit a dose-dependence increase in phosphorylated AKT. Additionally, NaDeca at 30 µM concentration stimulated the glucose cell uptake moderately (62%) in 3T3-L1 adipocytes. Finally, an insulin release assay in βTC-6 cells (30 µM concentration) showed that sodium orthovanadate (MetV) and MetfDeca enhanced insulin release by 0.7 and 1-fold, respectively. Full article

(This article belongs to the Special Issue New Trends on Vanadium Chemistry, Biochemistry, and Medicinal Chemistry)

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Review

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11 pages, 1517 KiB

Open AccessReview

An Overview of Vanadium and Cell Signaling in Potential Cancer Treatments

by Valeria Alejandra Ferretti and Ignacio Esteban León

Inorganics 2022, 10(4), 47; https://doi.org/10.3390/inorganics10040047 - 1 Apr 2022

Cited by 21 | Viewed by 3269

Abstract

Vanadium is an ultratrace element present in higher plants, animals, algae, and bacteria. In recent years, vanadium complexes have been studied to be considered as a representative of a new class of nonplatinum metal anticancer drugs. Nevertheless, the study of cell signaling pathways related to vanadium compounds has scarcely been reported on and reviewed thus far; this information is highly critical for identifying novel targets that play a key role in the anticancer activity of these compounds. Here, we perform a review of the activity of vanadium compounds over cell signaling pathways on cancer cells and of the underlying mechanisms, thereby providing insight into the role of these proteins as potential new molecular targets of vanadium complexes. Full article

(This article belongs to the Special Issue New Trends on Vanadium Chemistry, Biochemistry, and Medicinal Chemistry)

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27 pages, 5726 KiB

Open AccessReview

Misinterpretations in Evaluating Interactions of Vanadium Complexes with Proteins and Other Biological Targets

by João Costa Pessoa and Isabel Correia

Inorganics 2021, 9(2), 17; https://doi.org/10.3390/inorganics9020017 - 9 Feb 2021

Cited by 41 | Viewed by 3773

Abstract

In aqueous media, V^IV- and V^V-ions and compounds undergo chemical changes such as hydrolysis, ligand exchange and redox reactions that depend on pH and concentration of the vanadium species, and on the nature of the several components present. In particular, the behaviour of vanadium compounds in biological fluids depends on their environment and on concentration of the many potential ligands present. However, when reporting the biological action of a particular complex, often the possibility of chemical changes occurring has been neglected, and the modifications of the complex added are not taken into account. In this work, we highlight that as soon as most vanadium(IV) and vanadium(V) compounds are dissolved in a biological media, they undergo several types of chemical transformations, and these changes are particularly extensive at the low concentrations normally used in biological experiments. We also emphasize that in case of a biochemical interaction or effect, to determine binding constants or the active species and/or propose mechanisms of action, it is essential to evaluate its speciation in the media where it is acting. This is because the vanadium complex no longer exists in its initial form. Full article

(This article belongs to the Special Issue New Trends on Vanadium Chemistry, Biochemistry, and Medicinal Chemistry)

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