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Advances in Vanadium Complexes
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Advances in Vanadium Complexes

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Inorganic Chemistry".

Deadline for manuscript submissions: 30 April 2024 | Viewed by 3529

Special Issue Editor

Prof. Dr. Mannar R. Maurya

E-Mail Website
Guest Editor
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247667, India
Interests: structural and functional models of vanadium haloperoxidases; immobilization of complexes on inorganic/organic polymers; catalytic oxidation of organic substrates; single-pot multi component reactions; oxygen transfer reaction

Special Issue Information

Dear Colleagues,

Vanadium has been reported to be an essential bio-element for certain organisms, including tunicates, bacteria and some fungi. The physiological role of vanadium is not known, but its importance has been indicated for normal growth and development. The presence of vanadium in vanadium-based enzymes, e.g., vanadate-dependent haloperoxidases and vanadium nitrogenase, has attracted the attention of researchers to develop vanadium coordination chemistry in search of good models for these enzymes. In fact, the model oxidovanadium (IV/V) complexes activate H2O2 for the oxidation of halides, consequently producing halogenated compounds. Further, these complexes in high-oxidation states have widely been used as homogeneous as well as heterogeneous (supported) catalysts in oxidation processes of industrial importance, and in the multicomponent one-pot synthesis of various biomolecules.

Vanadium complexes were also widely used as a therapeutic agent in the late 18th century to treat a variety of diseases, including anemia, tuberculosis, rheumatism and diabetes. An in vitro antiamoebic activity of vanadium complexes has also been reported. Several types of neutral and low-molecular-weight vanadium (IV) complexes with organic ligands have been designed and investigated in animal model systems for the treatment of diabetes.

This Special Issue aims to collect scientific papers on the recent advances in vanadium complexes. Preference is not limited to the above research fields, as any relevant area(s) where new vanadium complexes—or known ones with bioinorganic chemistry, green chemistry and environmental aspects—are also welcome for submission.

Prof. Dr. Mannar R. Maurya
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • vanadium complexes
  • catalytic activity
  • oxidation transformation catalysed by vanadium complexes
  • multicomponent one-pot reaction catalysed by vanadium complexes
  • antiamoebic activity
  • antidiabetic activity
  • anticancer activity
  • antifungal activity
  • cytotoxicity
  • green chemistry
  • bioinorganic chemistry
  • environmental chemistry

Published Papers (4 papers)

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Research

13 pages, 2360 KiB  
Article
Theoretical Insights into Different Complexation Modes of Dioxovanadium(V) Compounds with Pyridoxal Semicarbazone/Thiosemicarbazone/S-Methyl-iso-thiosemicarbazone Ligands
by Odeh Abdullah Odeh Alshammari, Sawsan Maisara, Badriah Alshammari, Maha Raghyan Alshammari, Violeta Rakic, Jasmina Dimitrić Marković, Violeta Jevtovic and Dušan Dimić
Molecules 2024, 29(6), 1213; https://doi.org/10.3390/molecules29061213 - 08 Mar 2024
Viewed by 443
Abstract
Vanadium complexes have gained considerable attention as biologically active compounds. In this contribution, three previously reported dioxovanadium(V) complexes with pyridoxal semicarbazone, thiosemicarbazone, and S-methyl-iso-thiosemicarbazone ligands are theoretically examined. The intermolecular stabilization interactions within crystallographic structures were investigated by Hirshfeld surface analysis. These experimental [...] Read more.
Vanadium complexes have gained considerable attention as biologically active compounds. In this contribution, three previously reported dioxovanadium(V) complexes with pyridoxal semicarbazone, thiosemicarbazone, and S-methyl-iso-thiosemicarbazone ligands are theoretically examined. The intermolecular stabilization interactions within crystallographic structures were investigated by Hirshfeld surface analysis. These experimental structures were optimized at the B3LYP-D3BJ/6-311++G(d,p)(H,C,N,O,S)/def2-TZVP(V) level of theory, and crystallographic and optimized bond lengths and angles were compared. High correlation coefficients and low mean absolute errors between these two data sets proved that the selected level of theory was appropriate for the description of the system. The changes in structures and stability were examined by adding explicit solvent molecules. The Quantum Theory of Atoms in Molecules (QTAIM) was employed to analyze the intramolecular interactions with special emphasis on the effect of substituents. A good correlation between electron density/Laplacian and interatomic distance was found. Through molecular docking simulations towards Bovine Serum Albumin (BSA), the binding affinity of complexes was further investigated. The spontaneity of binding in the active position of BSA was shown. Further experimental studies on this class of compounds are advised. Full article
(This article belongs to the Special Issue Advances in Vanadium Complexes)
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22 pages, 4389 KiB  
Article
Biospeciation of Oxidovanadium(IV) Imidazolyl–Carboxylate Complexes and Their Action on Glucose-Stimulated Insulin Secretion in Pancreatic Cells
by Vital Ugirinema, Frank Odei-Addo, Carminita L. Frost and Zenixole R. Tshentu
Molecules 2024, 29(3), 724; https://doi.org/10.3390/molecules29030724 - 04 Feb 2024
Viewed by 1074
Abstract
The reaction of the vanadyl ion (VO2+) with imidazole-4-carboxylic acid (Im4COOH), imidazole-2-carboxylic acid (Im2COOH) and methylimidazole-2-carboxylic acid (MeIm2COOH), respectively, in the presence of small bioligands (bL) [oxalate (Ox), lactate (Lact), citrate (Cit) and phosphate (Phos)] and high-molecular-weight (HMW) human serum proteins [...] Read more.
The reaction of the vanadyl ion (VO2+) with imidazole-4-carboxylic acid (Im4COOH), imidazole-2-carboxylic acid (Im2COOH) and methylimidazole-2-carboxylic acid (MeIm2COOH), respectively, in the presence of small bioligands (bL) [oxalate (Ox), lactate (Lact), citrate (Cit) and phosphate (Phos)] and high-molecular-weight (HMW) human serum proteins [albumin (HSA) and transferrin (hTf)] were studied in aqueous solution using potentiometric acid–base titrations. The species distribution diagrams for the high-molecular-mass (HMM) proteins with oxidovanadium(IV) under physiological pH were dominated by VO(HMM)2, VOL(HMM) for unsubstituted ligands (L− = Im4COO− and Im2COO−). However, for the N-substituted MeIm2COOH, the species distribution diagrams under physiological pH were dominated by VOL2, VO(HMM)2 and VO2L2(HMM). These species were further confirmed by LC-MS, MALDI-TOF-MS and EPR studies. The glucose-stimulated insulin secretion (GSIS) action of the complexes was investigated using INS-1E cells at a 1 µM concentration, which was established through cytotoxicity studies via the MTT assay. The neutral complexes, especially VO(MeIm2COO)2, showed promising results in the stimulation of insulin secretion than the cationic [VO(MeIm2CH2OH)2]2+ complex and the vanadium salt. Oxidovanadium(IV) complexes reduced insulin stimulation significantly under normoglycaemic levels but showed positive effects on insulin secretion under hyperglycaemic conditions (33.3 mM glucose media). The islets exposed to oxidovanadium(IV) complexes under hyperglycaemic conditions displayed a significant increase in the stimulatory index with 1.19, 1.75, 1.53, 1.85, 2.20 and 1.29 observed for the positive control (sulfonylurea:gliclazide), VOSO4, VO(Im4COO)2, VO(Im2COO)2, VO(MeIm2COO)2 and VO(MeIm2CH2OH)22+, respectively. This observation showed a potential further effect of vanadium complexes towards type 2 diabetes and has been demonstrated for the first time in this study. Full article
(This article belongs to the Special Issue Advances in Vanadium Complexes)
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17 pages, 2764 KiB  
Article
Synthesis, Spectroscopic Characterization, Catalytic and Biological Activity of Oxidovanadium(V) Complexes with Chiral Tetradentate Schiff Bases
by Grzegorz Romanowski, Justyna Budka and Iwona Inkielewicz-Stepniak
Molecules 2023, 28(21), 7408; https://doi.org/10.3390/molecules28217408 - 03 Nov 2023
Cited by 3 | Viewed by 824
Abstract
New oxidovanadium(V) complexes, VOL1–VOL10, with chiral tetradentate Schiff bases obtained by monocondensation reaction of salicylaldehyde derivatives with 1S,2S-(+)-2-amino-1-(4-nitrophenyl)-1,3-propanediol. All complexes have been characterized using different spectroscopic methods, viz. IR, UV-Vis, circular dichroism, one- ( [...] Read more.
New oxidovanadium(V) complexes, VOL1–VOL10, with chiral tetradentate Schiff bases obtained by monocondensation reaction of salicylaldehyde derivatives with 1S,2S-(+)-2-amino-1-(4-nitrophenyl)-1,3-propanediol. All complexes have been characterized using different spectroscopic methods, viz. IR, UV-Vis, circular dichroism, one- (1H, 51V) and two-dimensional (COSY, NOESY) NMR spectroscopy, and elemental analysis. Furthermore, the catalytic ability of all compounds in the epoxidation of styrene, cyclohexene, and its naturally occurring monoterpene derivatives, i.e., S(−)-limonene and (−)-α-pinene has also been studied, using two different oxidants, i.e., aqueous 30% H2O2 or tert-butyl hydroperoxide (TBHP). In addition, the biological properties of these chiral oxidovanadium(V) compounds, but also cis-dioxidomolybdenum(VI) complexes with the same chiral Schiff bases, were studied. Their cytotoxic and cytoprotective activity studies with the HT-22 hippocampal neuronal cells revealed a concentration-dependent effect in the range of 10–100 μM. Moreover, vanadium(V) complexes, in contrast to cis-dioxidomolybdenum(VI) compounds, demonstrated higher cytotoxicity and lack of cytoprotective ability against H2O2-induced cytotoxicity. Full article
(This article belongs to the Special Issue Advances in Vanadium Complexes)
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18 pages, 6041 KiB  
Article
Extractive Spectrophotometric Determination and Theoretical Investigations of Two New Vanadium(V) Complexes
by Kiril B. Gavazov, Petya V. Racheva, Antoaneta D. Saravanska, Galya K. Toncheva and Vasil B. Delchev
Molecules 2023, 28(18), 6723; https://doi.org/10.3390/molecules28186723 - 20 Sep 2023
Cited by 1 | Viewed by 747
Abstract
Two new vanadium (V) complexes involving 6-hexyl-4-(2-thiazolylazo)resorcinol (HTAR) and tetrazolium cation were studied. The following commercially available tetrazolium salts were used as the cation source: tetrazolium red (2,3,5-triphenyltetrazol-2-ium;chloride, TTC) and neotetrazolium chloride (2-[4-[4-(3,5-diphenyltetrazol-2-ium-2-yl)phenyl]phenyl]-3,5-diphenyltetrazol-2-ium;dichloride, NTC). The cations (abbreviated as TT+ and NTC+ [...] Read more.
Two new vanadium (V) complexes involving 6-hexyl-4-(2-thiazolylazo)resorcinol (HTAR) and tetrazolium cation were studied. The following commercially available tetrazolium salts were used as the cation source: tetrazolium red (2,3,5-triphenyltetrazol-2-ium;chloride, TTC) and neotetrazolium chloride (2-[4-[4-(3,5-diphenyltetrazol-2-ium-2-yl)phenyl]phenyl]-3,5-diphenyltetrazol-2-ium;dichloride, NTC). The cations (abbreviated as TT+ and NTC+) impart high hydrophobicity to the ternary complexes, allowing vanadium to be easily extracted and preconcentrated in one step. The complexes have different stoichiometry. The V(V)–HTAR–TTC complex dimerizes in the organic phase (chloroform) and can be represented by the formula [(TT+)[VO2(HTAR)]]2. The other complex is monomeric (NTC+)[VO2(HTAR)]. The cation has a +1 charge because one of the two chloride ions remains undissociated: NTC+ = (NT2+Cl−)+. The ground-state equilibrium geometries of the constituent cations and final complexes were optimized at the B3LYP and HF levels of theory. The dimer [(TT+)[VO2(HTAR)]]2 is more suitable for practical applications due to its better extraction characteristics and wider pH interval of formation and extraction. It was used for cheap and reliable extraction–spectrophotometric determination of V(V) traces in real samples. The absorption maximum, molar absorptivity coefficient, limit of detection, and linear working range were 549 nm, 5.2 × 104 L mol−1 cm−1, 4.6 ng mL−1, and 0.015–2.0 μg mL−1, respectively. Full article
(This article belongs to the Special Issue Advances in Vanadium Complexes)
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