Search Results (22)

The development of efficient technologies for processing secondary technogenic raw materials represents a promising approach to replenishing vanadium resources. This study investigates the processes of sulfuric acid reductive leaching of vanadium from spent vanadium catalysts using oxalic acid and metallic iron as reducing agents. It was established that oxalic acid provides vanadium extraction of up to 95.2%, whereas the use of metallic iron (2–3 wt.% of the catalyst mass) enables a vanadium recovery rate of 91–92% at a solid-to-liquid ratio of 1:7 and pH 1.3–1.5, offering a more cost-effective alternative. Thermodynamic modeling of the V–Fe–P–SO₄–C₂O₄–H₂O system was performed using the Medusa software package over a pH range of 0–3. The results showed that vanadium(IV) predominantly exists as the VOSO₄ complex in sulfuric acid solutions, whereas the formation of oxalate and phosphate complexes is thermodynamically insignificant. Iron(III) was found to exhibit a strong affinity toward phosphate ions, promoting their selective precipitation as an iron phosphate phase while maintaining vanadium in solution. The obtained results provide a scientific basis for the efficient preliminary separation of iron and vanadium and for improving the selectivity of subsequent vanadium sorption. Full article

The disadvantages of Cisplatin in anticancer treatment are connected to its poor selectivity, resistance developed of cancers to the drug, and its toxicity against normal organs. An important strategy in anticancer treatment is the synthesis and clinical investigation of non-platinum metal complexes with superior anticancer activity and improved selectivity compared to Cisplatin, combined with lower toxicity, fewer side effects and decreased resistance of cancer to the drug. In the current study, we aim to summarize the potential of important non-platinum metal-based organic compounds as therapeutic agents against different cancer cell types. The review covers the general principles of chemotherapy. A literature analysis shows that organic complexes of the metalloids arsenic (As), boron (B), antimony (Sb), and selenium (Se), and of metals, such as Ag, Au, Co, Cu, Fe, Mn, Mo, Ni, Zn, Ce, Ga, Gd, Ir, Os, Pd, Re, Rh, Ru, Ti, and V, have been investigated for potential applications in cancer therapy. This is due to their antiproliferative effects against different cancer types: lung [Cd(II), Co(II), Cu(II), Ni(II), Mn(II), Ru(II), Zn(II)]; breast [Ag(I), Cu(I), Cu(II), Ir(III), Ni(II), Mn(II),. Rh(III), Ru(II)]; gastric [Cu(II), Cu(II)-La(III)]; colon [Ag(I), Cu(II), Ir(III), Pd(II), Rh(III), Ru(II), vanadium(V)]; colorectal [Ag(I), Co(II), Cu(II), Zn(II)]; liver [Ag(I), Co(II), Cu(II), Gd(III), vanadium(V)]; pancreatic [vanadium(IV)]; bladder [Ag(I), Cu(II), Ru(II)]; cervical [Ag(I), Au(I), Cu(I), Cu(II), Fe(II), Ir(III), Rh(III), Ru(II)]; testicular [vanadium(IV)]; prostate [Cu(II), Pd(II), Zn(II)]; leukemia [Ag(I), Co(II), Cu(II), Pd(II), Zn(II)]; sarcoma [Co(II), Ni(II), Zn(II)]; mesothelioma [Cu(II)]; neuroblastoma [Cu(II)]; glioma [Cu(II)]; and melanoma [Au(I), Cu(II), Pd(II), Ru(II)]. The main goals for increasing anticancer metal-based complexes include increasing anticancer activity and selectivity, reducing toxicity, and avoiding cancer cell resistance. Compared to Cisplatin, organocomplexes of copper, ferrocene, and ruthenium are more active. Ruthenium and copper complexes, in particular, are also more selective. Notably, ruthenium and ferrocene derivatives are less toxic than Cisplatin. Lastly, cancers appear to exhibit less resistance against copper, gold, ruthenium, palladium, and ferrocene complexes. Full article

Redox flow batteries (RFBs) are an emerging class of large-scale energy storage devices, yet the commercial benchmark—vanadium redox flow batteries (VRFBs)—is highly constrained by a modest open-circuit potential (1.26 V) while posing an expensive and volatile material procurement costs. This review focuses on recent progress in diversifying redox-active species to overcome these limits, highlighting chemistries that increase overall cell voltage, energy density, and efficiency while maintaining long cycle life and safety. The study dwells deeper into manganese-based systems (e.g., Mn/Ti, Mn/V, Mn/S, M/Zn) that leverage Mn’s high positive potential while addressing Mn(III) disproportionation reactions; iron-based hybrids (Fe/Cr, Fe/Zn, Fe/Pb, Fe/V, Fe/S, Fe/Cd) that exploit the low cost, and its abundance, along with membrane and electrolyte strategies to prevent the potential issue involving crossover; cerium-anchored catholytes (Ce/Pb, V/Ce, Eu/Ce, Ce/S, Ce/Zn) that deliver high operational voltage by implementing an acid-base media, along with selective zeolite membranes; and halide systems (Zn–I, Zn–Br, Sn–Br, polysulfide–bromine/iodide) that combine fast redox kinetics and high solubility with advances such as carbon-coated membranes, bromine complexation, and ambipolar electrolytes. Across these various families of RFBs, the review highlights the modifications made to the flow-fields, membranes, and electrodes by utilizing a zero-gap serpentine flow field, sulfonated poly(ether ether ketone) (SPEEK) membranes, carbon-modified and zeolite separators, electrolyte additives to enhance the voltage (VE%), and thereby energy (EE%) efficiency, while reducing the overall system cost. These modifications to the existing RFB technology offer a promising alternative to traditional approaches, paving the way for improved performance and widespread adoption of RFB technology in large-scale grid-based energy storage solutions. Full article

The polymerization of norbornene can occur via ring-opening metathesis polymerization (ROMP) or vinyl-addition pathways, each yielding polynorbornene with distinct structures and properties. This study reports on the synthesis and catalytic application of a new class of vanadium(III) and nickel(II) complexes bearing N-heterocyclic carbene ligands, based on the IPr* framework, for the polymerization of norbornene. The vanadium(III) complexes, activated by diethylaluminum chloride and in the presence of ethyl trichloroacetate, showed activity in ROMP. In contrast, the nickel(II) complexes, activated by methylaluminoxane, exhibited catalytic activity toward vinyl-addition polymerization. Characterization by GPC, NMR, and FTIR confirmed the formation of both ring-opening metathesis polymerization and vinyl-type-derived polynorbornenes, with vinyl-type polymers showing significantly higher molecular weights. Structural variations in the N-heterocyclic carbene ligands, particularly the linker length between imidazole donors, were found to strongly influence polymer molecular weight and the morphology of polynorbornenes. Full article

We report the synthesis and characterization of five novel metal complexes. Three of them are vanadium complexes with the general formula [VO(Lⁿ)₂], where Lⁿ are Schiff bases derived from the condensation of 2-carbaldehyde-8-hydroxyquinoline with either 4-(2-aminoethyl)morpholine (L¹), 3-morpholinopropylamine (L²) or 1-(2-aminoethyl)piperidine (L³). The two other metal complexes are [Ni(L¹)₂] and [Fe(L¹)₂]Cl. They were characterized by analytical, spectroscopic (Fourier transform infrared, UV-visible absorption), and mass spectrometric techniques as well as by single-crystal X-ray diffraction (for all [VO(Lⁿ)₂] complexes and [Ni(L¹)₂]). While, in the crystal structure, the V(IV)O complexes show distorted square–pyramidal geometry with the ligands bound as bidentate through quinolate NO donors, the Ni(II) complex shows octahedral geometry with two ligand molecules coordinated through NNO donors. Stability studies in aqueous media revealed that the vanadium complexes are not stable, undergoing oxidation to VO₂(L), which was corroborated by ⁵¹V NMR and MS. This behavior is also observed in organic media, though at a significantly slower rate. The Ni complex exhibited small spectral changes over time in aqueous media. Nonetheless, all compounds show enhanced stability in the presence of bovine serum albumin (BSA). Fluorescence studies carried out for the Ni(II) and Fe(III) complexes indicate reversible binding to albumin. The cytotoxicity of the L¹ metal complexes was assessed on melanoma (B16F10 and A375) and colon cancer (CT-26 and HCT-116) cell lines, with 5-fluorouracil (5-FU) as a reference drug. The V- and Ni complexes showed the lowest IC₅₀ values (<10 μM) in either A375 or HCT-116 cells after 48 h of incubation, while the Fe(III) complex presented minimal antiproliferative effects. The complexes were generally more cytotoxic to human than murine cancer cells. Synergistic in vitro studies with 5-FU revealed antagonism in most cases, except in A375 cells, where an additive effect was observed for the combination with the V-complex. Overall, these compounds show promising potential for cancer treatment, mostly for melanoma. Full article

Three-dimensional (3D)-printing technology is revolutionizing orthopedic oncology by providing precise, customized solutions for complex bone defects following tumor resection. Traditional modular endoprostheses are prone to complications such as fretting corrosion and implant failure, underscoring the need for innovative approaches. This case series reports on three patients treated with 3D-printed, patient-specific prostheses and cutting guides. Preoperative CT and MRI data were used to design implants tailored to each patient’s anatomy, manufactured using electron beam melting technology with a titanium–aluminum–vanadium alloy. Functional outcomes showed significant improvements: in Case I, AOFAS improved from 71 to 96, and VAS decreased from 6 to 1; in Case II, AOFAS increased from 65 to 79, and VAS decreased from 5 to 3. Radiographic evaluations demonstrated stable prosthesis placement and early evidence of bone integration in Cases I and II, while in Case III, localized disease control was achieved before systemic progression. This case series highlights the transformative potential of 3D-printed prostheses in addressing the challenges of reconstructing anatomically complex defects. By enabling precise tumor resection and improving functional outcomes, this approach can advance current practices in orthopedic oncology. Further research should explore larger cohorts and use cost-effectiveness analyses to validate these findings and facilitate broader clinical adoption. Full article

Despite the high biocompatibility of titanium and its alloys, the need to remove titanium implants is increasingly being debated due to the potential for adverse effects associated with long-term retention. Therefore, new solutions are being sought to enhance the biocompatibility of titanium implants. One of them is to increase the thickness of the passive layer of the implant made of titanium dioxide. We were the first to evaluate the effect of hard-anodized (type II) Ti-6Al-4V alloy discs on the cytotoxicity, mitochondrial function, and redox balance of fibroblasts mitochondria compared to standard-anodized (type III) and non-anodized discs. The study used fibroblasts obtained from human gingival tissue. The test discs were applied to the bottom of 12-well plates. Cells were cultured for 24 h and 7, 14, and 21 days and mitochondria were isolated. We demonstrated the occurrence of oxidative stress in the mitochondria of fibroblasts of all tested groups, regardless of the presence and type of anodization. Type II anodization prevented changes in complex II activity (vs. control). The lowest degree of citrate synthase inhibition occurred in mitochondria exposed to titanium discs with type II anodization. In the last phase of culture, the presence of type II anodization reduced the degree of cytochrome c oxidase inhibition compared to the other tests groups and the control group, and prevented apoptosis. Throughout the experiment, the release of titanium, aluminium, and vanadium ions from titanium discs with a hard-anodized passive layer was higher than from the other titanium discs, but decreased with time. The obtained results proved the existence of dysfunction and redox imbalance in the mitochondria of fibroblasts exposed to hard-anodized titanium discs, suggesting the need to search for new materials perhaps biodegradable in tissues of the human body. Full article

In Earth’s regions accessible for living organisms (Earth’s crust, crude oil, water sanctuaries and lower atmosphere), vanadium is present in the oxidation states +III and—essentially—+IV (cationic) and +V (cationic and anionic), with the redox interchange and biochemical recycling often monitored by bacteria. Organisms having available vanadium-containing (bio)molecules with essential functions for life include marine brown algae (haloperoxidases), ascidians and fan worms, as well as terrestrial organisms, viz., nitrogen-fixing bacteria (associated with the roots of legumes), and the fly agaric mushroom. The hypohalite generated by the algal haloperoxidases in turn is involved in the emission of bromoform into the atmosphere. Nitrogen fixation (N₂ ε NH₄⁺) is a process of immanent importance for life on our planet. Other bacterial issues include the reduction of vanadate to VO²⁺. Medicinal applications of vanadium coordination compounds are directed towards the treatment of diabetes mellitus (vanadium complexes with hypoglycemic activity) and cancer—although boundaries are set due to side effects such as oxidative damage elicited by vanadium-induced hyperoxide formation. Physiological actions of vanadium are often invoked due to the structural and physiological similarity between vanadate and phosphate. An additional field of medicinal applications addresses the treatment of cancer, such as leukaemia, malignant melanoma and bone cancer. Full article

The biological activity of the vanadium Schiff base complexes, which can be potentially used as insulin-mimetic compounds, was extensively studied in the last decade. Pharmacological data showed that these compounds produced a significant decrease in blood glucose level and improved liver and kidney function after two weeks of daily use. The vanadium complexes obtained so far with Schiff bases create problems, most often with cytotoxicity, very low solubility in water, difficulty in studying the crystal structure, instability at pH = 2 and transport to cells. Therefore, it is necessary to search for new organic vanadium compounds to optimize their pharmaceutical activity. Lastly, several hundred vanadium(III–V) complexes with Schiff bases were tested, controlling both the starting vanadium compound for the synthesis of complexes, as well as changing the substituents in the aromatic ring of aldehyde and hydrazide—Schiff base components. The obtained neutral compounds were highly soluble in organic solvents; however, they were insoluble in water. Therefore, the DMSO-H₂O mixture was used to test the stability of the complexes. In the last studies, the synthesis and physicochemical characterization of the vanadium(V) complex with triethylamine as a cation—HTEA[VO₂(L)] (where L = Schiff base formed from 5-bromosalicylaldehyde and 2-hydroxybenzhydrazide)—was described. In the formed ionic complexes, the crystal studies show additional hydrogen interactions between the cation and the complex anion. The ionic structure of such compounds should increase the solubility of the complexes in water, thus maximizing their availability in the biological systems studied. Full article

The search for less expensive and viable products is always one of the challenges for research development. Commonly, the synthesis of coordination compounds involves expensive ligands, through expensive and low-yield routes, in addition to generating toxic and unusable residues. In this work, the organic ligand used is derived from the resin of a reforestation tree, Pinus elliottii var. elliottii. The synthesis method used Pinus resin and an aqueous solution of vanadium(III) chloride at a temperature of 80 °C. The procedure does not involve organic solvents and does not generate toxic residues, thus imparting the complex formation reaction a green chemistry character. The synthesis resulted in an unprecedented oxovanadium(IV)-bis(abietate) complex, which was characterized by mass spectrometry (MS), chemical analysis (CHN), vibrational (FTIR) and electronic spectra (VISIBLE), X-ray diffraction (XRD), and thermal analysis (TG/DTA). Colorimetric studies were performed according to the CIELAB color space. The structural formula found, consisted of a complex containing two abietate ligands, [VO(C₂₀H₂₉O₂)₂]. The VO(IV)-bis(abietate) complex was applied against microorganisms and showed promising results in antibacterial and antifungal activity. The best result of inhibitory action was against the strains of Gram-positive bacteria S. aureus and L. monocytogenes, with minimum inhibitory concentration (MIC) values of 62.5 and 125 μmol L⁻¹, respectively. For Gram-negative strains the results were 500 μmol L⁻¹ for E. coli; and 1000 μmol L⁻¹ for Salmonella enterica Typhimurium. Antifungal activity was performed against Candida albicans, where the MIC was 15.62 μmol L⁻¹, and for C. tropicalis it was 62.5 μmol L⁻¹. According to the MFC analysis, the complex presented, in addition to the fungistatic action, a fungicidal action, as there was no growth of fungi on the plates tested. The results found for the tests demonstrate that the VO(IV)-bis(abietate) complex has great potential as an antimicrobial and mainly antifungal agent. In this way, the pigmented ink with antimicrobial activity could be used in environments with a potential risk of contamination, preventing the spread of microorganisms harmful to health. Full article

The reactions of newly designed lithiated triamidoamines Li₃L^R (R = iPr, Pen, and Cy₂) with VCl₃(THF)₃ under N₂ yielded dinitrogen–divanadium complexes with a μ-N₂ between vanadium atoms [{V(L^R)}₂(μ-N₂)] (R = iPr (1) and Pen (2)) for the former two, while not dinitrogen–divanadium complexes but a mononuclear vanadium complex with a vacant site, [V(L^Cy2)] (R = Cy₂ (3)), were obtained for the third ligand. The V–N_N2 and N–N distances were 1.7655(18) and 1.219(4) Å for 1 and 1.7935(14) and 1.226(3) Å for 2, respectively. The ν(¹⁴N–¹⁴N) stretching vibrations of 1 and 2, as measured using resonance Raman spectroscopy, were detected at 1436 and 1412 cm^–1, respectively. Complex 3 reacted with potassium metal in the presence of 18-crown-6-ether under N₂ to give a hetero-dinuclear vanadium complex with μ-N₂ between vanadium and potassium, [VK(L^Cy2)(μ-N₂)(18-crown-6)] (4). The N–N distance and ν(¹⁴N–¹⁴N) stretching for 4 were 1.152(3) Å and 1818 cm⁻¹, respectively, suggesting that 4 is more activated than complexes 1 and 2. The complexes 1, 2, 3, and 4 reacted with HOTf and K[C₁₀H₈] to give NH₃ and N₂H₄. The yields of NH₃ and N₂H₄ (per V atom) were 47 and 11% for 1, 38 and 16% for 2, 77 and 7% for 3, and 80 and 5% for 4, respectively, and 3 and 4, which have a ligand L^Cy2, showed higher reactivity than 1 and 2. Full article

The technology of simultaneously recovering V and Ti from vanadium slag via ammonium salt roasting has proven to be an efficient route. However, due to the phase stability and complex chemical composition of vanadium slag, intermediate materials containing Fe, V, Ti and Mn are difficult to be characterized critically. This work aims to investigate the decomposition and transformation of vanadium slag during ammonium salt roasting, using a combination of FT-IR, XRD, XPS and SEM techniques. It was found that the lattice structure of Fe-contained spinel would be transformed from FeV₂O₄ to Fe²⁺V_nFe_2−nO₄ (0 < n < 2) during directly roasting in the air. However, there is no obvious change for Ti-contained and Mn-contained spinel. Using NH₄HSO₄ (ABS) as an additive and roasting the slag in the N₂ atmosphere, those spinels would be decomposed into various sulfate salts. Meanwhile, when the slag was roasted with NH₄HSO₄ in the air, a part of Fe(II) in (NH₄)₂Fe(SO₄)₂ would be transferred into Fe(III), but V(III), Ti(IV) and Mn(II) from those salts would remain the same valance state. Ultimately, about 88% V and 81% Ti were recovered, when vanadium slag was roasted at 663.15 K with a 1:5 ratio of slag-to-NH₄HSO₄ and followed by 8 vol.% H₂SO₄ leaching. Full article

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

We present a molecular mechanics force field in AMBER format for the mixed-valence manganese vanadium oxide cluster [Mn${}_4$V${}_4$O${}_{17}$(OAc)${}_3$]${}^{3-}$—a synthetic analogue of the oxygen-evolving complex that catalyzes the water oxidation reaction in photosystem II—with parameter sets for two different oxidation states. Most force field parameters involving metal atoms have been newly parametrized and the harmonic terms refined using hybrid quantum mechanics/molecular mechanics reference simulations, although some parameters were adapted from pre-existing force fields of vanadate cages and manganese oxo dimers. The characteristic Jahn–Teller distortions of d${}^4$ Mn${}^{\mathrm{III}}$ ions in octahedral environments are recovered by the force field. As an application, the developed parameters have been used to calculate the redox potential of the [Mn${}^{\mathrm{III}}$Mn${}_3^{\mathrm{IV}}$] ⇌ [Mn${}_4^{\mathrm{IV}}$]+e${}^{-}$ half-reaction in acetonitrile by means of Marcus theory. Full article

Fe(II)-bearing minerals (magnetite, siderite, green rust, etc.) are common products of microbial Fe(III) reduction, and they provide a reservoir of reducing capacity in many subsurface environments that may contribute to the reduction of redox active elements such as vanadium; which can exist as V(V), V(IV), and V(III) under conditions typical of near-surface aquatic and terrestrial environments. To better understand the redox behavior of V under ferrugenic/sulfidogenic conditions, we examined the interactions of V(V) (1 mM) in aqueous suspensions containing 50 mM Fe(II) as magnetite, siderite, vivianite, green rust, or mackinawite, using X-ray absorption spectroscopy at the V K-edge to determine the valence state of V. Two additional systems of increased complexity were also examined, containing either 60 mM Fe(II) as biogenic green rust (BioGR) or 40 mM Fe(II) as a mixture of biogenic siderite, mackinawite, and magnetite (BioSMM). Within 48 h, total solution-phase V concentrations decreased to <20 µM in all but the vivianite and the biogenic BiSMM systems; however, >99.5% of V was removed from solution in the BioSMM and vivianite systems within 7 and 20 months, respectively. The most rapid reduction was observed in the mackinawite system, where V(V) was reduced to V(III) within 48 h. Complete reduction of V(V) to V(III) occurred within 4 months in the green rust system, 7 months in the siderite system, and 20 months in the BioGR system. Vanadium(V) was only partially reduced in the magnetite, vivianite, and BioSMM systems, where within 7 months the average V valence state stabilized at 3.7, 3.7, and 3.4, respectively. The reduction of V(V) in soils and sediments has been largely attributed to microbial activity, presumably involving direct enzymatic reduction of V(V); however the reduction of V(V) by Fe(II)-bearing minerals suggests that abiotic or coupled biotic–abiotic processes may also play a critical role in V redox chemistry, and thus need to be considered in modeling the global biogeochemical cycling of V. Full article