Search Results (79)

Pyrochlore Bi_1.8Mn_0.5Ni_0.5Ta₂O_9-Δ (sp.gr. Fd-3m, a = 10.5038(9) Å) was synthesized by the solid-phase reaction method and characterized by vibrational and X-ray spectroscopy. According to scanning electron microscopy, the ceramics are characterized by a porous microstructure formed by randomly oriented oblong grains. The average crystallite size determined by X-ray diffraction is 65 nm. The charge state of transition element cations in the pyrochlore was analyzed by soft X-ray spectroscopy using synchrotron radiation. For mixed pyrochlore, a characteristic shift of Bi4f and Ta4f and Ta5p spectra to the region of lower energies by 0.25 and 0.90 eV is observed compared to the binding energy in Bi₂O₃ and Ta₂O₅ oxides. XPS Mn2p spectrum of pyrochlore has an intermediate energy position compared to the binding energy in MnO and Mn₂O₃, which indicates a mixed charge state of manganese (II, III) cations. Judging by the nature of the Ni2p spectrum of the complex oxide, nickel ions are in the charge state of +(2+ζ). The relative permittivity of the sample in a wide temperature (up to 350 °C) and frequency range (25–10⁶ Hz) does not depend on the frequency and exhibits a constant low value of 25. The minimum value of 4 × 10⁻³ dielectric loss tangent is exhibited by the sample at a frequency of 10⁶ Hz. The activation energy of conductivity is 0.7 eV. The electrical behavior of the sample is modeled by an equivalent circuit containing a Warburg diffusion element. Full article

Chemically demethoxylated and Ca-cross-linked orange-peel waste was engineered as a biosorbent for Mn(II) removal from water. A three-factor Box–Behnken design (biosorbent dose 3–10 g L⁻¹, initial Mn²⁺ 100–300 mg L⁻¹, contact time 3–8 h; pH 5.5 ± 0.1, 25 °C) required only 16 runs to locate the optimum (10 g L⁻¹, 100 mg L⁻¹, 8 h), at which the material removed 94.8% ± 0.3% manganese removal under the optimized conditions (10 g L⁻¹, 100 mg L⁻¹, 8 h, pH 5.5) of dissolved manganese and reached a Langmuir capacity of 29.7 mg g⁻¹. Equilibrium data fitted the Freundlich (R² = 0.968) and Sips (R² = 0.969) models best, indicating a heterogeneous surface, whereas kinetic screening confirmed equilibrium within 6 h. FTIR and SEM–EDX verified abundant surface –COO⁻/–OH groups and showed Mn deposits that partially replaced residual Ca, supporting an ion-exchange component in the uptake mechanism. A preliminary cost analysis (<USD 10 kg⁻¹) and > 90% regeneration efficiency over three cycles highlight the economic and environmental promise of this modified agro-waste for polishing Mn-laden effluents. Full article

Carbon nanodots have recently attracted attention as fluorescence imaging probes and magnetic resonance imaging (MRI) contrast agents in diagnostic and therapeutic applications due to their unique optical properties. In this work we report the synthesis of biocompatible Mn (II)-doped carbon nanodots and their performance as fluorescence and MRI contrast agents in in vitro assays. The thermal decomposition of a Diphenylhydantoin–Mn(II) complex assured the incorporation of manganese (II) ions in the carbon dots. The obtained materials display a favorable spin density for MRI applications. The synthesized Mn(II)-CNDs also displayed remarkable photoluminescence, with a bright blue emission and good response in in vitro fluorescence imaging. Cytotoxicity investigations revealed good cell viability on malignant melanoma cell lines in a large concentration range. A cytotoxic effect was observed for MG-63 osteosarcoma and breast adenocarcinoma cell lines. The in vitro MRI assays demonstrated the potentialities of the Mn(II)-CNDs as T2 contrast agents at low dosages, with relaxivity values higher than those of commercial ones. Due to the simplicity of their synthetic pathway and their low cytotoxicity, the prepared Mn(II)-CNDs are potential alternatives to currently used contrast agents based on gadolinium complexes. Full article

In recent years, extensive attention has been paid to advanced oxidation processes (AOPs) with peracetic acid (PAA), a widely used disinfectant, using transition metal ions for the degradation of organic contaminants within water environments. Mn(II) has been widely used as an effective homogeneous transition metal catalyst for oxidant activation, but it has shown poor performances with PAA. Since the stability of manganese species can be enhanced through the addition of ligands, this study systematically investigated a novel AOP for the oxidation of carbamazepine (CBZ) using an Mn(II)/PAA system with several different ligands added. The reactive species were explored through UV-vis spectrometry, scavengers, and probe compounds. The results suggest that Mn(III)–ligand complexes and other high-valent Mn species (Mn(V)) were generated and contributed obviously toward efficient CBZ oxidation, while radicals like CH₃CO₂^• and CH₃CO₃^• were minor contributors. The oxidation efficiency of Mn(II)/PAA/ligands depended highly on ligand species, as ethylene diamine tetraacetic acid (EDTA) and oxalate (SO) could promote the oxidation of CBZ, while pyrophosphate (PPP) showed modest enhancement. The results obtained here might contribute to the removal of residue pharmaceuticals under manganese-rich waters and also shed light on PAA-based AOPs that could help broaden our present knowledge of manganese chemistry for decontamination in water treatment. Full article

Next-generation recycling technologies must be urgently innovated to tackle huge volumes of spent batteries, photovoltaic panels or printed circuit boards (WPCBs). Current e-waste recycling industrial technology is dominated by traditional recycling technologies. Herein, ionic liquids (ILs), deep eutectic solvents (DESs) and promising oxidizing additives that can overcome some traditional recycling methods of metal ions from e-waste, used in our works from last year, are presented. The unique chemical environments of ILs and DESs, with the application of low-temperature extraction procedures, are important environmental aspects known as “Green Methods”. A closed-loop system for recycling zinc and manganese from the “black mass” (BM) of waste, Zn-MnO₂ batteries, is presented. The leaching process achieves a high efficiency and distribution ratio using the composition of two solvents (Cyanex 272 + diethyl phosphite (DPh)) for Zn(II) extraction. High extraction efficiency with 100% zinc and manganese recovery is also achieved using DESs (cholinum chloride/lactic acid, 1:2, DES 1, and cholinum chloride/malonic acid, 1:1, DES 2). New, greener recycling approaches to metal extraction from the BM of spent Li-ion batteries are presented with ILs ([N_8,8,8,1][Cl], (Aliquat 336), [P_6,6,6,14][Cl], [P_6,6,6,14][SCN] and [Benzet][TCM]) eight DESs, Cyanex 272 and D2EHPA. A high extraction efficiency of Li(I) (41–92 wt%) and Ni(II) (37–52 wt%) using (Cyanex 272 + DPh) is obtained. The recovery of Ni(II) and Cd(II) from the BM of spent Ni-Cd batteries is also demonstrated. The extraction efficiency of DES 1 and DES 2, contrary to ILs ([P_6,6,6,14][Cl] and [P_6,6,6,14][SCN]), is at the level of 30 wt% for Ni(II) and 100 wt% for Cd(II). In this mini-review, the option to use ILs, DESs and Cyanex 272 for the recovery of valuable metals from end-of-life WPCBs is presented. Next-generation recycling technologies, in contrast to the extraction of metals from acidic leachate preceded by thermal pre-treatment or from solid material only after thermal pre-treatment, have been developed with ILs and DESs using the ABS method, as well as Cyanex 272 (only after the thermal pre-treatment of WPCBs), with a process efficiency of 60–100 wt%. In this process, four new ILs are used: didecyldimethylammonium propionate, [N_10,10,1,1][C₂H₅COO], didecylmethylammonium hydrogen sulphate, [N_10,10,1,H][HSO₄], didecyldimethylammonium dihydrogen phosphate, [N_10,10,1,1][H₂PO₄], and tetrabutylphosphonium dihydrogen phosphate, [P_4,4,4,4][H₂PO₄]. The extraction of Cu(II), Ag(I) and other metals such as Al(III), Fe(II) and Zn(II) from solid WPCBs is demonstrated. Various additives are used during the extraction processes. The Analyst 800 atomic absorption spectrometer (FAAS) is used for the determination of metal content in the solid BM. The ICP-OES method is used for metal analysis. The obtained results describe the possible application of ILs and DESs as environmental media for upcycling spent electronic wastes. Full article

With increasing energy demands, fuel cells are a popular avenue for portability and low waste emissions. Hydrogen fuel cells are popular due to their potential output power and clean waste. However, due to storage and transport concerns, hydrogen peroxide fuel cells are a promising alternative. Although they have a lower output potential compared to hydrogen fuel cells, peroxide can act as both the oxidizing and reducing agent, simplifying the structure of the cell. In addition to reducing the complexity, hydrogen peroxide is stable in liquid form and can be stored in less demanding methods. This paper investigates chelated metals as electrode material for hydrogen peroxide fuel cells. Chelated metal complexes are ring-like structures that form from binding organic or inorganic compounds with metal ions. They are used in medical imaging, water treatment, and as catalysts for reactions. Copper(II) phthalocyanine, phthalocyanine green, poly(copper phthalocyanine), bis(ethylenediamine)copper(II) hydroxide, iron(III) ferrocyanine, graphene oxide decorated with Fe₃O₄, zinc phthalocyanine, magnesium phthalocyanine, manganese(II) phthalocyanine, cobalt(II) phthalocyanine are investigated as electrode materials for peroxide fuel cells. In this study, the performance of these materials is evaluated using cyclic voltammetry. The voltammograms are compared, as well as observations are made during the materials’ use to measure their effectiveness as electrode material. There has been limited research comparing the use of these chelated metals in the context of hydrogen peroxide fuel cells. Through this research, the goal is to further the viability of hydrogen peroxide fuel cells. Poly(copper phthalocyanine) and graphene oxide doped with iron oxides had strong redox catalytic activity for use in acidic peroxide single-compartment fuel cells, where the poly(copper phthalocyanine) electrode compound generated the highest peak power density of 7.92 mW/cm² and cell output potential of 0.634 V. Full article

This study presents data on the water quality of the Guarani Aquifer based on samples collected from distinct groundwater wells in the western region of Santa Catarina State, Brazil. Among the analyses performed, the results indicated the need for treatment to ensure suitability for human consumption, particularly concerning Fe³⁺ and Mn²⁺ ions. Accordingly, natural (NCLIN) and activated clinoptilolite (ACLIN) zeolites were evaluated for ion removal from synthetic aqueous solutions through adsorption. NCLIN demonstrated excellent performance in adsorbing Fe³⁺ and Mn²⁺ ions, achieving removal efficiencies of over 98% and 95%, respectively, at a controlled pH of 6.0 (NCLIN) or 4.0 (ACLIN). A non-linear approach to modeling adsorption kinetics indicated that the pseudo-second-order model best represented the experimental data. This finding suggests that the interaction between the adsorbent and Fe³⁺ and Mn²⁺ ions occur through electron sharing and chemisorption. Equilibrium modeling analysis revealed that adsorption on NCLIN occurred in a monolayer, whereas adsorption on ACLIN followed a multilayer pattern. This behavior is attributed to the activation process with H₂SO₄, which led to dealumination and the formation of HSO₃⁻ groups on the adsorbent surface. Full article

In this study, we investigate the magnetic properties of the molecular compound [Mn(mal)(H₂O)]ₙ (mal = dianion of malonic acid) by integrating microscopic and macroscopic characterization, combining unpolarized neutron diffraction and magnetometry measurements. Neutron diffraction, though non-commonly applied to molecular compounds, proved essential for fully resolving the magnetic structure, as well as overcoming challenges such as hydrogen-related incoherent scattering and difficulties in accurately locating light atoms. Our neutron data provided critical structural details, including the precise location of hydrogen atoms, especially those associated with crystallization water molecules. By conducting low-temperature measurements below the magnetic ordering temperature, we identified the correct Shubnikov space group (Pc’a2₁’) and established a magnetic model consistent with the observed weak ferromagnetism. Our findings reveal that the compound presents a spin-canted structure with a weak ferromagnetic signal along the b-axis. This signal originates primarily from antisymmetric exchange interactions rather than single-ion anisotropy, consistent with the isotropic nature of the Mn(II) (⁶A₁g) ground state. The combined neutron diffraction and magnetometry results provide a comprehensive understanding of how structural and symmetry factors influence the magnetic properties of malonate-based manganese compounds. Full article

Monensic acid is a natural polyether ionophore and is a therapeutic of first choice in veterinary medicine for the control of coccidiosis. Although known as a sodium-binding ligand, it can also form a variety of coordination species depending on experimental conditions applied. In this study, we present the crystal structures and properties of Co(II) and Mn(II) complexes of sodium monensinate (MonNa) derived from the reaction of MonNa with cobalt or manganese dinitrates. The newly obtained coordination compounds have the same composition [M(MonNa)₂(NO₃)₂] but the transition metal ions are placed in a different environment. The two nitrate ligands behave mono- or bidentately bound in the Co(II)- and Mn(II)-containing species, respectively, while the monensinate ligands act in a similar manner through their monodentate carboxylate functions. The formed CoO₄ and MnO₆ units determine the geometry of the corresponding inner coordination cores of the complexes as a tetrahedron in the case of Co(II), and as a strongly distorted octahedral structure in Mn(II) species. The effect of inorganic anions on the antibacterial performance of sodium monensinate appears to be negligible, while the presence of Co(II) or Mn(II) cations preserves or enhances the activity of unmodified MonNa, which differentially affects the growth of Bacillus subtilis, Bacillus cereus, Kocuria rhizophila, Staphilococcus aureus, and Staphilococcus saprophyticus strains. Full article

One of the challenges for experimental structural biology in the 21st century is to see chemical reactions happen. Staphylococcus aureus (S. aureus) DNA gyrase is a type IIA topoisomerase that can create temporary double-stranded DNA breaks to regulate DNA topology. Drugs, such as gepotidacin, zoliflodacin and the quinolone moxifloxacin, can stabilize these normally transient DNA strand breaks and kill bacteria. Crystal structures of uncleaved DNA with a gepotidacin precursor (2.1 Å GSK2999423) or with doubly cleaved DNA and zoliflodacin (or with its progenitor QPT-1) have been solved in the same P6₁ space-group (a = b ≈ 93 Å, c ≈ 412 Å). This suggests that it may be possible to observe the two DNA cleavage steps (and two DNA-religation steps) in this P6₁ space-group. Here, a 2.58 Å anomalous manganese dataset in this crystal form is solved, and four previous crystal structures (1.98 Å, 2.1 Å, 2.5 Å and 2.65 Å) in this crystal form are re-refined to clarify crystal contacts. The structures clearly suggest a single moving metal mechanism—presented in an accompanying (second) paper. A previously published 2.98 Å structure of a yeast topoisomerase II, which has static disorder around a crystallographic twofold axis, was published as containing two metals at one active site. Re-refined coordinates of this 2.98 Å yeast structure are consistent with other type IIA topoisomerase structures in only having one metal ion at each of the two different active sites. Full article

Nickel manganese oxide (NiMnO₃) combines magnetic and dielectric properties, making it a promising material for sensor and supercapacitor applications, as well as for catalytic water splitting. The efficiency of its utilization is notably influenced by particle size. In this study, we investigate the influence of thermal treatment parameters on the phase composition of products from alkali co-precipitation of nickel and manganese (II) ions and identify optimal conditions for synthesizing phase-pure nickel manganese oxide. Ultrafine nanoparticles of NiMnO₃ (with sizes as small as 2 nm) are obtained via liquid-phase ultrasonic dispersion, exhibiting a narrow size distribution. A systematic exploration of the solvent nature (water, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylformamide) on the efficiency of ultrasonic dispersion of NiMnO₃ nanoparticles is provided. It is demonstrated that particle size is influenced not only by absorbed acoustic power, dependent on the physical properties of the used solvent (boiling temperature, gas solubility, viscosity, density) but also by the chemical stability of the solvent under prolonged ultrasonic treatment. Our findings provide insights for designing ultrasonic treatment protocols for nanoparticle dispersions with tailored particle sizes. Full article

Ovalbumin (OVA), a protein vital for chick embryo nutrition, hydration, and antimicrobial protection, together with other egg-white proteins, migrates to the amniotic fluid and is orally absorbed by the embryo during embryogenesis. Recently, it has been shown that for optimal eggshell quality, the hen diet can be supplemented with manganese. Although essential for embryonic development, manganese in excess causes neurotoxicity. This study investigates whether OVA may be involved in the regulation of manganese levels. The binding of Mn(II) to OVA was investigated using electron paramagnetic resonance (EPR) spectroscopy. The results show that OVA binds a maximum of two Mn(II) ions, one with slightly weaker affinity, even in a 10-fold excess, suggesting it may have a protective role from Mn(II) overload. It seems that the binding of Mn(II), or the presence of excess Mn(II), does not affect OVA’s tertiary structure, as evidenced from fluorescence and UV/vis measurements. Comparative analysis with bovine and human serum albumins revealed that they exhibit higher affinities for Mn(II) than OVA, most likely due to their essentially different physiological roles. These findings suggest that OVA does not play a role in the transport and storage of manganese; however, it may be involved in embryo protection from manganese-induced toxicity. Full article

This study aimed to assess the sorption capacity of a natural sorbent, specifically birch bark (BB), and its modification using chemical reagents, including nitric and hydrochloric acid, sodium hydroxide, and chloride. The objective of the chemical modification was to enhance the sorption capacity of the heavy metals cadmium(II), chromium(VI), and manganese(II). The most effective modification for adsorbing cadmium and manganese from aqueous solutions was achieved by treating the sorbent with a 0.1 M sodium hydroxide solution (BBNa). Conversely, in the case of chromium, each modification adversely affected its adsorption by the sorbent. Concentrations of the solutions were analyzed using atomic absorption spectrometry at appropriate time intervals. The adsorption process was described using Langmuir, Freundlich, and Temkin isotherms. The Freundlich isotherm provided the best fit for cadmium and chromium (R² = 0.988 and 0.986, respectively), while the Langmuir isotherm was most suitable for manganese (R² = 0.996). The sorption capacity varied for each metal ion: Cd (II)—33.13 mg/g, Cr (VI)—35.98 mg/g, and Mn (II)—24 mg/g for the highest concentration tested. This study employed pseudo–first-rate order, pseudo–second-rate order model kinetics, and the Weber–Morris model to examine the adsorption kinetics. The pseudo–second-rate order kinetics demonstrated the best fit (R² > 0.94) for each heavy metal, which underlines the process’s chemical nature. Full article

This work presents the research results on the development of an innovative, hydrometallurgical technology for the production of manganese(II) perrhenate dihydrate from recycled waste. These wastes are scraps of Ni-based superalloys containing Re and scraps of Li–ion batteries containing Mn—specifically, solutions from the leaching of black mass. This work presents the conditions for the production of Mn(ReO₄)₂·2H₂O. Thus, to obtain Mn(ReO₄)₂·2H₂O, manganese(II) oxide was used, precipitated from the solutions obtained after the leaching of black mass from Li–ion batteries scrap and purified from Cu, Fe and Al (pH = 5.2). MnO₂ precipitation was carried out at a temperature < 50 °C for 30 min using a stoichiometric amount of KMnO₄ in the presence of H₂O₂. MnO₂ precipitated in this way was purified using a 20% H₂SO₄ solution and then H₂O. Purified MnO₂ was then added alternately with a 30% H₂O₂ solution to an aqueous HReO₄ solution. The reaction was conducted at room temperature for 30 min to obtain a pH of 6–7. Mn(ReO₄)₂·2H₂O precipitated by evaporating the solution to dryness was purified by recrystallization from H₂O with the addition of H₂O₂ at least twice. Purified Mn(ReO₄)₂·2H₂O was dried at a temperature of 100–110 °C. Using the described procedure, Mn(ReO₄)₂·2H₂O was obtained with a purity of >99.0%. This technology is an example of the green transformation method, taking into account the 6R principles. Full article

The homoleptic cationic complex formed by reacting suitable manganese(II) salts with 2,2′-bipyridine-1,1′-dioxide (bipyO₂) has been subjected to several studies in the past because of its peculiar absorption and electrochemical features. Here, the first single-crystal X-ray structure determination of a [Mn(bipyO₂)₃]²⁺ salt is reported, where the charge of the cation is balanced by perchlorate anions. The hydrated salt [Mn(bipyO₂)₃](ClO₄)₂ crystallizes in the monoclinic system (P2₁/n space group) and the asymmetric unit contains three cationic complexes and six perchlorate anions. The environment of the manganese(II) ions is best described as octahedral, with scarce variations among the three cations in the asymmetric unit. The bipyO₂ ligands exhibit κ² coordination mode, forming seven-membered metallacycles. The X-ray outcomes have been used as the starting point for DFT and TDDFT calculations, aimed to elucidate the charge transfer origin of the noticeable absorption in the visible range. The MLCT nature is confirmed by the hole and electron distributions associated with the spin-allowed transitions. DFT calculations on the related manganese(III) complex indicate that the geometry of [Mn(bipyO₂)₃]²⁺ changes only slightly upon oxidation, in agreement with the reversible electrochemical behaviour experimentally observed. Full article