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Search Results (476)

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Keywords = Fe (II) complex

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16 pages, 1937 KiB  
Article
Anti-Bacterial and Anti-Fungal Properties of a Set of Transition Metal Complexes Bearing a Pyridine Moiety and [B(C6F5)4]2 as a Counter Anion
by Ahmed K. Hijazi, Mohammad El-Khateeb, Ziyad A. Taha, Mohammed I. Alomari, Noor M. Khwaileh, Abbas I. Alakhras, Waleed M. Al-Momani, Ali Elrashidi and Ahmad S. Barham
Molecules 2025, 30(15), 3121; https://doi.org/10.3390/molecules30153121 - 25 Jul 2025
Viewed by 227
Abstract
Background: Transition metal complexes incorporating fluorinated counter anions represent a significant class of compounds with broad applications in industry, pharmaceuticals, and biomedicine. These fluorinated anions are known to enhance the solubility, stability, and reactivity of the complexes, thereby expanding their functional utility in [...] Read more.
Background: Transition metal complexes incorporating fluorinated counter anions represent a significant class of compounds with broad applications in industry, pharmaceuticals, and biomedicine. These fluorinated anions are known to enhance the solubility, stability, and reactivity of the complexes, thereby expanding their functional utility in various chemical and biological contexts. Methods: A set of metal(II) complexes of the general formula [MPy6][B(C6F5)4]2 where (Py = pyridine, M = Mn (1), Fe (2), Co (3), Ni (4), Cu (5), Zn (6)) have been synthesized by direct reaction of metal halides and pyridine in the presence of Ag[B(C6F5)4]. The complexes were characterized using different techniques to assure their purity, such as elemental analysis (EA), electron paramagnetic resonance (EPR) spectroscopy, thermogravimetric analysis (TGA), ultraviolet–visible (UV–Vis) spectroscopy, 11B-NMR, 1H-NMR, and FT-IR spectroscopy. The antimicrobial and antifungal properties against different types of bacteria and fungi were studied for all prepared complexes. Results: The synthesized complexes exhibited broad-spectrum antimicrobial activity, demonstrating variable efficacy compared to the reference antibiotic, oxytetracycline (positive control). Notably, complex 6 displayed exceptional antibacterial activity against Streptococcus pyogenes, with a minimum inhibitory concentration (MIC) of 4 µg/mL, outperforming the control (MIC = 8 µg/mL). Complexes 1, 2, and 4 showed promising activity against Shigella flexneri, Klebsiella pneumoniae, and Streptococcus pyogenes, each with MIC values of 8 µg/mL. Conversely, the lowest activity (MIC = 512 µg/mL) was observed for complexes 3, 5, and 6 against Pseudomonas aeruginosa, Escherichia coli, and Klebsiella pneumoniae, respectively. Regarding antifungal properties, complexes 5 and 6 demonstrated the highest activity against Candida albicans, with MIC values of 8 µg/mL, equivalent to that of the positive control, fluconazole. Density functional theory (DFT) calculations confirmed an overall octahedral coordination geometry for all complexes, with tetragonal distortions identified in complexes 3, 4, and 5. Full article
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19 pages, 4875 KiB  
Article
Synthesis, Characterization, and Biological Evaluation of Some 3d Metal Complexes with 2-Benzoylpyridine 4-Allylthiosemicarbazone
by Vasilii Graur, Ianina Graur, Pavlina Bourosh, Victor Kravtsov, Carolina Lozan-Tirsu, Greta Balan, Olga Garbuz, Victor Tsapkov and Aurelian Gulea
Inorganics 2025, 13(7), 249; https://doi.org/10.3390/inorganics13070249 - 21 Jul 2025
Viewed by 316
Abstract
The eight new copper(II), nickel(II), zinc(II), and iron(III) coordination compounds [Cu(L)Cl]2 (1), [Cu(L)Br]2 (2), [Cu(L)(NO3)]2 (3), [Cu(phen)(L)]NO3 (4), [Ni(HL)2](NO3)2·H2O (5 [...] Read more.
The eight new copper(II), nickel(II), zinc(II), and iron(III) coordination compounds [Cu(L)Cl]2 (1), [Cu(L)Br]2 (2), [Cu(L)(NO3)]2 (3), [Cu(phen)(L)]NO3 (4), [Ni(HL)2](NO3)2·H2O (5), [Ni(HL)2]Cl2 (6), [Zn(L)2]·0.125H2O (7), and [Fe(L)2]Cl (8), where HL stands for 2-benzoylpyridine 4-allylthiosemicarbazone, were synthesized and characterized. 1H, 13C NMR, and FTIR spectroscopies were used for characterization of the HL thiosemicarbazone. The elemental analysis, the FTIR spectroscopy, and the study of molar electrical conductivity were used for characterization of the coordination compounds 18. Also, the crystal structures of HL, its salts ([H2L]Cl; [H2L]NO3), and complexes 1, 3, 5, 7, and 8 were determined using single-crystal X-ray diffraction analysis. Complexes 5, 7, 8 have mononuclear structures, while copper(II) complexes 1 and 3 have a dimeric structure with the sulfur atoms of the thiosemicarbazone ligand bridging two copper atoms together. Thiosemicarbazone HL and the complexes manifest antibacterial and antifungal activities. The studied substances are more active towards Gram-negative bacteria than towards Gram-positive bacteria and fungi. Complex 1 is the most active one towards Gram-positive bacteria and C. albicans, while the introduction of 1,10-phenanthroline into the inner sphere enhances the activity towards Gram-negative bacteria. Thiosemicarbazone and complexes 6 and 7 manifest antiradical activity that exceeds the activity of Trolox. HL and complex 1 manifest antiproliferative activity towards HL-60 cancer cells which exceeds the activity of their analogs with 2-formyl-/2-acetylpyridine 4-allylthiosemicarbazone. Full article
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30 pages, 7220 KiB  
Article
Automated Hyperspectral Ore–Waste Discrimination for a Gold Mine: Comparative Study of Data-Driven and Knowledge-Based Approaches in Laboratory and Field Environments
by Mehdi Abdolmaleki, Saleh Ghadernejad and Kamran Esmaeili
Minerals 2025, 15(7), 741; https://doi.org/10.3390/min15070741 - 16 Jul 2025
Viewed by 377
Abstract
Hyperspectral imaging has been increasingly used in mining for detailed mineral characterization and enhanced ore–waste discrimination, which is essential for optimizing resource extraction. However, the full deployment of this technology still faces challenges due to the variability of field conditions and the spectral [...] Read more.
Hyperspectral imaging has been increasingly used in mining for detailed mineral characterization and enhanced ore–waste discrimination, which is essential for optimizing resource extraction. However, the full deployment of this technology still faces challenges due to the variability of field conditions and the spectral complexity inherent in real-world mining environments. In this study, we compare the performance of two approaches for ore–waste discrimination in both laboratory and actual mine site conditions: (i) a data-driven feature extraction (FE) method and (ii) a knowledge-based mineral mapping method. Rock samples, including ore and waste from an open-pit gold mine, were obtained and scanned using a hyperspectral imaging system under laboratory conditions. The FE method, which quantifies the frequency absorption peaks at different wavelengths for a given rock sample, was used to train three discriminative models using the random forest classifier (RFC), support vector classification (SVC), and K-nearest neighbor classifier (KNNC) algorithms, with RFC achieving the highest performance with an F1-score of 0.95 for the laboratory data. The mineral mapping method, which quantifies the presence of pyrite, calcite, and potassium feldspar based on prior geochemical analysis, yielded an F1-score of 0.78 for the ore class using the RFC algorithm. In the next step, the performance of the developed discriminative models was tested using hyperspectral data of two muck piles scanned in the open-pit gold mine. The results demonstrated the robustness of the mineral mapping method under field conditions compared to the FE method. These results highlight hyperspectral imaging as a valuable tool for improving ore-sorting efficiency in mining operations. Full article
(This article belongs to the Section Mineral Exploration Methods and Applications)
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15 pages, 3736 KiB  
Article
Molecular Characterization of a Restriction Endonuclease PsaI from Pseudomonas anguilliseptica KM9 and Sequence Analysis of the PsaI R-M System
by Beata Furmanek-Blaszk, Iwona Mruk and Marian Sektas
Int. J. Mol. Sci. 2025, 26(14), 6548; https://doi.org/10.3390/ijms26146548 - 8 Jul 2025
Viewed by 199
Abstract
A restriction enzyme PsaI, an isoschizomer of the type II restriction endonuclease HindIII, has been purified to homogeneity from Gram-negative bacilli Pseudomonas anguilliseptica KM9 found in a wastewater treatment plant in Poland. Experimental data revealed that R.PsaI is highly active in the presence [...] Read more.
A restriction enzyme PsaI, an isoschizomer of the type II restriction endonuclease HindIII, has been purified to homogeneity from Gram-negative bacilli Pseudomonas anguilliseptica KM9 found in a wastewater treatment plant in Poland. Experimental data revealed that R.PsaI is highly active in the presence of Co2+, Mg2+, and Zn2+ and reached a maximal level of activity between 2.5 and 10 mM while its activity was significantly decreased in the presence of Ca2+, Fe2+, Mn2+, and Ni2+. Moreover, we found that the purified R.PsaI did not require NaCl for enzyme activity. Restriction cleavage analysis followed by sequencing confirmed 5′-AAGCTT-3′ as the recognition site. The genes for restriction–modification system PsaI were identified and characterized. Downstream of the psaIM gene, we noticed an ORF that shares extensive similarity with recombinase family protein specifically involved in genome rearrangements. Sequence analysis revealed that the PsaI R-M gene complex showed striking nucleotide sequence similarity (>98%) with the genes of the PanI R-M system from a P. anguilliseptica MatS1 strain identified in a soil sample from Sri Lanka. Full article
(This article belongs to the Special Issue Genetic Engineering in Microbial Biotechnology)
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31 pages, 9591 KiB  
Article
Deformable Fricke-XO-Gelatin Radiochromic Dosimeter of Ionizing Radiation and Its Applications in Quality Assurance Tests for Radiation Therapy
by Michał Piotrowski, Piotr Maras, Zbigniew Stempień, Radosław Wach and Marek Kozicki
Materials 2025, 18(13), 3135; https://doi.org/10.3390/ma18133135 - 2 Jul 2025
Viewed by 353
Abstract
This work presents a Fricke radiochromic gel dosimeter with xylenol orange (XO) and a gelatin matrix modified with sorbitol. The dosimeter, combined with 2D scanning using a flatbed scanner and data processing using dedicated software packages, creates a radiotherapy dosimetry measurement system. The [...] Read more.
This work presents a Fricke radiochromic gel dosimeter with xylenol orange (XO) and a gelatin matrix modified with sorbitol. The dosimeter, combined with 2D scanning using a flatbed scanner and data processing using dedicated software packages, creates a radiotherapy dosimetry measurement system. The dosimeter reacts to ionizing radiation by changing color as a result of the formation of complexes of Fe3+ and XO molecules. It was characterized in terms of thermal and chemical stability and mechanical properties. The presence of sorbitol improved the mechanical and thermal properties of the dosimeter. The dosimeter maintains chemical stability, enabling its use in dosimetric applications, for at least six weeks. The dose–response characteristics of the dosimeter are discussed and indicate a dynamic dose–response of the dosimeter (up to saturation) of about 20 Gy and a linear dose–response of about 12.5 Gy. The following applications of the dosimeter are discussed: (i) as a 2D dosimeter in a plastic container for performing a coincidence test of radiation and mechanical isocenters of a medical accelerator, and (ii) for in vivo dosimetry as a 2D dosimeter alone and simultaneously as a bolus and a 2D dosimeter. Research has shown that the dosimeter has promise in many applications. Full article
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17 pages, 1489 KiB  
Article
Nanomaterials Reduce Cadmium Bioavailability in Paddy Soils Through Redox-Driven Immobilization and Microbial Dynamics
by Buyun Du, Jiasai Fei, Laiyong You, Jing Zhou and Jun Zhou
Agronomy 2025, 15(6), 1423; https://doi.org/10.3390/agronomy15061423 - 11 Jun 2025
Viewed by 816
Abstract
Cadmium (Cd) mobilization in paddy soils during redox fluctuations poses significant risks to rice safety. This study investigated the efficacy of nano-calcium carbonate (NCC), nano-hydroxyapatite (NHAP), and their composite (C+P) in immobilizing Cd under simulated flooding–drainage cycles. Soil treatments (0.5% and 1.0% w [...] Read more.
Cadmium (Cd) mobilization in paddy soils during redox fluctuations poses significant risks to rice safety. This study investigated the efficacy of nano-calcium carbonate (NCC), nano-hydroxyapatite (NHAP), and their composite (C+P) in immobilizing Cd under simulated flooding–drainage cycles. Soil treatments (0.5% and 1.0% w/w) were subjected to 40 day anaerobic and 20 day aerobic incubation. The results demonstrated that NCC and C+P elevated the soil pH by 1.35–1.39 and 0.72–1.01 units during the anaerobic and aerobic phases, respectively. These amendments suppressed Fe(II) and Mn(II) release by 41–75%, correlating with reduced Cd bioavailability. While nanomaterials minimally influenced Cd speciation during flooding, aerobic conditions triggered a marked shift: residual Cd fractions increased by 80.8–116.4% under NCC, driven by CdCO3 precipitation and phosphate complexation. Cd release rates decreased by 53.6–66.8% in NCC and C+P treatments during oxidation. Microbial analysis revealed diminished bacterial diversity but enriched Firmicutes (up to 58.9%), which positively correlated with pH and residual Cd. Redundancy analysis identified pH and Fe/Mn dynamics as key regulators of the microbial community structure. NCC emerged as the most effective amendment. This study highlights the potential of NCC-based strategies for mitigating Cd risks in acidic paddy soils, particularly during post-flooding drainage. Full article
(This article belongs to the Special Issue Agricultural Pollution: Toxicology and Remediation Strategies)
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21 pages, 6026 KiB  
Article
Tectonic Setting of the Neoproterozoic Gabbroic Intrusions in the Luanchuan Area, Southern Margin of the North China Craton: Constraints from Ilmenite and Biotite Mineralogy
by Jianhan Huang, Zhenzhen Huang, Danli Chen, Kekun Li, Xiaoxiao Huang, Minghao Ren and Yazhou Fan
Minerals 2025, 15(6), 602; https://doi.org/10.3390/min15060602 - 3 Jun 2025
Viewed by 340
Abstract
The Luanchuan Neoproterozoic gabbroic intrusions are located at the southern margin of the North China Craton (NCC), intruding into the marble and schist from the Nannihu and Meiyaogou Formations of the Neoproterozoic Luanchuan Group. The gabbroic rocks consist of plagioclase (30%–50%) and amphibole [...] Read more.
The Luanchuan Neoproterozoic gabbroic intrusions are located at the southern margin of the North China Craton (NCC), intruding into the marble and schist from the Nannihu and Meiyaogou Formations of the Neoproterozoic Luanchuan Group. The gabbroic rocks consist of plagioclase (30%–50%) and amphibole (40%–60%), with minor ilmenite (2%–5%), biotite (1%–3%), and titanite (~1%). Based on the occurrence and mineral chemistry, two types of biotites were identified. The first type of biotite (Bt I) is brown, with a fine- to micro-grained anhedral texture, occurring around the magmatic ilmenite and coexisting with titanite. Bt I is characterized by high TiO2 and FeO contents, with TiO2 > 2 wt% (2.03 wt%–3.15 wt%) and FeO ranging from 19.94 wt% to 22.08 wt%. The other type of biotite (Bt II) is light grayish-brown to dark reddish-brown, with a medium- to coarse-grained euhedral texture, coexisting with grayish-green amphibole. Bt II exhibits lower TiO2 (1.40 wt%–1.90 wt%) and FeO contents (18.03 wt%–21.42 wt%). The K2O (7.56 wt%–9.32 wt%) and SiO2 (34.49 wt%–37.04 wt%) contents of Bt I are slightly lower than those of Bt II (8.28 wt%–9.73 wt% and 35.18 wt%–37.52 wt%, respectively). Despite the low Ti content in biotites, the mineral occurrence indicates that both types of biotite yield a magmatic origin, resulting from the reactions between early crystallized minerals and residual magma. Bt I originated from the reaction between ilmenite and residual magma, while Bt II resulted from the production of the reaction between clinopyroxne and residual magma. Ilmenite exhibits low MgO and Fe2O3 contents but high FeO and MnO contents, suggesting genetic similarities to the Skaergaard and Panzhihua intrusions. Both types of biotites record consistent temperatures (T = 766 to 818 °C), pressures (P = 5.30–8.80 kbar), and oxygen fugacities (log fO2 = −12.35 to −14.06), aligning with those of the Fanshan complex and the Falcon Island intrusion. The mineralogy of ilmenite and biotite indicates that the Luanchuan gabbroic intrusions formed in a continental rift setting, which is considered to be associated with the breakup of the Rodinia supercontinent. Full article
(This article belongs to the Section Mineral Deposits)
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24 pages, 8136 KiB  
Review
Recent Advances in the Electron Transfer Mechanism of Fe-Based Electro-Fenton Catalysts for Emerging Organic Contaminant Degradation
by Lu Huang, Yufeng Zhao, Yu Bai, Junxi Song and Guojin Sun
Catalysts 2025, 15(6), 549; https://doi.org/10.3390/catal15060549 - 1 Jun 2025
Viewed by 814
Abstract
Heterogeneous electro-Fenton (HEF) technology utilizing iron-based cathode catalysts has emerged as an efficient advanced oxidation process for wastewater treatment, demonstrating outstanding performance in degrading emerging organic contaminants (EOCs) while maintaining environmental sustainability. The performance of this technology is governed by two critical processes: [...] Read more.
Heterogeneous electro-Fenton (HEF) technology utilizing iron-based cathode catalysts has emerged as an efficient advanced oxidation process for wastewater treatment, demonstrating outstanding performance in degrading emerging organic contaminants (EOCs) while maintaining environmental sustainability. The performance of this technology is governed by two critical processes: the accumulation of H2O2 and the electron transfer mechanisms governing the Fe(III)/Fe(II) redox cycle. This review comprehensively summarizes recent advances in understanding the electron transfer mechanisms in iron-based HEF systems and their applications for EOC degradation. Five representative catalyst categories are critically analyzed, including zero-valent iron/alloys, iron oxides, iron-carbon/nitrogen-doped carbon composites, iron sulfides/phosphides, and iron-based MOFs, with a particular focus on their structural design, catalytic performance, and electron transfer mechanisms. A particular focus is placed on strategies enhancing Fe(III)/Fe(II) cycling efficiency and the interplay between radical (OH) and non-radical (1O2) oxidation pathways, including their synergistic effects in complex wastewater systems. Major challenges, including catalyst stability, pH adaptability, and selective oxidation in complex matrices, are further discussed. Potential solutions to these limitations are also discussed. This review provides fundamental insights for designing high-efficiency iron-based HEF catalysts and outlines future research directions to advance practical applications. Full article
(This article belongs to the Special Issue Efficient Electro-Fenton-Catalysis)
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35 pages, 5248 KiB  
Review
Effect of Remote Amine Groups on Ground- and Excited-State Properties of Terpyridyl d-Metal Complexes
by Anna Kryczka, Joanna Palion-Gazda, Katarzyna Choroba and Barbara Machura
Molecules 2025, 30(11), 2386; https://doi.org/10.3390/molecules30112386 - 29 May 2025
Viewed by 630
Abstract
Over the last nine decades, 2,2′:6′,2″-terpyridine (terpy) derivatives and their transition d-metal complexes have been extensively explored due to their unique and widely tuned optical, electrochemical, and biological properties. Terpyridyl transition metal complexes occupy a prominent position among functional molecular materials for applications [...] Read more.
Over the last nine decades, 2,2′:6′,2″-terpyridine (terpy) derivatives and their transition d-metal complexes have been extensively explored due to their unique and widely tuned optical, electrochemical, and biological properties. Terpyridyl transition metal complexes occupy a prominent position among functional molecular materials for applications in optoelectronics, life science, catalysis, and photocatalysis, as well as they have played a key role in determining structure–property relationships. This review summarizes the developments of amine-functionalized R-C6H4-terpy systems and their d-metal complexes, largely concentrating on their photophysical and electrochemical properties. Functionalization of the terpy core with the electron-rich group, attached to the central pyridine ring of the terpy backbone via the phenylene linker, gives rise to organic push–pull systems showing the photoinduced charge flow process from the peripheral donor substituent to the terpy acceptor. The introduction of amine-functionalized R-C6H4-terpy systems into the coordination sphere of a d-metal ion offers an additional way for controlling the photophysics of these systems, in agreement with the formation of the excited state of intraligand charge transfer (ILCT) nature. Within this review, a detailed discussion has been presented for R-C6H4-terpys modified with acyclic and cyclic amine groups and their Cr(III), Mn(I), Re(I), Fe(II), Ru(II), Os(II), Pt(II), and Zn(II) coordination compounds. Full article
(This article belongs to the Special Issue Advances in Coordination Chemistry, 3rd Edition)
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22 pages, 3601 KiB  
Article
Fast Removal of Naphthol Blue Black B Dye from Water Using Polyethyleneimine Functionalized Zinc, Iron, and Manganese Porphyrinic Complexes: Structural Characterization, Kinetic, and Isotherms Studies
by Sahar Y. Rajeh, Aljazi Abdullah Alrashidi, Raoudha Soury and Mahjoub Jabli
Polymers 2025, 17(11), 1494; https://doi.org/10.3390/polym17111494 - 28 May 2025
Viewed by 367
Abstract
In the present work, meso-tetrakis(2,4,6-trimethylphenyl) porphyrinato)zinc(II): ([Zn(TMP)] (1), meso-tetrakis-(tetraphenyl)porphyrin iron(III))chloride): [Fe(TPP)Cl] (2), and meso-tetrakis(phenyl)porphyrin manganese(III) chloride): [Mn(TPP)Cl] (3) were synthesized. Then, the three prepared porphyrinic complexes (13) were functionalized with branched polyethyleneimine (PEI). The prepared complexes were thoroughly analyzed [...] Read more.
In the present work, meso-tetrakis(2,4,6-trimethylphenyl) porphyrinato)zinc(II): ([Zn(TMP)] (1), meso-tetrakis-(tetraphenyl)porphyrin iron(III))chloride): [Fe(TPP)Cl] (2), and meso-tetrakis(phenyl)porphyrin manganese(III) chloride): [Mn(TPP)Cl] (3) were synthesized. Then, the three prepared porphyrinic complexes (13) were functionalized with branched polyethyleneimine (PEI). The prepared complexes were thoroughly analyzed using several analytical techniques, including 1H NMR, FT-IR, UV-vis, XRD, XRF, TGA-DTA, SEM, and EDX. The presence of sharp main peaks at 2θ between 10° and 80°, in XRD analysis, for all studied compounds suggested the crystalline nature of the porphyrinic complexes. The morphological properties of the porphyrininc complexes were significantly affected by the chemical modification with polyethyleneimine. EDX result confirmed the complexation of zinc, iron, and manganese metals with the porphyrinic core. The increase in carbon and nitrogen contents after the addition of polyethyleneimine to the complexes (13) was noticeable. After thermal decomposition, the total mass loss was equal to 92.97%, 66.77%, and 26.78% for complexes (1), (2), and (3), respectively. However, for the complex (1)-PEI, complex (2)-PEI, and complex (3)-PEI, the total mass losses were 83.12%, 81.88%, and 35.78%, respectively. The synthetic compounds were additionally utilized for the adsorption of Naphthol blue black B from water. At optimum adsorption conditions (T = 20 °C, time = 60 min, pH = 5), the highest adsorption capacities were 154 mg/g, 139 mg/g, and 119 mg/g for complex (3)-PEI, complex (2)-PEI, and complex (1)-PEI, respectively. The adsorption mechanism followed the pseudo second order, the Freundlich, and the Temkin models. The results indicated that the adsorption process is reliant on chemical interactions. It was also governed by intraparticular diffusion and other kinetic phenomena. Full article
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16 pages, 2562 KiB  
Article
Metal Recovery from Discarded Lithium-Ion Batteries by Bioleaching Coupled with Minimal Mechanical Pre-Treatment
by Lidia Garcia, Joan Morell, Conxita Lao, Montserrat Solé-Sardans and Antonio D. Dorado
Minerals 2025, 15(6), 566; https://doi.org/10.3390/min15060566 - 26 May 2025
Viewed by 904
Abstract
The rising demand for lithium-ion batteries (LIBs), driven by the growing consumption of electronic devices and the expansion of electric vehicles, is leading to a concerning depletion of primary metal resources and a significant accumulation of electronic waste. This urgent challenge highlights the [...] Read more.
The rising demand for lithium-ion batteries (LIBs), driven by the growing consumption of electronic devices and the expansion of electric vehicles, is leading to a concerning depletion of primary metal resources and a significant accumulation of electronic waste. This urgent challenge highlights the need for sustainable recovery methods to extract valuable metals from spent LIBs, aligning with circular economy principles. In this study, the preparation of spent batteries for the bioleaching process was achieved with minimal manipulation. This included a preliminary discharge to ensure safety in subsequent processes and a brief crushing to facilitate the access of leaching agents to valuable metals. Unlike most studies that grind batteries to obtain powders between 70 and 200 microns, our approach works with particles sized around 5 mm. Additionally, our preparation process avoids any thermal or chemical treatments. This straightforward pre-treatment process marks a significant advancement by reducing the complexity and cost of processing. A systematic study was conducted on various fractions of the large particle sizes, using Fe (III) produced through bio-oxidation by A. ferrooxidans and biogenically obtained H2SO4 from A. thiooxidans. The highest metal extraction rates were achieved using the unsorted fraction, directly obtained from the black mass after the grinding process, without additional particle separation. When treated with bio-oxidized Fe (III), this fraction achieved a 95% recovery of Cu, Ni, and Al within 20 min, and over 90% recovery of Co, Mn, and Li within approximately 30 min. These recovery rates are attributed to the combined reducing power of Al and Cu already present in the black mass and the Fe (II) generated during the oxidation reactions of metallic Cu and Al. These elements actively facilitate the reduction of transition metal oxides into their more soluble, lower-valence states, enhancing the overall metal solubilization process. The extraction was carried out at room temperature in an acidic medium with a pH no lower than 1.5. These results demonstrate significant potential for efficient metal recovery from spent batteries with minimal pre-treatment, minimizing environmental impact. Additionally, the simplified residue preparation process can be easily integrated into existing waste management facilities without the need for additional equipment. Full article
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26 pages, 6337 KiB  
Article
Facile Synthesis and Characterization of Novel Analcime@Calcium Aluminate@Polyethylene Glycol 400 Nanocomposite for Efficient Removal of Zn(II) Ions from Aqueous Media
by Ehab A. Abdelrahman, Abdulrahman G. Alhamzani, Mortaga M. Abou-Krisha, Fawaz A. Saad and Abdalla M. Khedr
Inorganics 2025, 13(5), 174; https://doi.org/10.3390/inorganics13050174 - 20 May 2025
Viewed by 831
Abstract
Excessive Zn(II) ions in aquatic environments pose significant risks to both human health and ecological systems due to their toxic effects, bioaccumulation potential, and interference with essential biological processes. To address this issue, a novel analcime@calcium aluminate@polyethylene glycol 400 (ACP) nanocomposite was fabricated [...] Read more.
Excessive Zn(II) ions in aquatic environments pose significant risks to both human health and ecological systems due to their toxic effects, bioaccumulation potential, and interference with essential biological processes. To address this issue, a novel analcime@calcium aluminate@polyethylene glycol 400 (ACP) nanocomposite was fabricated using the hydrothermal technique, alongside an analcime@calcium aluminate (AC) nanocomposite for the efficient elimination of Zn(II) ions from aqueous media. X-ray diffraction (XRD) analysis affirmed the successful formation of crystalline phases, revealing average crystallite sizes of 72.93 nm for AC and 63.60 nm for ACP. Energy-dispersive X-ray spectroscopy (EDX) confirmed the elemental composition of the nanocomposites, showing that AC primarily contained oxygen, sodium, aluminum, silicon, and calcium, whereas ACP incorporated 19.3% carbon due to the polyethylene glycol 400. Field emission scanning electron microscopy (FE-SEM) revealed that AC exhibited hexagonal and platelet-like structures, whereas ACP displayed more dispersed and layered morphologies. High-resolution transmission electron microscopy (HR-TEM) confirmed the presence of stacked platelet-like structures in AC and more defined, separated nanosheets in ACP. The maximum adsorption capacities of AC and ACP were 149.93 and 230.95 mg/g, respectively. The adsorption pathway of Zn(II) ions onto ACP nanocomposite involved three primary interactions: electrostatic attraction facilitated by calcium aluminate, ion exchange provided by analcime, and complexation promoted by polyethylene glycol 400. Thermodynamic analysis indicated that the adsorption process was exothermic, spontaneous, and primarily chemical in nature. Kinetic modeling confirmed that adsorption followed the pseudo-second-order model, while isotherm studies demonstrated adherence to the Langmuir model, indicating monolayer adsorption on homogeneous sites. Full article
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21 pages, 3742 KiB  
Article
Mixed 3d-3d’-Metal Complexes: A Dicobalt(III)Iron(III) Coordination Cluster Based on Pyridine-2-Amidoxime
by Sotiris G. Skiadas, Christina D. Polyzou, Zoi G. Lada, Rodolphe Clérac, Yiannis Sanakis, Pierre Dechambenoit and Spyros P. Perlepes
Inorganics 2025, 13(5), 171; https://doi.org/10.3390/inorganics13050171 - 17 May 2025
Viewed by 1018
Abstract
In the present work, we describe the use of the potentially tridentate ligand pyridine-2-amidoxime (NH2paoH) in Fe-Co chemistry. The 1:1:3 FeIII(NO3)3·9H2O/CoII(ClO4)2·6H2O/NH2paoH reaction mixture [...] Read more.
In the present work, we describe the use of the potentially tridentate ligand pyridine-2-amidoxime (NH2paoH) in Fe-Co chemistry. The 1:1:3 FeIII(NO3)3·9H2O/CoII(ClO4)2·6H2O/NH2paoH reaction mixture in MeOH gave complex [CoIII2FeIII(NH2pao)6](ClO4)2(NO3) (1) in ca. 55% yield, the cobalt(II) being oxidized to cobalt(III) under the aerobic conditions. The same complex was isolated using cobalt(II) and iron(II) sources, the oxidation now taking place at both metal sites. The structure of 1 contains two structurally similar, crystallographically independent cations [CoIII2FeIII(NH2pao)6]3+ which are strictly linear by symmetry. The central high-spin FeIII ion is connected to each of the terminal low-spin CoIII ions through the oximato groups of three 2.1110 (Harris notation) NH2pao ligands, in such a way that the six O atoms are bonded to the octahedral FeIII center ({FeIIIO6} coordination sphere). Each terminal octahedral CoIII ions is bonded to six N atoms (three oximato, three 2-pyridyl) from three NH2pao groups ({CoIIIN6} coordination sphere). The IR and Raman spectra of the complex are discussed in terms of the coordination mode of the organic ligand, and the non-coordinating nature of the inorganic ClO4 and NO3 counterions. The UV/VIS spectrum of the complex in EtOH shows the two spin-allowed d-d transitions of the low-spin 3d6 cobalt(III) and a charge-transfer NH2pao → FeIII band. The δ and ΔΕQ 57Fe-Mössbauer parameter of 1 at 80 K show the presence of an isolated high-spin FeIII center. Variable-temperature (1.8 K–300 K) and variable-field (0–7 T) magnetic studies confirm the isolated character of FeIII. A critical discussion of the importance of NH2paoH and its anionic forms (NH2pao, NHpao2−) in homo- and heterometallic chemistry is also attempted. Full article
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18 pages, 2959 KiB  
Article
Evaluating Performance of Metal-Organic Complexes as Electrodes in Hydrogen Peroxide Fuel Cells
by Faraz Alderson, Raveen Appuhamy and Stephen Andrew Gadsden
Energies 2025, 18(10), 2598; https://doi.org/10.3390/en18102598 - 17 May 2025
Viewed by 346
Abstract
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 [...] Read more.
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 article belongs to the Section D: Energy Storage and Application)
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31 pages, 3410 KiB  
Article
Novel 8-Hydroxyquinoline-Derived V(IV)O, Ni(II), and Fe(III) Complexes: Synthesis, Characterization, and In Vitro Cytotoxicity Against Tumor Cells
by Joana Lopes, Leonor Côrte-Real, Íris Neto, Alice Alborghetti, Maël Dejoux, Nora V. May, Xavier Fontrodona, Isabel Romero, Alexandra M. M. Antunes, Catarina Pinto Reis, Maria Manuela Gaspar and Isabel Correia
Inorganics 2025, 13(5), 150; https://doi.org/10.3390/inorganics13050150 - 6 May 2025
Viewed by 1104
Abstract
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 (L [...] Read more.
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
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