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20 pages, 4628 KiB  
Article
Achieving 3-D Structural Uniformity in Cellulose Gel Beads via Salt Screening
by Matthew T. Garnett, Seyed Armin Seyed Esfahani, Andrew P. Yingst, Luke T. May and Symone L. M. Alexander
Polymers 2024, 16(24), 3519; https://doi.org/10.3390/polym16243519 - 18 Dec 2024
Viewed by 358
Abstract
Cellulose microgel beads fabricated using the dropping technique suffer from structural irregularity and mechanical variability. This limits their translation to biomedical applications that are sensitive to variations in material properties. Ionic salts are often uncontrolled by-products of this technique, despite the known effects [...] Read more.
Cellulose microgel beads fabricated using the dropping technique suffer from structural irregularity and mechanical variability. This limits their translation to biomedical applications that are sensitive to variations in material properties. Ionic salts are often uncontrolled by-products of this technique, despite the known effects of ionic salts on cellulose assembly. In this study, the coagulation behavior of cellulose/salt solutions was explored as a way to combat these challenges. An ionic salt (NaCl) was added to a cellulose solution (cellulose/NaOH/urea) prior to coagulation in a hydrochloric acid bath. Quantification of the bead geometry and characterization of the pore architecture revealed that balancing the introduction of salt with the resultant solution viscosity is more effective at reducing structural variability and diffusion limitations than other pre-gelling techniques like thermal gelation. Three-dimensional visualization of the internal pore structure of neat cellulose, thermo-gel, and salt-gel beads revealed that adding salt to the solution is the most effective way to achieve 3-D structural uniformity throughout the bead. Coupled with nanoindentation, we confirmed that the salt produced during coagulation plays a critical role in mechanical variability, and that adding salt to the solution before dropping into the coagulation bath completely screens this effect, producing uniform microgel beads with reproducible mechanical properties. Full article
(This article belongs to the Special Issue Advanced Preparation and Application of Cellulose: 2nd Edition)
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Figure 1

Figure 1
<p>Cellulose microgel beads are formed using a dropping technique in a 2M HCl coagulation bath.</p>
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<p>(<b>a</b>) Computational heat maps were used to predict thermal gradients present in cellulose solutions over time as a function of bath temperature. A 25 °C water bath resulted in the lowest thermal gradient as a function of radial distance and time, indicating the least amount of thermal stress. (<b>b</b>) Experimental temperature vs. time data were used to validate the model (r = 0.00 m) and determine the time required to reach thermal equilibrium for water bath temperatures of 25, 45, and 65 °C. (<b>c</b>–<b>e</b>) Solutions were visually examined for signs of thermal stress (transition from colorless to yellow) and precipitation (transition from transparent to opaque). Signs of thermal stress increased as a function of bath temperature, with the 25 °C water bath (<b>c</b>) showing the least signs of thermal stress after 30 min compared to the 45 °C (<b>d</b>) and 65 °C (<b>e</b>) water baths.</p>
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<p>Electrophoretic mobility and dynamic viscosity were compared for a CNF solution and CNF suspensions. The presence of NaOH in solution leads to opposite trends for CNF suspensions. In DI water, the CNFs display a net negative charge that decreases as the salt concentration increases. In a NaOH/Urea solution, the CNFs display a net positive charge that becomes more negative as the salt concentration increases. Dissolved CNFs in a NaOH solution displayed an electrophoretic mobility near zero that became more negative as the salt concentration increased. Both of the CNF suspensions displayed negligible changes in viscosity as the salt concentration increased compared to the CNF solution. The electrophoretic mobility and viscosity of the suspensions and solutions were measured at 20 °C.</p>
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<p>(<b>a</b>) Neat cellulose, thermo-gel, and salt-gel beads were examined for tail formation using ImageJ. The red square indicates a bead with tail formation. Salt-gel beads had the lowest degree of tail formation compared to neat cellulose and thermo-gel beads. (<b>b</b>,<b>c</b>) The circularity of the thermo-gel beads slightly increased compared to that of the neat cellulose beads and had lower variability. The diameter of the thermo-gel beads was smaller than that of the neat cellulose beads. (<b>d</b>,<b>e</b>) Salt-gel beads with a salt concentration of 0.5 wt% did not improve bead geometry, while 1 and 2 wt% salt increased circularity and decreased variability compared to both neat cellulose and thermo-gel beads. A t-test was used to determine if there were significant differences between the diameter and circularity of neat and thermo-gel cellulose beads. A one-way ANOVA was used to determine if the means of the diameter and circularity were significantly different between the neat and salt-gel beads. *** <span class="html-italic">p</span> &lt; 0.001, **** <span class="html-italic">p</span> &lt; 0.0001, and no * = not significant.</p>
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<p>(<b>a</b>–<b>c</b>) Cross-sectional SEM images were taken of (<b>a</b>) neat (no pre-gel), (<b>b</b>) thermo-gel, and (<b>c</b>) salt-gel beads. SEM revealed that neat and thermo-gel beads had a tighter cellulose network that limited the diffusion of salt, while salt-gel beads had a larger network that allowed salt to diffuse and improve uniformity throughout the network. Neat cellulose and thermo-gel beads displayed a porosity of 54.62% and 53.09%, while the salt-gel beads displayed a porosity of 75.80%. All scale bars = 80 µm, corresponding to 2000X magnification. (<b>d</b>–<b>f</b>) 3-D nano-CT scans were taken of (<b>d</b>) neat (no pre-gel) cellulose, (<b>e</b>) thermo-gel, and (<b>f</b>) salt-gel beads fabricated in a 2M HCl coagulation bath. Nano-CT revealed that adding salt into the solution generated a uniform network structure throughout the bead. Access to 360° rotations for each bead are available in the <a href="#app1-polymers-16-03519" class="html-app">Supplementary Information</a>. All scale bars = 500 µm.</p>
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<p>Increasing the concentration of salt into solution prior to coagulation effectively screens the salt produced via the neutralization reaction and provides elasticity to the cellulose network. Neat and thermo-gel solutions have salt concentrations that cause competition between cellulose chains during aggregation due to the lack of salt screening effects. In contrast, introducing salt into solution helps avoid this problem and leads to more uniform beads with less structural variability.</p>
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<p>Nanoindentation was performed on (<b>a</b>) neat cellulose, (<b>b</b>) thermo-gel, and (<b>c</b>) salt-gel beads in a control (water), simulated gastric fluid (SGF), and simulated intestinal fluid (SIF) environment to compare the changes in Young’s moduli. The Young’s moduli of the neat cellulose, thermo-gel, and salt-gel beads were also compared to see if there were significant differences in the beads when subjected to (<b>d</b>) water, (<b>e</b>) SGF, and (<b>f</b>) SIF. Overall, salt-gel beads displayed lowest variability and lowest Young’s modulus compared to both thermo-gel and neat cellulose beads. (<b>a</b>–<b>c</b>) A one-way ANOVA was used to determine if the means of the three groups tested were significantly different. (<b>d</b>–<b>f</b>) A two-way ANOVA was used to determine if the means of the bead type and environment were statically significant. * <span class="html-italic">p</span> &lt; 0.05, *** <span class="html-italic">p</span> &lt; 0.001, **** <span class="html-italic">p</span> &lt; 0.0001, and no * = not significant.</p>
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18 pages, 3357 KiB  
Article
Deep Eutectic Solvent (TOPO/D2EHPA/Menthol) for Extracting Metals from Synthetic Hydrochloric Acid Leachates of NMC-LTO Batteries
by Arina V. Kozhevnikova, Nikita A. Milevskii, Dmitriy V. Lobovich, Yulia A. Zakhodyaeva and Andrey A. Voshkin
Metals 2024, 14(12), 1441; https://doi.org/10.3390/met14121441 - 16 Dec 2024
Viewed by 317
Abstract
The recycling of lithium-ion batteries is increasingly important for both resource recovery and environmental protection. However, the complex composition of cathode and anode materials in these batteries makes the efficient separation of metal mixtures challenging. Hydrometallurgical methods, particularly liquid extraction, provide an effective [...] Read more.
The recycling of lithium-ion batteries is increasingly important for both resource recovery and environmental protection. However, the complex composition of cathode and anode materials in these batteries makes the efficient separation of metal mixtures challenging. Hydrometallurgical methods, particularly liquid extraction, provide an effective means of separating metal ions, though they require periodic updates to their extraction systems. This study introduces a hydrophobic deep eutectic solvent composed of trioctylphosphine oxide, di(2-ethylhexyl)phosphoric acid, and menthol, which is effective for separating Ti(IV), Co(II), Mn(II), Ni(II), and Li+ ions from hydrochloric acid leachates of NMC (LiNixMnyCo1−x−yO2) batteries with LTO (Li4Ti5O12) anodes. By optimising the molar composition of the trioctylphosphine oxide/di(2-ethylhexyl)phosphoric acid/menthol mixture to a 4:1:5 ratio, high extraction efficiency was achieved. The solvent demonstrated stability over 10 cycles, and conditions for its regeneration were successfully established. At room temperature, the DES exhibited a density of 0.89 g/mL and a viscosity of 56 mPa·s, which are suitable for laboratory-scale extraction processes. Experimental results from a laboratory setup with mixer-settlers confirmed the efficiency of separating Ti(IV) and Co(II) ions in the context of their extraction kinetics. Full article
(This article belongs to the Section Extractive Metallurgy)
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<p>A photo and scheme of a laboratory installation in operation: <span class="html-italic">a</span>—raffinate solution, <span class="html-italic">b</span>—extract solution, <span class="html-italic">c</span>—initial solution with appropriate metal concentration and HCl, <span class="html-italic">d</span>—HDES, P—pump, E—extractor.</p>
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<p>Dependence of density (<b>a</b>) and dynamic viscosity (<b>b</b>) of the HDES composed of TOPO/D2EHPA/menthol in a 4:1:5 ratio on temperature.</p>
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<p>Dependence of the degree of extraction of metal ions on the menthol content in the HDES. HDES phase: χ<sub>TOPO</sub>/χ<sub>D2EHPA</sub> = 1:1. Aqueous phase: [HCl] = 8 mol/L; V<sub>aq</sub>/V<sub>HDES</sub> = 1/1; mixing time was 30 min.</p>
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<p>The dependence of the degree of extraction of metal ions on the content of TOPO and D2EHPA in the HDES. HDES phase: χ<sub>menthol</sub> = 4. Aqueous phase: [HCl] = 8 mol/L, 0.069 g/L Li, 0.589 g/L Co, 0.587 g/L Ni, 0.549 g/L Mn, and 0.479 g/L Ti; V<sub>aq</sub>/V<sub>HDES</sub> = 1/1; mixing time was 30 min.</p>
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<p>Dependence of the degree of metal ion extraction on the molar fraction of D2EHPA. Aqueous phase: [HCl] = 8 mol/L, 0.069 g/L Li, 0.589 g/L Co, 0.587 g/L Ni, 0.549 g/L Mn, and 0.479 g/L Ti. HDES phase: χ<sub>TOPO</sub> = 4; V<sub>aq</sub>/V<sub>HDES</sub> = 1/1; mixing time was 30 min.</p>
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<p>Dependence of the degree of extraction of metal ions on the phase contact time. HDES phase: TOPO/D2EHPA/menthol = 4:1:5. Aqueous phase: [HCl] = 6 mol/L, 0.069 g/L Li, 0.589 g/L Co, 0.587 g/L Ni, 0.549 g/L Mn, and 0.479 g/L Ti; V<sub>aq</sub>/V<sub>HDES</sub> = 1/1.</p>
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<p>The dependence of the degree of extraction of metal ions on the concentration of HCl. HDES phase: TOPO/D2EHPA/menthol = 4:1:5. Aqueous phase: 0.069 g/L Li, 0.589 g/L Co, 0.587 g/L Ni, 0.549 g/L Mn, and 0.479 g/L Ti; V<sub>aq</sub>/V<sub>HDES</sub> = 1/1; mixing time was 30 min.</p>
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<p>Dependence of the degree of extraction of metal ions on the volume ratio of the aqueous and organic phases. HDES phase: TOPO/D2EHPA/menthol = 4:1:5. Aqueous phase: 0.069 g/L Li, 0.589 g/L Co, 0.587 g/L Ni, 0.549 g/L Mn, and 0.479 g/L Ti; mixing time was 30 min.</p>
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<p>Isotherms of the Me extraction with TOPO/D2EHPA/menthol = 4:1:5. Aqueous phase: [HCl] = 1, 6, 9 mol/L for Ti(IV), Co(II), and Mn(II) ions, respectively; V<sub>aq</sub>/V<sub>HDES</sub> = 1/1; mixing time was 30 min.</p>
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<p>Dependence of the degree of stripping of Ti(IV), Co(II), and Mn(II) ions on the phase contact time. Extraction conditions for Ti(IV), Co(II), and Mn(II): [HCl] = 1, 6, and 9 mol/L, respectively. Stripping conditions for Ti(IV): [H<sub>3</sub>PO<sub>4</sub>] = 3 mol/L, 3 vol.% H<sub>2</sub>O<sub>2</sub>; for Co(II) and Mn(II): [HCl] = 1 mol/L.</p>
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<p>The possibility of the reuse of TOPO/D2EHPA/menthol 4:1:5. Conditions for the stripping of Ti(IV): [H<sub>3</sub>PO<sub>4</sub>] = 3 mol/L, 3 vol.% H<sub>2</sub>O<sub>2</sub>; Co(II) and Mn(II) ions: [HCl] = 1 mol/L.</p>
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<p>Dependence of the degree of extraction of metals from HCl 1 mol/L solution (<b>a</b>) and Co(II) and Mn(II) from HCl 6 mol/L solution (<b>b</b>) on the volume flow rate of the phases.</p>
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24 pages, 7747 KiB  
Article
Bio-Based Corrosion Inhibition of Carbon Steel Using Ammi visnaga L. Essential Oil in Acidic Mediums: Experimental Analysis and Molecular Modeling
by Aouatife Zaher, Hassane Lgaz, Asmaa Boukhraz, Ali Aldalbahi, Han-seung Lee, Brahim Bourkhiss and Mohammed Ouhssine
Coatings 2024, 14(12), 1556; https://doi.org/10.3390/coatings14121556 - 12 Dec 2024
Viewed by 440
Abstract
Bio-based corrosion inhibitor formulations are incredibly promising for mitigating corrosion, offering an environmentally sustainable approach while providing effective protection against material degradation. This study explores the corrosion inhibition potential of Ammi visnaga essential oil (AVEO) on carbon steel (CS) in a 1 mol/L [...] Read more.
Bio-based corrosion inhibitor formulations are incredibly promising for mitigating corrosion, offering an environmentally sustainable approach while providing effective protection against material degradation. This study explores the corrosion inhibition potential of Ammi visnaga essential oil (AVEO) on carbon steel (CS) in a 1 mol/L hydrochloric acid (HCl) medium, combining electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PDP), linear polarization resistance (LPR), weight loss (WL) analysis, density functional theory (DFT), density-functional tight-binding (DFTB) modeling, and molecular dynamics (MD) simulation. The AVEO was extracted through hydrodistillation, and its chemical profile was characterized to identify key active compounds. EIS and PDP results revealed that the AVEO effectively inhibited corrosion through the formation of a protective layer on the steel surface, exhibiting inhibition efficiencies of up to 84% at 3 g/L, with a mixed-type corrosion inhibition action. Nyquist plots displayed an increased polarization resistance with the AVEO concentration, indicating an enhanced surface coverage and reduction in active corrosion sites. WL studies further supported these findings, showing decreased corrosion rates proportional to the AVEO concentration, while temperature variation studies showed a decreased performance at higher temperatures. Scanning electron microscope (SEM) analysis supported the formation of an effective protective layer on the CS surface upon the addition of AVEO to the HCl medium. DFTB modeling and MD simulations were employed to evaluate the interaction between major AVEO constituents and the steel surface, providing insight into the adsorption behavior and the electronic contributions at the molecule–metal interface. The combined experimental and theoretical findings indicate that AVEO holds promise as a natural, eco-friendly corrosion inhibitor, with implications for sustainable metal protection in acidic environments. Full article
(This article belongs to the Special Issue Corrosion Protection of Metals and Alloys in Extreme Environments)
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Figure 1
<p>Gravimetric data for carbon steel in 1 mol/L HCl with and without different concentrations of AVEO at 303 K. Label (<b>a</b>) represents the variation of corrosion rate and inhibition efficiency as a function of AVEO concentration; label (<b>b</b>) represents the variation of corrosion rate and inhibition efficiency in absence and presence of 3 g/L AVEO as a function of temperature.</p>
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<p>Potentiodynamic polarization curves registered for CS in 1.0 mol/L HCl in the presence and absence of AVEO concentrations at 303 K.</p>
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<p>Electrochemical impedance results and electrical equivalent circuit used for fitting experimental data for carbon steel in 1.0 mol/L with and without AVEO concentration. Label (<b>a</b>–<b>c</b>) represent Nyquist plots, Bode modulus plots, and phase angle values as a function of AVEO concentration. Label (<b>d</b>) represents the equivalent circuit used to fit the experimental EIS data.</p>
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<p>SEM images for the corrosion inhibition of CS in 1.0 mol/L HCl (<b>a</b>) without and (<b>b</b>) with 3 g/L AVEO after 12 h immersion time.</p>
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<p>Frontier molecular orbitals HOMO and LUMO densities distributed over optimized AVEO major molecules along with HOMO, LUMO, and energy gap values.</p>
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<p>Optimized geometry of investigated molecules in label (<b>a</b>), while label (<b>b</b>) and (<b>c</b>) represent condensed Fukui functions <math display="inline"><semantics> <mrow> <msubsup> <mrow> <mi>f</mi> </mrow> <mrow> <mi>k</mi> </mrow> <mrow> <mo>−</mo> </mrow> </msubsup> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <msubsup> <mrow> <mi>f</mi> </mrow> <mrow> <mi>k</mi> </mrow> <mrow> <mo>+</mo> </mrow> </msubsup> </mrow> </semantics></math>, respectively.</p>
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<p>DFTB-optimized adsorption geometry of AVEO major molecules. Labels (<b>a</b>–<b>d</b>) refer to 2m2m, 2mI, LAI, and LIN, respectively. Bond distances are in Å.</p>
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<p>PDOS of s and p orbitals of AVEO’s major molecules and the 3d orbitals of Fe atoms at their isolated state, 6 Å far from the iron surface. Labels (<b>a</b>–<b>d</b>) refer to 2m2m, 2mI, LAI and LIN molecules, respectively.</p>
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<p>PDOS of s and p orbitals of AVEO’s major molecules and the 3d orbitals for Fe atoms at their adsorbed state. Labels (<b>a</b>–<b>d</b>) refer to 2m2m, 2mI, LAI and LIN molecules, respectively.</p>
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<p>Adsorption configurations of AVEO major molecules on Fe(110) surface obtained from MD simulations in presence of a simulated solution at 303 K. Labels (<b>a</b>–<b>d</b>) refer to 2m2m, 2mI, LAI, and LIN, respectively.</p>
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17 pages, 4418 KiB  
Article
Enrichment of Ginseng Rare Sapogenin 25-OH-PPT and Its Protective Effect on Myocardial Fibrosis
by Zixuan Jin, Yuemin Wu, Yanyan Zhang, Siqi Feng, Guotao Hu, Hairong Liu, Yuqing Zhao and Jing Xu
Molecules 2024, 29(23), 5813; https://doi.org/10.3390/molecules29235813 - 9 Dec 2024
Viewed by 422
Abstract
Ginseng (Panax ginseng C. A. Meyer), a traditional Chinese medicine, and the rare ginsenosides contained in it have various physiological activities. 25-OH-PPT (T19) is a rare natural dammarane-type ginseng sapogenin. Pharmacological studies have shown that T19 has good hypoglycemic, antioxidant, and anti-inflammatory [...] Read more.
Ginseng (Panax ginseng C. A. Meyer), a traditional Chinese medicine, and the rare ginsenosides contained in it have various physiological activities. 25-OH-PPT (T19) is a rare natural dammarane-type ginseng sapogenin. Pharmacological studies have shown that T19 has good hypoglycemic, antioxidant, and anti-inflammatory activities. In the research, we optimized the T19 enrichment process and explored the potential mechanism of T19 in myocardial oxidative stress. Firstly, we studied a hydrolysis process on ginseng stems and leaves ginsenosides. Optimization factors include acid types, acid concentrations, ultrasound time, and ultrasound temperature. To develop safer preparation conditions more suitable for production scaleup, we studied the difference in hydrolysis between inorganic acid and food acids. The results show that using hydrochloric acid to hydrolyze ginsenosides in ginseng stems and leaves can increase the content of T19 to 12.16%. When using edible citric acid, the maximum content of T19 is 1.9%. However, using citric acid for hydrolysis has higher safety and non-toxic properties. Meanwhile, the myocardial protective effect of T19 was evaluated, indicating that T19 could effectively reduce isoproterenol (ISO)-induced oxidative stress injury by reducing the levels of LDH and CK-MB and regulating the contents of antioxidant enzymes SOD, lipid peroxidation product MDA, and non-enzymatic antioxidant GSH in cardiomyocytes. Further study demonstrated that regulation of fibrosis markers Collagen I, Collagen III, and α-SMA was involved in the potential mechanism of T19 efficiency. Full article
(This article belongs to the Section Photochemistry)
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Figure 1
<p>Comparison of determination results for three strong acids of (<b>A</b>) hydrochloric acid; (<b>B</b>) sulfuric acid; and (<b>C</b>) phosphoric acid. ** <span class="html-italic">p</span> &lt; 0.01, *** <span class="html-italic">p</span> &lt; 0.001, vs. the lowest acid concentration group.</p>
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<p>Comparison of hydrolysis results for ginseng sapogenins under different conditions of (<b>A</b>) hydrochloric acid mass fraction; (<b>B</b>) hydrolysis time; and (<b>C</b>) hydrolysis temperature. ** <span class="html-italic">p</span> &lt; 0.01, *** <span class="html-italic">p</span> &lt; 0.001 vs. the lowest T19 content; <sup>#</sup> <span class="html-italic">p</span> &lt; 0.05, <sup>###</sup> <span class="html-italic">p</span> &lt; 0.001 vs. the lowest PPT content; <sup>^^</sup> <span class="html-italic">p</span> &lt; 0.01, <sup>^^^</sup> <span class="html-italic">p</span> &lt; 0.001 vs. the lowest PT content; <sup>&amp;&amp;</sup> <span class="html-italic">p</span> &lt; 0.01, <sup>&amp;&amp;&amp;</sup> <span class="html-italic">p</span> &lt; 0.001 vs. the lowest T16 content.</p>
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<p>Comparison of hydrolysis results for ginseng sapogenins under different conditions of (<b>A</b>) hydrochloric acid mass fraction; (<b>B</b>) hydrolysis time; and (<b>C</b>) hydrolysis temperature. ** <span class="html-italic">p</span> &lt; 0.01, *** <span class="html-italic">p</span> &lt; 0.001 vs. the lowest T19 content; <sup>#</sup> <span class="html-italic">p</span> &lt; 0.05, <sup>###</sup> <span class="html-italic">p</span> &lt; 0.001 vs. the lowest PPT content; <sup>^^</sup> <span class="html-italic">p</span> &lt; 0.01, <sup>^^^</sup> <span class="html-italic">p</span> &lt; 0.001 vs. the lowest PT content; <sup>&amp;&amp;</sup> <span class="html-italic">p</span> &lt; 0.01, <sup>&amp;&amp;&amp;</sup> <span class="html-italic">p</span> &lt; 0.001 vs. the lowest T16 content.</p>
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<p>Comparison of determination results for (<b>A</b>) succinic acid molarity; (<b>B</b>) malic acid molarity; (<b>C</b>) tartaric acid molarity; and (<b>D</b>) citric acid molarity. ** <span class="html-italic">p</span> &lt; 0.01, *** <span class="html-italic">p</span> &lt; 0.001 vs. the lowest acid concentration group.</p>
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<p>Comparison of determination results for four acids of (<b>A</b>) reaction time and (<b>B</b>) reaction temperature. ** <span class="html-italic">p</span> &lt; 0.01, *** <span class="html-italic">p</span> &lt; 0.001 vs. the lowest T19 content in succinic acid hydrolysis; <sup>###</sup> <span class="html-italic">p</span> &lt; 0.001 vs. the lowest T19 content in malic acid hydrolysis; <sup>^</sup> <span class="html-italic">p</span> &lt; 0.05, <sup>^^^</sup> <span class="html-italic">p</span> &lt; 0.001 vs. the lowest T19 content in tartaric acid hydrolysis; <sup>&amp;</sup> <span class="html-italic">p</span> &lt; 0.05, <sup>&amp;&amp;</sup> <span class="html-italic">p</span> &lt; 0.01, <sup>&amp;&amp;&amp;</sup> <span class="html-italic">p</span> &lt; 0.001 vs. the lowest T19 content in citric acid hydrolysis.</p>
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<p>Molecular docking showed the direct binding analysis of T19 to its potential target proteins (<b>A</b>) alpha-smooth muscle actin (α-SMA, UniProt ID: P62736); (<b>B</b>) Collagen alpha-1 (I) chain (Collagen I, UniProt ID: P02452); and (<b>C</b>) Collagen alpha-1 (III) chain (Collagen III, UniProt ID: P02461).</p>
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<p>H9c2 cardiomyocyte survival rate measured by MTT assay: (<b>A</b>) effect of T19 on H9c2 cell survival rate; (<b>B</b>) effect of ISO on H9c2 cell survival rate at 24 h and 48 h (<span class="html-italic">n</span> = 3, mean ± SD; <sup>###</sup> <span class="html-italic">p</span> &lt; 0.001; * compared with the 24 h group, *** <span class="html-italic">p</span> &lt; 0.001); and (<b>C</b>) effect of T19 on ISO-induced H9c2 cell survival rate (<span class="html-italic">n</span> = 3, mean ± SD; <sup>###</sup> <span class="html-italic">p</span> &lt; 0.001; <span class="html-small-caps">*</span> compared with the model group, * <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01, *** <span class="html-italic">p</span> &lt; 0.001).</p>
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<p>Effect of T19 on the activity of LDH and CK-MB enzymes in ISO-induced H9c2 cardiomyocytes: (<b>A</b>) LDH and (<b>B</b>) CK-MB (<span class="html-italic">n</span> = 3, mean ± SD; <sup>###</sup> <span class="html-italic">p</span> &lt; 0.001; * compared with the model group, * <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01, *** <span class="html-italic">p</span> &lt; 0.001).</p>
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<p>Effect of T19 on oxidative stress levels in ISO-induced H9c2 cardiomyocytes: (<b>A</b>) SOD; (<b>B</b>) GSH; and (<b>C</b>) MDA (<span class="html-italic">n</span> = 3, mean ± SD, <sup>###</sup> <span class="html-italic">p</span> &lt; 0.001; * compared with the model group, * <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01, *** <span class="html-italic">p</span> &lt; 0.001).</p>
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<p>Protein expression of fibrosis markers in ISO-induced cardiomyocytes by T19 (<span class="html-italic">n</span> = 3, mean ± SD, <sup>###</sup> <span class="html-italic">p</span> &lt; 0.001; * compared with the model group, * <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01, *** <span class="html-italic">p</span> &lt; 0.001).</p>
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<p>mRNA expression of fibrosis markers in ISO-induced cardiomyocytes by T19 (<span class="html-italic">n</span> = 3, mean ± SD, <sup>##</sup> <span class="html-italic">p</span> &lt; 0.01, <sup>###</sup> <span class="html-italic">p</span> &lt; 0.001; * compared with the model group, * <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01, *** <span class="html-italic">p</span> &lt; 0.001).</p>
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<p>Chemical structures of four ginseng sapogenins.</p>
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21 pages, 5867 KiB  
Article
Assessing the Photocatalytic Degradation of Penconazole on TiO2 in Aqueous Suspensions: Mechanistic and Ecotoxicity Studies in Aerated and Degassed Systems
by Ákos Székely, Erzsébet Szabó-Bárdos, Orsolya Fónagy and Ottó Horváth
Catalysts 2024, 14(12), 898; https://doi.org/10.3390/catal14120898 - 7 Dec 2024
Viewed by 474
Abstract
Penconazole (C12H15Cl2N3) is widely used to prevent fungal infection of fruits. Since this toxic fungicide is recalcitrant to biological degradation, it has harmful impacts on aquatic ecosystems. TiO2-based heterogeneous photocatalysis proved to be [...] Read more.
Penconazole (C12H15Cl2N3) is widely used to prevent fungal infection of fruits. Since this toxic fungicide is recalcitrant to biological degradation, it has harmful impacts on aquatic ecosystems. TiO2-based heterogeneous photocatalysis proved to be an efficient method for its mineralization. To monitor the processes occurring under the influence of illumination, the light absorbance, the pH, and the TOC of the samples were measured. The concentration of the model compound and the degradation products were determined by HPLC and IC. Penconazole did not decompose under UV light (λmax = 371 nm) without a catalyst. In the presence of TiO2, mineralization took place. The initial degradation rate in air (7.7 × 10−4 mM s−1) was 5 times higher than under argon. The formation rate of hydrochloric acid (1.04 × 10−3 mM s−1) in the former case significantly contributed to the acidification of the liquid phase. NH4+ also formed, at the rate of 5.9 × 10−4 mM s−1, and very slightly transformed to NO3. Due to the intermediates identified by HPLC-MS, hydroxylation, H abstraction, and Cl elimination are involved in the degradation mechanism, in which photogenerated HO radicals, conduction-band electrons, and (under air) superoxide radical anions (O2●−) play considerable roles. The intermediates proved to be much less toxic than penconazole. Full article
(This article belongs to the Special Issue Commemorative Special Issue for Prof. Dr. David Ollis)
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<p>Structural formula of penconazole.</p>
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<p>Variation in light absorption at 220 nm during adsorption–desorption equilibrium.</p>
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<p>Changes in light absorption for UV and Vis photocatalysis at 220 nm.</p>
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<p>Comparison of TOC results in heterogeneous photocatalytic experiments with UV and Vis light.</p>
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<p>Changes with time accompanying the degradation of penconazole by UV heterogeneous photocatalysis in an argon atmosphere.</p>
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<p>Changes as a function of time accompanying the degradation of penconazole in a UV heterogeneous photocatalysis process in an air atmosphere.</p>
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<p>Changes in chloride ion (<b>a</b>) and nitrate ion (<b>b</b>) concentrations during experiments in air atmosphere.</p>
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<p>Comparison of changes in H<sup>+</sup> ion and inorganic ion concentrations during illumination in an aerated system.</p>
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<p>Ammonia concentration changes during photocatalysis in air and argon atmospheres.</p>
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<p>Comparison of ammonium ion and nitrate ion concentrations.</p>
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<p>Nitrogen balance during photocatalysis in the presence of air.</p>
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<p>Changes in light absorption during photocatalysis in (<b>a</b>) air and (<b>b</b>) argon.</p>
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<p>Variation in light absorption in the 250–320 nm range during photocatalysis in (<b>a</b>) air and (<b>b</b>) argon.</p>
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<p>Variation in light absorption at typical wavelengths in (<b>a</b>) air and (<b>b</b>) argon.</p>
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<p>Variation in carbon-containing intermediate concentrations with time in (<b>a</b>) air and (<b>b</b>) argon.</p>
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<p>Simplified scheme for the degradation routes of penconazole in TiO<sub>2</sub>-based photocatalysis in aerated system.</p>
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<p>Variation in toxicity of samples treated under different conditions.</p>
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<p>Experimental setup with UV (<b>a</b>) and Vis (<b>b</b>) light sources.</p>
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<p>A simplified mechanism for the photocatalytic degradation of penconazole (PEN) on TiO<sub>2</sub>.</p>
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15 pages, 2830 KiB  
Article
Characterizations of Pectin from Choerospondias axillaris Fruit Pulp: Comparison of Different Extraction Methods
by Zian Luyang, Zhibin Bu, Jijun Wu, Yuanshan Yu, Lina Cheng, Jian Peng and Yujuan Xu
Foods 2024, 13(23), 3920; https://doi.org/10.3390/foods13233920 - 4 Dec 2024
Viewed by 426
Abstract
Generally, the extraction method has a great influence on the quality of pectin. However, there is little study on the effect of extraction method on the properties of Choerospondias axillaris fruit pulp pectin (CAPP). Accordingly, the physicochemical, structural, and functional properties of CAPP [...] Read more.
Generally, the extraction method has a great influence on the quality of pectin. However, there is little study on the effect of extraction method on the properties of Choerospondias axillaris fruit pulp pectin (CAPP). Accordingly, the physicochemical, structural, and functional properties of CAPP extracted by hot water (HWE), hydrochloric acid (HAE), ultrasound (UAE), and ultrahigh pressure (UPE) were investigated. Among these four CAPPs, UPE had the highest yield (15.79%) and GalA content (60.44%). UAE showed the most abundant side chains and RG-I region (55.12%). The lowest molecular weight (233.13 kDa) and yield (8.64%) were found in HAE. Though HWE exhibited better yield than HAE, its Mw was the highest. Different from physicochemical characteristics, the extraction method had a small effect on the structure of CAPP. The crystalline structure and functional group composition of different CAPPs were similar, while the surface structure of UAE and UPE had irregular circular holes in comparison with HWE and HAE. Furthermore, the extraction method also showed a great impact on the function. Compared with HWE and HAE, UAE and UPE presented better thermal stability and emulsifying properties. Meanwhile, HAE and UAE showed better antioxidant ability and prebiotic properties among these four CAPPs. The above results indicated that UAE showed better yield and functional properties. Hence, ultrasound extraction could be used as an effective method to extract CAPP. Full article
(This article belongs to the Section Food Engineering and Technology)
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<p>Extraction yield (<b>A</b>), DE (<b>A</b>), monosaccharide composition (<b>A</b>), and molecular features (<b>B</b>) of CAPP. In each figure, different letters represent significant differences (<span class="html-italic">p</span> &lt; 0.05).</p>
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<p>XRD spectra (<b>A</b>) and FTIR spectra (<b>B</b>), and SEM images (<b>C</b>) of CAPP.</p>
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<p>TGA curves (<b>A</b>) and DTG curves (<b>B</b>) of CAPP.</p>
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<p>The storage stability (<b>A</b>), EA (<b>B</b>), ES (<b>B</b>), particle size (d<sub>3,2</sub>) (<b>C</b>), and zeta potential (<b>C</b>) of CAPP. In each figure, different letters represent significant differences (<span class="html-italic">p</span> &lt; 0.05).</p>
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<p>The antioxidant capacity and prebiotic activity of CAPP. ABTS radical scavenging activity (<b>A</b>), ferric reducing antioxidant capacity (<b>B</b>), viable counts of <span class="html-italic">L. plantarum</span> (<b>C</b>), viable counts of <span class="html-italic">L. fermentum</span> (<b>D</b>), and viable counts of <span class="html-italic">L. rhamnosus</span> (<b>E</b>). In each figure, different letters represent significant differences (<span class="html-italic">p</span> &lt; 0.05).</p>
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14 pages, 1434 KiB  
Article
Carbon Dioxide-Based Neutralization of High-Density Sludge Effluents as a Sustainable Climate and Water Quality Alternative to the Use of Strong Mineral Acids
by Julio C. Gastañadui-Cruz, Iván A. Reyes-Lopez, Agusberto Cortijo-Garcia, Hans R. Portilla-Rodriguez, John A. Bush, Johan Vanneste and Pablo A. Garcia-Chevesich
Sustainability 2024, 16(23), 10363; https://doi.org/10.3390/su162310363 - 27 Nov 2024
Viewed by 483
Abstract
The neutralization of high-density sludge (HDS) effluent is a required process involved in the treatment of acid mine drainage (AMD). In their last treatment stage, effluents with high pH values are acidified to reach legal standards before being released to the environment using [...] Read more.
The neutralization of high-density sludge (HDS) effluent is a required process involved in the treatment of acid mine drainage (AMD). In their last treatment stage, effluents with high pH values are acidified to reach legal standards before being released to the environment using hydrochloric or sulfuric acid. In this investigation, CO2 was tested as an alternative way to decrease the pH of the HDS effluent, together with an economic analysis comparing the results with the use of strong mineral acids, considering a full-scale 300 m3/h plant. HDS samples were collected from a PAN American Silver operation in Cajamarca, northern Peru. Four acidification tests were carried out on 20 L containers, with a subsequent evaluation of reaction time and CO2 consumption to regulate the final pH of the treated solution. The results suggest that by adding CO2 (0.5 L/min) to the solution, the pH was successfully decreased from 10–10.5 to 6.5–7.5 (which falls within the legal limits) in a matter of minutes. An average of 130 g of CO2 was sequestrated per m3 of solution to decrease the pH within legal limits, representing around USD 0.031/m3 in terms of treatment cost for a full-scale plant. While this is more expensive than using other acids, with a CO2 credit of USD 100/ton, sequestrated CO2 neutralization is 12% cheaper and only 6% more expensive than using H2SO4 and HCl, respectively. Moreover, in terms of the costs per ton of avoided CO2 of USD 133 and USD 262 for replacing hydrochloric and sulfuric acid, respectively, it is markedly lower than the cost of other CO2 abatement technologies, like, for instance, solar photovoltaic panels (PV) that can cost between USD 368 and USD 684/ton of avoided CO2 in Peru and require substantial capital investments. Moreover, the use of CO2 implicates a series of additional safety, operational, and environmental advantages that should be considered. Therefore, the use of CO2 to decrease HDS effluent’s pH should be further explored in Peru and elsewhere as a sustainable alternative. Full article
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<p>Map of Peru (red color in South America) and the location of the study site (blue dot) within the Department of Cajamarca. Source: Wikipedia under Creative Commons License (Genérica de Atribución/Compartir-Igual 3.0). Available at: <a href="https://es.m.wikipedia.org/wiki/Archivo:Peru_location_map.svg" target="_blank">https://es.m.wikipedia.org/wiki/Archivo:Peru_location_map.svg</a> (accessed on 12 October 2024).</p>
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<p>Mass balance of the operation (courtesy of Julio César Gastañadui-Cruz, co-author).</p>
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<p>Graphical representation of the four tests to lower AMD’s pH over time using CO<sub>2</sub>, with S1, S2, S3, and S4 collected water samples.</p>
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15 pages, 3908 KiB  
Article
Mechanism and Experimental Study on the Recovery of Rare Earth Elements from Neodymium Iron Boron Waste Using the ZnF2 Fluorination Method
by Youwei Liu, Yuan Zhong, Xiang Lei and Jinliang Wang
Materials 2024, 17(23), 5807; https://doi.org/10.3390/ma17235807 - 27 Nov 2024
Viewed by 424
Abstract
We conducted a mechanistic and experimental study on zinc fluoride roasting for the recovery of NdFeB waste to address the difficulties faced during this pyrometallurgical recovery process, such as the high dependence on the quality of raw materials, the high energy consumption involved [...] Read more.
We conducted a mechanistic and experimental study on zinc fluoride roasting for the recovery of NdFeB waste to address the difficulties faced during this pyrometallurgical recovery process, such as the high dependence on the quality of raw materials, the high energy consumption involved in roasting transformations, and the low added value of mixed rare earth products. Thermodynamic calculations showed the feasibility of fluorinating rare earths in NdFeB waste, and one-factor experiments were performed. The results showed that at a roasting temperature of 850 °C, a reaction time of 90 min, and 100% ZnF2 addition, the fluorination rate of rare earths could reach 95.69%. In addition, after analyzing the mesophase composition of a clinker under different roasting temperature conditions, it was found that, when the roasting temperature exceeded 850 °C, the fluorination rate of rare earths was reduced, which was consistent with the thermodynamic results. On this basis, response surface methodology (RSM) was used to carry out experiments to investigate in depth the effects of various factors and their interactions on the fluorination rate of rare earths, which provides a sufficient experimental basis for the recovery of NdFeB waste via fluorination roasting. The results of this study show that ZnF2 addition had the greatest influence on the rare earth fluorination reaction, followed by roasting temperature and roasting time. According to the optimization results of the model, the optimal roasting conditions were determined as follows: 119% ZnF2 addition at 828 °C, a roasting time of 91 min, and a rare earth element fluorination rate of 97.29%. The purity of the mixed fluorinated rare earths was as high as 98.92% after leaching the roasted clinker with 9 M hydrochloric acid at a leaching temperature of 80 °C, a liquid–solid ratio of 4 mL/g, and a leaching time of 2.5 h. This study will lay the foundation for promoting the application of pyrometallurgical technology in the recycling of NdFeB waste. Full article
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<p>XRD pattern of NdFeB waste.</p>
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<p>Plot of the reaction <math display="inline"><semantics> <mrow> <msubsup> <mrow> <mi mathvariant="sans-serif">Δ</mi> <mi>G</mi> </mrow> <mrow> <mi>T</mi> </mrow> <mrow> <mi>θ</mi> </mrow> </msubsup> </mrow> </semantics></math> versus T for the roasting process.</p>
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<p>(<b>a</b>) Effect of the ZnF<sub>2</sub>-to-raw material mass ratio on rare earth element fluorination rate; (<b>b</b>) XRD spectra of the clinker with different ZnF<sub>2</sub> dosages.</p>
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<p>(<b>a</b>) Effect of roasting temperature on rare earth element fluorination rate; (<b>b</b>) XRD spectra of the clinker with different roasting temperatures.</p>
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<p>(<b>a</b>) Effect of roasting time on leaching; (<b>b</b>) XRD spectra of the clinker with different roasting times.</p>
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<p>Comparison between predicted and actual values of rare earth element fluorination rates.</p>
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<p>Surface plot of the response of the interaction between different factors on the rare earth element fluorination rate: (<b>a</b>) roasting temperature and roasting time, (<b>b</b>) roasting temperature and mass ratio of ZnF<sub>2</sub> to raw material, and (<b>c</b>) mass ratio of ZnF<sub>2</sub> to raw material and roasting time.</p>
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<p>XRD graph of leached products.</p>
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<p>Scanning electron microscope images of the leachate product at different scales: (<b>a</b>) 1 µm; (<b>b</b>) 500 nm; (<b>c</b>) 200 nm; (<b>d</b>) 100 nm.</p>
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<p>Process flow for recovering rare earths from NdFeB waste through the fluorination reaction.</p>
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22 pages, 3999 KiB  
Article
Leather Waste Hydrolysation, Carbonization, and Microbial Treatment for Nitrogen Recovery by Ryegrass Cultivation
by Ksawery Kuligowski, Dawid Skrzypczak, Katarzyna Mikula, Katarzyna Chojnacka, Paulina Bandrów, Robert Tylingo, Szymon Mania, Adrian Woźniak and Adam Cenian
Materials 2024, 17(23), 5741; https://doi.org/10.3390/ma17235741 - 23 Nov 2024
Viewed by 605
Abstract
Leather waste contains up to 10% nitrogen (N); thus, combustion or gasification only for the energy recovery would not be rational, if safety standards are met. On the other hand, the chromium (Cr) content exceeding 5% in half of the waste stream ( [...] Read more.
Leather waste contains up to 10% nitrogen (N); thus, combustion or gasification only for the energy recovery would not be rational, if safety standards are met. On the other hand, the chromium (Cr) content exceeding 5% in half of the waste stream (w/w) is too significant to be applied in agriculture. In this work, four acid hydrolysates from leather waste shavings, both wet-white free of Cr and wet-blue with Cr, were used: two with a mixture of acids and supplemented with Cu, Mn, and Zn, and the other two as semi-products from collagen extraction using hydrochloric acid. Additionally wet-green leather waste shavings, e.g., impregnated with olive extract, were used followed by the two treatments: amendment with a biochar from “wet white” leather waste shavings and amendment with this biochar incubated with the commercial phosphorus stimulating microbial consortia BactoFos. They were applied as organic nitrogen-based fertilizers in a glasshouse experiment, consisting of 4–5 subsequent harvests every 30 days, under spring–autumn conditions in northern Poland. Biochar-amended wet-greens provided the highest nitrogen use efficiencies, exceeding 100% after 4 months of growth (for 20 kg N/ha) and varying from 17% to 37% in particular months. This is backed up by another parameter (relative agronomic effectiveness) that for these materials exceeded 150% for a single month and in total was around 33%. Biochar amendments significantly increased agronomic parameters for wet-greens, and their microbial treatment enhanced them even further. Recycling this type of waste can replace inorganic fertilizers, reducing greenhouse gas emissions and carbon footprint. Full article
(This article belongs to the Special Issue Current Approaches to Biomass Waste Material Utilization)
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<p>Ryegrass biomass yields response (<b>left</b>) and nitrogen uptake (<b>right</b>) to tanned-leather-waste-based fertilizers after 4 subsequent harvests, as compared to the mineral fertilizer (MF) for harvests after 30, 60, 90, and 120 days.</p>
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<p>Ryegrass growth (as total dry matter yield) dynamics across four harvests for 7 treatments, mineral fertilizer, and a control: percentage of total dry matter and absolute values in each harvest (<b>bars</b>) and total cumulative dry matter in all the harvests (<b>black line</b>).</p>
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<p>Nitrogen utilization by ryegrass grown on soil amended with tanned-leather-waste-based fertilizers after 4 subsequent harvests, as compared to the mineral fertilizer (MF) for harvests after 30, 60, 90, and 120 days.</p>
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<p>Nitrogen utilization (as total amount per single treatment in kg/ha) dynamics across four harvests for 7 treatments, mineral fertilizer, and a control: percentage of N utilization in each harvest and absolute values (<b>bars</b>) and total cumulative N utilization in all the harvests (<b>black line</b>).</p>
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<p>Ryegrass dry matter yields (<b>left</b>), nitrogen uptake (<b>middle</b>), and nitrogen utilization (<b>right</b>) after an additional harvest (150 days) for 4 chosen treatments and mineral fertilizer.</p>
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<p>Cumulative ryegrass dry matter yields (<b>left</b>) and nitrogen utilization (<b>right</b>) for 7 chosen treatments and mineral fertilizer.</p>
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<p>Relative agronomic effectiveness comparison for the processed leather waste fractions across harvests includingdata from 2021.</p>
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<p>Nitrogen use efficiency (NUE) for the processed leather waste fractions across harvests (from 30 to 150 days) and cumulative values after 120 days.</p>
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<p>Soil physical properties after 120 days of growth.</p>
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17 pages, 2647 KiB  
Article
Biopharmaceutical Characterization and Stability of Nabumetone–Cyclodextrins Complexes Prepared by Grinding
by David Klarić, Željka Soldin, Anna Vincze, Rita Szolláth, György Tibor Balogh, Mario Jug and Nives Galić
Pharmaceutics 2024, 16(12), 1493; https://doi.org/10.3390/pharmaceutics16121493 - 21 Nov 2024
Viewed by 674
Abstract
Background: Nabumetone (NAB) is a poorly soluble nonsteroidal anti-inflammatory prodrug (BCS class II drug) whose solubility is significantly improved by complexation with cyclodextrins (CDs). Methods: The solid complexes, in a 1:1 molar ratio, were prepared by mechanochemical activation by grinding, using β-cyclodextrin [...] Read more.
Background: Nabumetone (NAB) is a poorly soluble nonsteroidal anti-inflammatory prodrug (BCS class II drug) whose solubility is significantly improved by complexation with cyclodextrins (CDs). Methods: The solid complexes, in a 1:1 molar ratio, were prepared by mechanochemical activation by grinding, using β-cyclodextrin (β-CD) and its derivatives, hydroxypropyl- and sulfobutylether-β-cyclodextrin (HP-β-CD and SBE-β-CD). The complexation was confirmed by differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), and attenuated total reflectance Fourier-transformed infrared spectroscopy (ATR–FTIR). Obtained products were further characterized regarding their solubility, in vitro dissolution, permeability and chemical stability. Results: Co-grinding with HP-β-CD and SBE-β-CD yielded products that showed in vitro dissolution profiles in hydrochloric acid medium (pH 1.2) that were substantially different from that of pure NAB, yielding dissolution efficiency enhancements of 34.86 ± 1.64 and 58.30 ± 0.28 times, respectively, for the optimized products. Their in vitro dissolution and gastrointestinal permeability were also studied in a low-volume environment at pH 6.8, corresponding to the intestinal environment. Both β-CD derivatives increased NAB dissolution rate and NAB mass transport across the biomimetic membrane. The effect of β-CD derivatives on NAB chemical stability was studied under the stress conditions by the developed and validated UHPLC–DAD–HRMS method. In acidic conditions, pure and complexed NAB was prone to hydrolytic degradation, yielding one degradation product—pharmacologically inactive NAB metabolite. However, under the oxidative conditions at elevated temperatures, 10 NAB degradation products were identified from co-ground samples. All systems were stable during photo- and long-term stability studies. Conclusions: NAB complexes with HP-β-CD and SBE-β-CD are promising candidates for pharmaceutical product development. Full article
(This article belongs to the Special Issue Supramolecular Systems for Gene and Drug Delivery, 2nd Edition)
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<p>Structural formulas of nabumetone (NAB), β-cyclodextrin (β-CD), and their derivatives.</p>
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<p>DSC thermograms (<b>left</b>) and XRPD diffractograms (<b>right</b>) of starting compounds (NAB and β-CD), ground and co-evaporated drug (NAB GR and NAB COE), physical mixture (NAB/β-CD PM), and complexes obtained by co-grinding (NAB/β-CD GR) and co-evaporation (NAB/β-CD COE). The results for the systems prepared with HP-β-CD and SBE-β-CD are presented in <a href="#app1-pharmaceutics-16-01493" class="html-app">Supporting Information (Figures S1 and S2, respectively)</a>.</p>
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<p>Saturation solubility of NAB and co-ground CD complexes in a hydrochloric acid medium pH 1.2 and a hydrochloric acid medium pH 1.2 with 2% (<span class="html-italic">w</span>/<span class="html-italic">V</span>) sodium lauryl sulfate (insert) at 37 °C. One asterisk (*) denotes a statistically significant difference (<span class="html-italic">p</span> &lt; 0.05) compared to pure NAB, two asterisks (**) denote a statistically significant difference (<span class="html-italic">p</span> &lt; 0.05) compared to β-CD complex, and three asterisks (***) denote a statistically significant difference (<span class="html-italic">p</span> &lt; 0.05) compared to HP-β-CD complex. Sample codes: NAB (A), NAB GR (B), NAB/β-CD GR (C), NAB/HP-β-CD GR 20 Hz/120 min (D), NAB/HP-β-CD GR 30 Hz/90 min (E), NAB/SBE-β-CD GR 20 Hz/120 min (F), and NAB/SBE-β-CD GR 30 Hz/120 min (G).</p>
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<p>In vitro dissolution profiles of NAB and its co-ground products with CDs in hydrochloric acid medium at 37 °C.</p>
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<p>The 4-hour dissolution profiles of NAB (A), NAB/HP-β-CD 30 Hz/90 min (E), and NAB/SBE-β-CD 30 Hz/120 min (G) in PBS, pH 6.8, at 37 °C (<b>left</b>) and the thermodynamic solubility of the samples at 24 h (37 °C, PBS pH 6.8) (<b>right</b>). Significant differences are indicated with an asterisk: * <span class="html-italic">p</span> &lt; 0.05 (n = 3, one-way ANOVA, Tukey’s multiple comparisons test).</p>
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<p>In vitro gastrointestinal flux (<b>left</b>) and permeability (<b>right</b>) of NAB (A), NAB/HP-β-CD 30 Hz/90 min (E), and NAB/SBE-β-CD 30 Hz/120 min (G). Significant differences are indicated with an asterisk: * <span class="html-italic">p</span> &lt; 0.05 (n = 3, one-way ANOVA, Tukey’s multiple comparisons test).</p>
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<p>HRMS spectrum of degradation product DP 1 (<span class="html-italic">t</span><sub>R</sub> = 10.9 min) formed during the acidic hydrolytic degradation.</p>
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<p>Proposed degradation products of NAB in hydrolytic (HCl) and oxidative conditions (H<sub>2</sub>O<sub>2</sub>). Experimental conditions: 2M HCl; 3% H<sub>2</sub>O<sub>2</sub> at 80 °C.</p>
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22 pages, 12709 KiB  
Article
Synergistic Reduction in Asphalt VOC Emissions by Hydrochloric Acid-Modified Zeolite and LDHs
by Haowei Zhao, Anqi Chen, Shaopeng Wu, Haiqin Xu, Huan Wang and Yang Lv
Materials 2024, 17(22), 5664; https://doi.org/10.3390/ma17225664 - 20 Nov 2024
Viewed by 444
Abstract
Asphalt releases a large number of irritating fumes during construction and use, which is a serious emission pollution that not only damages the atmospheric environment but also produces highly toxic and carcinogenic volatile organic compounds (VOCs), posing a health risk to human beings. [...] Read more.
Asphalt releases a large number of irritating fumes during construction and use, which is a serious emission pollution that not only damages the atmospheric environment but also produces highly toxic and carcinogenic volatile organic compounds (VOCs), posing a health risk to human beings. In this study, a compound-doped modified bitumen for reducing VOC emission was prepared by using zeolite as the main adsorbent material, modified by hydrochloric acid, and LDHs as a synergistic adsorbent material. By determining its basic and rheological properties, the results show that the compounding of LDHs and HCL-modified zeolite added to asphalt can improve the high-temperature performance of asphalt binder, but at the same time, the anti-fatigue property will be decreased. By GC-MS experimental analysis, a total of 72.2% fewer volatile organic compounds (VOCs) were released by the compound modified asphalt compound than by virgin asphalt, which resulted in a significant reduction in asphalt fume emissions. It shows that the asphalt VOC molecules are well adsorbed by the porous adsorption of LDHs and zeolite materials, and it is also found experimentally that they inhibit the emission of VOCs through the blocking and adsorption effects. This study provides a scientific basis for inhibiting the emission of VOCs during asphalt pavement construction. Full article
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<p>Compositional analysis of zeolite pretreatment.</p>
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<p>Infrared spectra of modified bitumen.</p>
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<p>The basic properties of the four types of asphalt are (<b>a</b>) softening point, (<b>b</b>) ductility, and (<b>c</b>) permeability. (<b>d</b>) viscosity.</p>
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<p>(<b>a</b>) Complex modulus of the five asphalts; (<b>b</b>) Phase angle of the five asphalts.</p>
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<p>High-temperature rutting factor (Rf) for five asphalts.</p>
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<p>Fatigue factor for five types of asphalt.</p>
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<p>Low-temperature rheological properties of five asphalts.</p>
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<p>VOCs composition of four types of asphalt settling time.</p>
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<p>Total VOC emissions from four types of asphalt.</p>
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<p>Concentrations of the 10 highest concentrations of VOCs.</p>
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<p>(<b>a<sub>(1)</sub></b>–<b>a<sub>(4)</sub></b>) Scanning electron microscope image of zeolite; (<b>b<sub>(1)</sub></b>–<b>b<sub>(4)</sub></b>) scanning electron microscope image of zeolite after treatment with hydrochloric acid.</p>
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<p>N<sub>2</sub> adsorption and desorption curves of zeolite.</p>
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<p>N<sub>2</sub> adsorption and desorption curves of HCl-treated zeolite.</p>
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<p>(<b>a</b>) TG curves of the four asphalts; (<b>b</b>) residual mass of the four asphalts.</p>
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<p>DTG curve of all binders.</p>
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26 pages, 9253 KiB  
Article
The Efficient and Environmentally Friendly Chlorination of Arene, Alcohol, Halobenzene, and Peroxide Catalyzed by Fe–Ba Binary Oxides Using Hydrochloric Acid as Chlorine Source and Aqueous H2O2 as Oxidant
by Sidra Chaudhary, Qin Pan, Yong Wu, Zainab Bibi, Xiaoyong Li, Qinxiang Jia and Yang Sun
Molecules 2024, 29(22), 5451; https://doi.org/10.3390/molecules29225451 - 19 Nov 2024
Viewed by 863
Abstract
A series of Fe–Ba mixed oxides, including a pure Fe-containing sample as a reference, have been synthesized via a sol–gel process using Fe3+ or Fe2+ salts and BaSO4 as raw materials, with Pluronic P123 serving as a template. These oxides [...] Read more.
A series of Fe–Ba mixed oxides, including a pure Fe-containing sample as a reference, have been synthesized via a sol–gel process using Fe3+ or Fe2+ salts and BaSO4 as raw materials, with Pluronic P123 serving as a template. These oxides have been thoroughly characterized and subsequently utilized as catalysts for the chlorination of various organic molecules. Commercial hydrochloric acid, known for its relative safety, and environmentally friendly aqueous hydrogen peroxide were employed as the chlorine source and oxidant, respectively. The pure Fe-containing catalyst displays excellent thermal stability between 600 and 800 °C and exhibited moderate to high conversions in the chlorination of toluene, benzene, and tert-butyl hydroperoxide, with remarkable ortho-selectivity in chlorination of toluene. The combination of Fe3+ salt with BaSO4 in the sol–gel process results in a Fe–Ba mixed oxide catalyst composed of BaO2, BaFe4O7, and Fe2O3, significantly enhancing the chlorination activity compared to that displayed by the pure Fe catalyst. Notably, the chlorination of tert-butyl hydroperoxide (TBHP) does not require additional oxidants such as H2O2, and involves both electrophilic substitution and nucleophilic addition. Notably, the chlorination of bromobenzene yields chlorobenzene as the sole product, a transformation that has not been previously reported. Overall, this catalytic chlorination system holds promise for advancing the chlorination industry and enhancing pharmaceutical production. Full article
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Graphical abstract

Graphical abstract
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<p>Representative chlorine-containing pharmaceuticals: (<b>a</b>) Vismodegib; (<b>b</b>) Regorafenib; (<b>c</b>) Roflumilast; (<b>d</b>) Lorcaserin.</p>
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<p>Three known chlorination processes facilitated by different chlorine sources.</p>
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<p>Synthesis of catalysts FB1–FB4 (asterisks in structure of Pluronic P123 means repetitive units).</p>
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<p>XPS survey scan for the synthesized catalysts: (<b>a</b>) FB1; (<b>b</b>) FB2; (<b>c</b>) FB3; (<b>d</b>) FB4.</p>
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<p>XPS measurements of the Fe 2p regions for synthesized catalysts: (<b>a</b>) FB1; (<b>b</b>) FB2; (<b>c</b>) FB3; (<b>d</b>) FB4.</p>
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<p>Wide-angle XRD diffractograms (2<span class="html-italic">θ</span> = 10°–80°): (<b>a</b>) FB1 (dark cubes, Fe<sub>2</sub>O<sub>3</sub>; white cubes, Fe<sub>3</sub>O<sub>4</sub>); (<b>b</b>) FB2 (arrows, Fe<sub>2</sub>O<sub>3</sub>; asterisks, BaFe<sub>4</sub>O<sub>7</sub>; circles, BaO<sub>2</sub>).</p>
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<p>XPS measurements of the Ba 3d regions for synthesized catalysts: (<b>a</b>) FB2; (<b>b</b>) FB3; (<b>c</b>) FB4.</p>
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<p>XPS measurements of the C 1s region: (<b>a</b>) FB1; (<b>b</b>) FB2; (<b>c</b>) FB3; (<b>d</b>) FB4.</p>
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<p>XPS measurements of the O 1s region: (<b>a</b>) FB1; (<b>b</b>) FB2; (<b>c</b>) FB3; (<b>d</b>) FB4.</p>
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<p>FT-IR spectra (adsorption mode) of synthesized catalysts: (<b>a</b>) FB1; (<b>b</b>) FB2; (<b>c</b>) FB3; (<b>d</b>) FB4.</p>
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<p>UV–vis spectra of synthesized catalysts FB1–FB4.</p>
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<p>Thermal analysis of synthesized catalysts FB1–FB4: (<b>a</b>) TGA; (<b>b</b>) DTG; (<b>c</b>) DSC.</p>
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<p>SEM images of synthesized catalysts: (<b>a</b>) FB1 (magnification 1770×); (<b>b</b>) FB1 (5280×); (<b>c</b>) FB1 (6640×); (<b>d</b>) FB2 (1400×); (<b>e</b>) FB2 (7440×); (<b>f</b>) FB3 (396×); (<b>g</b>) FB3 (1770×); (<b>h</b>) FB4 (8780×); (<b>i</b>) FB4 (39,240×).</p>
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<p>SEM and EDS mapping images of FB1: (<b>a</b>) SEM of FB1 (magnification 6640×, same as <a href="#molecules-29-05451-f013" class="html-fig">Figure 13</a>c with different scale bar); (<b>b</b>) EDS layered image; (<b>c</b>) O Kα1; (<b>d</b>) Fe Lα1,2; (<b>e</b>) Ba Mα; (<b>f</b>) S Kα1.</p>
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<p>SEM and EDS mapping images of FB2: (<b>a</b>) SEM of FB2 (magnification 7440×, same as <a href="#molecules-29-05451-f013" class="html-fig">Figure 13</a>e with different scale bar); (<b>b</b>) EDS layered image; (<b>c</b>) O Kα1; (<b>d</b>) Fe Lα1,2; (<b>e</b>) Ba Mα; (<b>f</b>) S Kα1.</p>
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<p>Proposed process for catalytic chlorination of <span class="html-italic">tert</span>-butyl hydroperoxide (TBHP).</p>
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13 pages, 2188 KiB  
Article
Solvolysis of Nylon: A Pathway to Sustainable Recycling and Circular Economy
by Nuno Gama, Jéssica Araújo, Bruno Godinho, Artur Ferreira and Ana Barros-Timmons
Sustainability 2024, 16(22), 9725; https://doi.org/10.3390/su16229725 - 8 Nov 2024
Viewed by 880
Abstract
Polyamides (PAs) are extensively utilized across various applications, yet the accumulation of PA residues presents significant ecological and environmental challenges. Given that a substantial portion of fishing nets are composed of nylon, a type of PA, this material’s disposal raises environmental concerns impacting [...] Read more.
Polyamides (PAs) are extensively utilized across various applications, yet the accumulation of PA residues presents significant ecological and environmental challenges. Given that a substantial portion of fishing nets are composed of nylon, a type of PA, this material’s disposal raises environmental concerns impacting marine life and the global ecosystem. Therefore, to enhance sustainability, they could be collected and recycled. This study introduces a method for the chemical recycling of PA waste using hydrochloric acid (HCl). Through solvolysis, a PA was depolymerized, and the effect of various reaction conditions on the depolymerization yield was analyzed, being the best conditions established in this work (100 °C, 4 h, and an HCl/PA ratio of 11:1, wt.wt−1). Next, a novel separation methodology was employed to isolate recycled products from salts formed during neutralization. Subsequently, these recycled products were incorporated as a partial substitute (up to 10% wt.wt−1) for a conventional PA in a new material production. The results indicate that the presence of recycled products enhances material stiffness due to crystallinity differences compared to the virgin matrix. In turn, the introduction of lower-molecular-weight species increases the materials’ glass transition temperature (Tg) and their melt flow index (MFI). This research underscores a sustainable pathway for PA recycling aligned with circular economy principles, contributing positively to environmental conservation efforts. Full article
(This article belongs to the Special Issue Recycling Materials for the Circular Economy—2nd Edition)
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<p>Methodology used to depolymerize the polyamide and purify the ensuing reaction products.</p>
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<p>Yields of reactions.</p>
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<p>FTIR spectra corresponding to a PA and the products obtained in the first experiment.</p>
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<p>TGA of the precipitate resulting from the supernatant treated with t-butanol.</p>
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<p><sup>1</sup>H-NMR spectrum of the solid residue obtained after t-butanol removal and chemical structure of aminocaproic acid and caprolactam, with corresponding peaks.</p>
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<p>Molecular weight distribution of dried supernatants.</p>
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<p>DMA results of recycled polyamide samples.</p>
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<p>DSC thermogram of recycled polyamide samples.</p>
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18 pages, 7206 KiB  
Article
Resource Recovery from Abandoned Mine Drainage Galleries via Ion Exchange: A Case Study from Freiberg Mining Area, Germany
by Janith Abeywickrama, Katayoun Karimi, Marlies Grimmer, Nils Hoth and Carsten Drebenstedt
Recycling 2024, 9(6), 105; https://doi.org/10.3390/recycling9060105 - 2 Nov 2024
Viewed by 1232
Abstract
The discharge of metal-loaded mining-influenced waters can significantly pollute downstream water bodies for many kilometers. Addressing this issue at the earliest discharge point is crucial to prevent further contamination of the natural environment. Additionally, recovering metals from these discharges and other sources of [...] Read more.
The discharge of metal-loaded mining-influenced waters can significantly pollute downstream water bodies for many kilometers. Addressing this issue at the earliest discharge point is crucial to prevent further contamination of the natural environment. Additionally, recovering metals from these discharges and other sources of contamination can reduce the environmental impacts of mining and support the circular economy by providing secondary raw materials. This study focused on optimizing zinc recovery from mining-influenced water in the Freiberg mining region in Germany, where significant loads of zinc are released into the Elbe River. By employing pretreatment techniques, conducting 100 mL scale ion-exchange column experiments, and refining the regeneration process, we aimed to identify optimal conditions for efficient zinc removal and recovery. Initial tests showed that aminophosphonic functionalized TP 260 resin had a high affinity for aluminum, occupying 93% of the resin’s capacity, while zinc capacity was limited to 0.2 eq/L. To improve zinc recovery, selective precipitation of aluminum at pH 6.0 was introduced as a pretreatment step. This significantly increased the zinc loading capacity of the resin to 1 eq/L. Under optimal conditions, a concentrated zinc solution of 18.5 g/L was obtained with 100% recovery. Sulfuric acid proved more effective than hydrochloric acid in eluting zinc from the resin. Further analysis using SEM-EDX revealed residual acid on the resin, indicating a need for additional study on long-term resin performance and capacity variation. The research also highlighted the environmental impact of the Freiberg mining area, where three drainage galleries currently contribute nearly 85 tons of zinc annually to the Elbe River. This study underscores the feasibility of efficient zinc recovery from these point sources of pollution using advanced ion-exchange processes, contributing to circular economy efforts and environmental conservation. Full article
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<p>(<b>a</b>) Pourbaix (Eh-pH) diagram; (<b>b</b>) Temperature versus electrical conductivity diagram of the Erzgebirge mine waters; (<b>c</b>) Ratio of Particulate to dissolve Al + Fe; (<b>d</b>) The relationship between Chloride and Sulfate.</p>
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<p>(<b>a</b>) Breakthrough curves of untreated mine water (Zn and Al) loaded into IX column with TP 260 resin; (<b>b</b>) breakthrough curves of pretreated mine water (after Al precipitation); (<b>c</b>) De-loading curves of Zn and Al in untreated (column A) and pretreated (column B) mine waters; (<b>d</b>) Mass balance of column A and B (L—loading, De—De-loading).</p>
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<p>De-loading curves for (<b>a</b>) zinc and (<b>b</b>) aluminum in columns V1 and V2; column V1 was regenerated with 5% HCl, and column V2 was regenerated with 5% H<sub>2</sub>SO<sub>4</sub> acid; (<b>c</b>) de-loading curves for column V3, and (<b>d</b>) column V4.</p>
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<p>SEM-EDX observation of the Initial stage of the TP 260 resin.</p>
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<p>Elemental composition of used TP 260 resins (<b>a</b>) regenerated with 5% HCl acid (<b>b</b>) regenerated with 5% sulfuric acid.</p>
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<p>Location of the Reiche Zeche Mine and the important Mine drainage galleries “Verträgliche Gesellschaft Stolln” (VGS), “Rothschönberger Stolln” (RSS), “Hauptstolln Umbruch” (HSU).</p>
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20 pages, 1113 KiB  
Article
Potential for the Recovery of Selected Metals and Critical Raw Materials from Slags from Polymineral Zn–Pb Ore Metallurgy—Part II
by Henryk Świnder, Paweł Lejwoda, Piotr Krawczyk, Magdalena Cempa and Arkadiusz Bauerek
Minerals 2024, 14(11), 1091; https://doi.org/10.3390/min14111091 - 28 Oct 2024
Viewed by 576
Abstract
This paper presents the results of research on the possibility to obtain CRMs (REEs) and industrial metals (Zn) from slag as a waste generated as part of zinc and lead extraction processes. Physicochemical methods were used to separate CRM and Zn concentrates: magnetic [...] Read more.
This paper presents the results of research on the possibility to obtain CRMs (REEs) and industrial metals (Zn) from slag as a waste generated as part of zinc and lead extraction processes. Physicochemical methods were used to separate CRM and Zn concentrates: magnetic separation, sintering with NaOH and leaching with selected mineral acids. After analysing the obtained results, it was found that the use of concentrated hydrochloric acid and a temperature of 363 K for leaching was effective in separating REEs from slags obtained from current production. The recovery rate in this case ranged from 83.73% for La to 98.03% for Eu. For slag samples (M1) obtained from current production from ZGH Bolesław S.A.(Poland) as well as HC Miasteczko Śląskie S.A. (Poland) and treated with concentrated HCl, the leaching level of Bi, Zn, Ni, Mn and P exceeded 90% compared to the content in the reference sample. For a historical slag sample from Ruda Śląska (Poland), treatment with concentrated HCl yielded a high leaching level of Cd (70.90%), Pb (78.66%), As (72.49%) and Mo (61.90%). A concentrate containing 1.64% of REEs and 67.1% of Zn was isolated from the solutions obtained after leaching by precipitation. An economic analysis of an REE concentrate extraction facility was also performed. For an operation of 17 years, the calculated NPV was −26,352,644 million EUR. The obtained results indicate that, for the analysed facility, recovering metals and critical raw materials from slag as a waste mass is not economically effective. Full article
(This article belongs to the Special Issue Characterization and Reuse of Slag)
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<p>Graphical interpretation of the sensitivity analysis: economic analysis results expressed as NPV.</p>
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<p>Graphical interpretation of the complex sensitivity analysis results: a simultaneous decrease in the costs of chemicals and an increase in the REE weight concentration in the slag at the reactor inlet.</p>
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