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Keywords = alkylative degradation

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22 pages, 3439 KiB  
Article
Metabolomics Analysis Reveals the Influence Mechanism of Different Growth Years on the Growth, Metabolism and Accumulation of Medicinal Components of Bupleurum scorzonerifolium Willd. (Apiaceae)
by Jialin Sun, Jianhao Wu, Weinan Li, Xiubo Liu and Wei Ma
Biology 2025, 14(7), 864; https://doi.org/10.3390/biology14070864 - 16 Jul 2025
Viewed by 221
Abstract
Bupleurum scorzonerifolium Willd. is a perennial herbaceous plant of the genus Bupleurum in the Apiaceae family. Also known as red Bupleurum, it is mainly distributed in Northeast China, North China and other regions and is a commonly used medicinal plant. It is [...] Read more.
Bupleurum scorzonerifolium Willd. is a perennial herbaceous plant of the genus Bupleurum in the Apiaceae family. Also known as red Bupleurum, it is mainly distributed in Northeast China, North China and other regions and is a commonly used medicinal plant. It is difficult for the wild plant resources of Bupleurum scorzonerifolium Willd. to meet the market demand. In artificial cultivation, there are problems such as a low yield per plant, low quality, weakened stress resistance and variety degradation. The contents of bioactive components and metabolites in traditional Chinese medicinal materials vary significantly across different growth years. The growth duration directly impacts their quality and clinical efficacy. Therefore, determining the optimal growth period is one of the crucial factors in ensuring the quality of traditional Chinese medicinal materials. In this study, Gas Chromatography–Mass Spectrometry (GC-MS) and High-performance liquid chromatography (HPLC) were comprehensively applied to analyze the metabolically differential substances in different parts of Bupleurum scorzonerifolium Willd. By comparing the compositions and content differences of chemical components in different growth years and different parts, the chemical components with significant differences were accurately screened out. In order to further explore the dynamic change characteristics and internal laws of metabolites, a metabolic network was constructed for a visual analysis and, finally, to see the optimal growth years of Bupleurum scorzonerifolium Willd. This result showed that with the accumulation of the growth cycle, the height, root width, fresh mass and saikosaponins content of Bupleurum scorzonerifolium Willd. increased year by year. Except for sodium and calcium elements in the main shoot, the other elements were significantly reduced. In addition, 59 primary metabolites were identified by GC-MS, with the accumulation of the growth cycle, the contents of organic acids, sugars, alcohols and amino acids gradually decreased, while the contents of alkyl, glycosides and other substances gradually increased. There were 53 positive correlations and 18 negative correlations in the triennial Bupleurum scorzonerifolium Willd. grid, all of which were positively correlated with saikosaponins. Therefore, the triennial Bupleurum scorzonerifolium Willd. was considered to be the suitable growth year. It not only provided a new idea and method for the quality evaluation of Bupleurum scorzonerifolium Willd., but also provided a scientific basis for the quality control of Chinese herbs. Full article
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20 pages, 7663 KiB  
Article
Evaluation of Imidazolium Ionenes: Solid–Solid Phase Change Materials as Heat Sinks
by Carolina Arriaza-Echanes, Gabriel I. Krüger, Bibiana Comesaña-Gándara, Claudio A. Terraza, Loreto Sanhueza and Pablo A. Ortiz
Polymers 2025, 17(13), 1782; https://doi.org/10.3390/polym17131782 - 27 Jun 2025
Viewed by 393
Abstract
Overheating in miniaturized electronic devices can reduce their useful life, where conventional heat sinks are insufficient. The utilization of ionenes as solid–solid phase change materials is proposed to enhance thermal dissipation without the risk of leakage. In this work, a series of imidazolium [...] Read more.
Overheating in miniaturized electronic devices can reduce their useful life, where conventional heat sinks are insufficient. The utilization of ionenes as solid–solid phase change materials is proposed to enhance thermal dissipation without the risk of leakage. In this work, a series of imidazolium ionenes with structural modifications in their aromatic core and aliphatic chain length were synthesized. The synthesis was carried out using the respective monomers diimidazole and alkyl dibromide, followed by counterion bromide exchange using lithium bis(trifluoromethanesulfonyl)imide, with yields over 90% in all cases. Thermal characterizations showed that all ionenes are heat-resistant, with degradation temperatures between 421 °C and 432 °C; moreover, they all presented only a solid–solid transition (Tg) as a phase change, between 59 °C and 28 °C, which varied depending on the aromatic core used and the length of the aliphatic chain. The obtained ionenes were introduced into an experimental device with an operating temperature of 40 °C, to be evaluated as solid–solid phase change materials in heat sinks. These demonstrated an average decrease in operating temperature of 9 °C compared to the device without ionenes. On the other hand, the stability of the ionenes was analyzed over 10 thermal cycles at 40 °C at a heating rate of 5 °C/min. This analysis demonstrated that the ionenes did not present changes or degradation during the evaluated cycles. These findings demonstrate that imidazolium ionenes are promising solid–solid phase change materials for use as efficient and self-repairing heat sinks in compact electronic devices. Full article
(This article belongs to the Section Polymer Applications)
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15 pages, 1066 KiB  
Article
Preparation and Evaluation of Long-Acting Injectable Levocetirizine Prodrug Formulation
by Jun-hyun Ahn
Pharmaceutics 2025, 17(7), 806; https://doi.org/10.3390/pharmaceutics17070806 - 21 Jun 2025
Viewed by 545
Abstract
Background/Objectives: Levocetirizine (LCZ) is a second-generation antihistamine with minimal central nervous system effects. However, its short half-life necessitates daily dosing, potentially reducing adherence in pediatric populations. This study aimed to develop a long-acting injectable LCZ formulation by synthesizing lipophilic prodrugs and evaluating [...] Read more.
Background/Objectives: Levocetirizine (LCZ) is a second-generation antihistamine with minimal central nervous system effects. However, its short half-life necessitates daily dosing, potentially reducing adherence in pediatric populations. This study aimed to develop a long-acting injectable LCZ formulation by synthesizing lipophilic prodrugs and evaluating their physicochemical stability, enzymatic hydrolysis, and pharmacokinetics in vivo. Methods: Two prodrugs of LCZ, LCZ decanoate (LCZ-D) and LCZ laurate (LCZ-L), were synthesized via esterification with alkyl alcohols. The compounds were characterized using NMR, FT-IR, and DSC. Prodrugs were formulated with an oil-based vehicle (castor oil and benzyl benozate), and their hydrolysis was evaluated using porcine liver esterase (PLE) and rat plasma. Pharmacokinetic profiles were assessed in Sprague Dawley rats after oral or intramuscular administration. Stability was tested at 25 °C, 40 °C, and 60 °C for 6 weeks. Results: LCZ-D and LCZ-L exhibited first-order hydrolysis kinetics, with rates following the order of PLE (2.0 > 0.5 units/mL) > plasma > PLE (0.2 units/mL). The Cmax of LCZ-D and LCZ-L were 13.95 and 5.12 ng/mL, respectively, with corresponding AUC0–45d values of 6423.12 and 2109.22 h·ng/mL. Formulations containing excipients with lower log P values led to increased systemic exposure. All formulations maintained therapeutic plasma concentrations for over 30 days. The inclusion of the antioxidant BHT (0.03% v/v) improved oxidative stability, reducing degradation at 60 °C from 4.72% to 1.17%. Conclusions: All formulations demonstrated potential for the long-acting delivery of LCZ, maintaining therapeutic plasma levels for over 30 days. Moreover, the release behavior and systemic exposure could be effectively modulated by excipient selection. Full article
(This article belongs to the Section Drug Delivery and Controlled Release)
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9 pages, 1522 KiB  
Article
Mild and Effective Decatungstate-Catalyzed Degradation of Methyl Orange Under Visible Light
by Wenfeng Wu, Lin Yu, Lei Zha, Feifei He, Jiajia Ma, Ouyang Wu, Huanhuan Zhang, Xinlan Chen, Shuyin Yu, Mengjing Lei, Lin-Lin Yang, Jiangang Chen and Xiai Luo
Catalysts 2025, 15(5), 494; https://doi.org/10.3390/catal15050494 - 20 May 2025
Viewed by 574
Abstract
Decatungstate (DT) is a highly promising photocatalyst for dioxygen (O2)-based reactions but has hardly been applied in the photocatalytic degradation technology of dye. Here, we synthesized hydrophilic DT–SO3H salts by incorporating tetra-alkyl cations with sulfonic acid groups, aiming to [...] Read more.
Decatungstate (DT) is a highly promising photocatalyst for dioxygen (O2)-based reactions but has hardly been applied in the photocatalytic degradation technology of dye. Here, we synthesized hydrophilic DT–SO3H salts by incorporating tetra-alkyl cations with sulfonic acid groups, aiming to enhance both the water solubility and catalytic efficiency of DT under visible light. Comprehensive characterization of DT–SO3H using ultraviolet–visible spectroscopy (UV–Vis), Fourier Transform Infrared Spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), Photocurrent (PTC), and Electrochemical Impedance Spectroscopy (EIS) confirmed its improved properties. DT–SO3H demonstrated outstanding photocatalytic performance, achieving 90% degradation of methyl orange within 25 min under continuous visible light irradiation. This study presents a cost-effective and efficient method for degrading methyl orange, representing a significant advancement in the development of high-performance photocatalysts and opening new avenues for the study and application of photocatalytic dye degradation technologies. Full article
(This article belongs to the Section Photocatalysis)
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15 pages, 11727 KiB  
Article
Prepubertal Exposure to Tris(2-chloroethyl) Phosphate Disrupts Blood-Testis Barrier Integrity via Ferritinophagy-Mediated Ferroptosis
by Yonggang Zhao, Mo Peng, Honglei Liu, Xiaoyu Zhang and Dan Fu
Toxics 2025, 13(4), 285; https://doi.org/10.3390/toxics13040285 - 8 Apr 2025
Viewed by 507
Abstract
Tris(2-chloroethyl) phosphate (TCEP) is a representative chlorinated organophosphate flame retardant (OPFR) that demonstrates greater persistence than other non-halogenated alkyl or aryl OPFRs. Although TCEP has been shown to accumulate significantly in the environment and contribute to testicular toxicity and spermatogenic dysfunction, the precise [...] Read more.
Tris(2-chloroethyl) phosphate (TCEP) is a representative chlorinated organophosphate flame retardant (OPFR) that demonstrates greater persistence than other non-halogenated alkyl or aryl OPFRs. Although TCEP has been shown to accumulate significantly in the environment and contribute to testicular toxicity and spermatogenic dysfunction, the precise underlying factors and mechanisms of action remain unclear. Herein, male ICR mice were gavaged with corn oil, 50 mg/kg body weight (bw) TCEP, or 100 mg/kg bw TCEP from postnatal day (PND) 22 to PND 35. TCEP exposure resulted in the disruption of blood-testis barrier (BTB) integrity and in abnormal testicular development. Considering that Sertoli cells constitute the primary target of toxicants and that TCEP induces oxidative stress in the testis and other organs, we focused on ferroptosis in Sertoli cells. Our findings revealed a significant increase in ferroptosis in the testes and Sertoli cells following TCEP exposure, and we observed functional restoration of Sertoli cell junctions upon treatment with the ferroptosis inhibitor ferrostatin-1. Furthermore, ferritin heavy chain 1 (FTH1) was markedly reduced in TCEP-exposed testes and Sertoli cells. Since nuclear receptor coactivator 4 (NCOA4)-mediated ferritinophagy is essential for the degradation of FTH1, we assessed ferritinophagic activity and found significant upregulation of NCOA4, ATG5, ATG7, and LC3B II/I in TCEP-exposed testes and Sertoli cells. These results strongly suggest that TCEP triggers Sertoli cell ferroptosis by activating ferritinophagy that leads to reduced expression of BTB-associated proteins, ultimately causing BTB disruption and testicular developmental toxicity. Full article
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23 pages, 5013 KiB  
Article
Study on the Impact of Diluent Dosages on the Epoxy–Polythiol Self-Healing System
by Jiajia Sheng, Yang Guo, Xin Pang, Wenjing Ma, Hailu Yang, Yalin Liu, Linbing Wang and Shanglin Song
Polymers 2025, 17(4), 538; https://doi.org/10.3390/polym17040538 - 19 Feb 2025
Viewed by 638
Abstract
Self-healing technology is an effective method for enhancing the crack resistance of cement-based composites. This study focuses on the impact of the environmentally friendly diluent C12-14 alkyl glycidyl ether (AGE) on the performance of the epoxy resin–polythiol (rimethylolpropane tris (3-mercaptopropionate), TMPMP) self-healing system, [...] Read more.
Self-healing technology is an effective method for enhancing the crack resistance of cement-based composites. This study focuses on the impact of the environmentally friendly diluent C12-14 alkyl glycidyl ether (AGE) on the performance of the epoxy resin–polythiol (rimethylolpropane tris (3-mercaptopropionate), TMPMP) self-healing system, examining core fluidity, microcapsule properties, molecular dynamics, and the mechanical properties of cured products. The results show that as the AGE dosage increases, the particle size distribution of microcapsules becomes more concentrated, and the dispersion of particles is improved. Fourier-transform infrared spectroscopy confirms the successful encapsulation of E-51 and AGE. Microcapsules maintain structural integrity at high temperatures of 423.15 K. The onset thermal degradation temperature of the mixture shows an increasing trend with reduced AGE dosage. Specifically, TMPMP35% exhibits an onset degradation temperature of 370.95 K, while that of TMPMP20% is increased by 57.57% compared to TMPMP35%. Conversely, the initial and peak temperatures of the curing reaction decrease with less AGE incorporation. Thermodynamic analysis reveals that activation energy (E) initially increases and then decreases with increasing AGE. The frequency factor (A) correlates positively with the heating rate, indicating that the curing reaction’s reactivity is closely linked to heating rate. Minor variations in the reaction rate constant (k) indicate that the self-healing system maintains stable reactive activity at low temperatures. Notably, the AGE dosage significantly affects the rigidity of the self-healing system; the average Young’s modulus inversely correlates with AGE dosage, with the most substantial decrease of 5.88% occurring when AGE increases from 30% to 35%. This study offers insights into optimizing diluent ratios to balance self-healing and mechanical properties, essential for developing high-performance self-healing cement materials. Full article
(This article belongs to the Section Smart and Functional Polymers)
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12 pages, 3506 KiB  
Article
Photoluminescence and Stability of Dion–Jacobson Tin-Based Halide Perovskites with Different Spacer Cation Chain Length
by Muhammad Umair Ali, Wen Ting Sun, Aleksandr A. Sergeev, Atta Ur Rehman, Kam Sing Wong, Aleksandra B. Djurišić and Jasminka Popović
Molecules 2025, 30(3), 703; https://doi.org/10.3390/molecules30030703 - 5 Feb 2025
Viewed by 911
Abstract
Two-dimensional tin halide perovskites are of significant interest for light emitting applications. Here, we investigate the effect of organic cation A on the stability of different Dion–Jacobson tin-based halide perovskites. The ASnBr4 materials using diammonium cation A with shorter alkyl chains are [...] Read more.
Two-dimensional tin halide perovskites are of significant interest for light emitting applications. Here, we investigate the effect of organic cation A on the stability of different Dion–Jacobson tin-based halide perovskites. The ASnBr4 materials using diammonium cation A with shorter alkyl chains are found to exhibit improved stability, exhibiting dramatic stability difference between the most stable HDASnBr4, where HDA denotes 1,6-hexanediammonium, and two materials with 8- and 10-carbon alkyl chain ammonium cations. The HDASnBr4 powders were thermally stable at 100 °C in an argon environment but exhibited decreasing photoluminescence with time in ambient air at 100 °C. The sample degradation at 100 °C is accelerated compared to room temperature, but it proceeds along similar pathways, namely phase transformation followed by perovskite decomposition. Light emission from HDASnBr4 thin films could be further enhanced by methanol vapor treatment, and warm white emission with Commission Internationale de l’Eclairage (CIE) coordinates (0.37, 0.34) could be obtained by combining HDASnBr4 with a blue-emitting polymer film, while direct mixing of blue phosphor and HDASnBr4 powder yields white emission with CIE coordinates of (0.34, 0.32). Full article
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18 pages, 3696 KiB  
Article
Investigation of Impurities in Peptide Pools
by Gaby Bosc-Bierne and Michael G. Weller
Separations 2025, 12(2), 36; https://doi.org/10.3390/separations12020036 - 2 Feb 2025
Cited by 1 | Viewed by 2357
Abstract
Peptide pools are important research tools in different biomedical fields. They consist of a complex mixture of defined peptides, which places high demands on the production and quality control of these products. Previously it has been shown that the combination of UHPLC with [...] Read more.
Peptide pools are important research tools in different biomedical fields. They consist of a complex mixture of defined peptides, which places high demands on the production and quality control of these products. Previously it has been shown that the combination of UHPLC with high-resolution mass-spectrometry (HRMS) is a fast and powerful method to confirm the relative concentration and the structural identity of all peptides expected to be in the pool. In this work, the additional information contained in the UV chromatograms and mass spectra is used to search for impurities due to synthesis by-products and degradation during storage and transportation and to identify possible analytical artifacts. It was shown that most impurities are only present in trace amounts and can be considered uncritical for most applications. The most frequent and perhaps unexpected impurities were homo- and heterodimers caused by the free cysteines contained in these peptide pools. Furthermore, pyroglutamate and aspartimide formation, deamidation, methionine oxidation, and amino acid deletions could be found. This list is not intended to be comprehensive, but rather a brief guide to quickly identify impurities and, in the long term, to suggest possible changes in the composition of the peptide pools to avoid such impurities by design or by special precautions. Full article
(This article belongs to the Special Issue Peptide Synthesis, Separation and Purification)
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18 pages, 2928 KiB  
Article
Differences in Rejuvenation Mechanisms and Physical Properties of Aged Styrene–Butadiene–Styrene (SBS)-Modified Bitumen by Mono-Epoxy and Di-Epoxy Compounds
by Kingsley C. K. Chiang, Bohan Zhu, Lingxiao Liu, Haozongyang Li, Cheng Chen, Shixian Tang and Chengwei Xing
Polymers 2025, 17(1), 86; https://doi.org/10.3390/polym17010086 - 31 Dec 2024
Cited by 1 | Viewed by 822
Abstract
Studying the mechanisms and effects of rejuvenators on SBS-modified bitumen is crucial for repairing degraded SBS and recycling aged SBS-modified bitumen (ASMB), thereby contributing to the sustainable development of bitumen pavements. This research examines the roles of mono-epoxy Alkyl (C12-C14) glycidyl ether (AGE) [...] Read more.
Studying the mechanisms and effects of rejuvenators on SBS-modified bitumen is crucial for repairing degraded SBS and recycling aged SBS-modified bitumen (ASMB), thereby contributing to the sustainable development of bitumen pavements. This research examines the roles of mono-epoxy Alkyl (C12-C14) glycidyl ether (AGE) and di-epoxy 1,6-Hexanediol diglycidyl ether (HDE) under the catalysis of N,N-dimethyl benzyl amine (BDMA) in repairing degraded SBS chains. Aromatic oil (ORSMB)-, AGE–aromatic oil (ARSMB)-, and HDE–aromatic oil (HRSMB)-rejuvenated bitumen are analyzed for their chemical structures, physical properties, and rheological properties. Fluorescence microscopy (FM) and Fourier transform infrared spectroscopy (FTIR) reveal that HDE chemically reconnects degraded SBS chains, enhancing ASMB properties, while AGE improves ASMB properties through physical softening. HDE balances high-temperature properties and improves mid-temperature fatigue resistance through a rigid repair effect and flexible chain structure. AGE enhances mid-temperature fatigue resistance but significantly reduces high-temperature rutting resistance due to a softening effect. The findings demonstrate that HDE restores ASMB ductility chemically, while AGE improves crack resistance through physical softening. These differences in rejuvenation mechanisms provide a theoretical basis for optimizing rejuvenator design and advancing bitumen pavement recycling. Full article
(This article belongs to the Special Issue Sustainable Polymeric Materials in Building and Construction)
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16 pages, 2379 KiB  
Article
Impact of Wash Oil Composition on Degradation: A Comparative Analysis of “Light” and “Heavy” Oils
by Denis Miroshnichenko, Artem Bannikov, Leonid Bannikov, Olexandr Borisenko, Andrei Shishkin, Pavels Gavrilovs and Volodymyr Tertychnyi
Resources 2025, 14(1), 5; https://doi.org/10.3390/resources14010005 - 27 Dec 2024
Cited by 1 | Viewed by 1755
Abstract
This study aims to address the limited understanding of wash oil degradation in benzene units by analysing changes in the composition and properties of fresh and operating oils from different manufacturers. The findings will provide insights into the degradation pathways and stability of [...] Read more.
This study aims to address the limited understanding of wash oil degradation in benzene units by analysing changes in the composition and properties of fresh and operating oils from different manufacturers. The findings will provide insights into the degradation pathways and stability of these oils. Gas chromatography/mass spectrometry was used to analyse the provided samples, and the dynamic viscosity of the oils was determined using a Brookfield LV DV2T rotational viscometer. During operation, the “heavy” oil (HO) becomes less volatile, while the ”light” oil (LO) becomes slightly more volatile. The viscosity of the HO increases 1.25 times during operation. The LO is characterised by a higher total concentration of alkyl derivatives (48 wt.% compared to 44 wt.% for the HO). LO is enriched with naphthalene and indene, while HO loses 1- and 2-methylnaphthalenes and shows an increase in the concentrations of dibenzofuran, fluorene, anthracene, and phenanthrene. The oxidation products of LO include oxidised alkyl groups, while HO shows oxidised non-substituted hydrocarbons. The practical value of such studies lies in guiding the selection of fresh oil under current operating conditions. LO is more resistant to degradation as an absorbent than heavier wash oil. Full article
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25 pages, 15912 KiB  
Article
Insight into the Thermal Washing Mechanism of Sodium Lignosulfonate Alkyl/Sodium Persulfate Compound on Oily Sludge
by Yun Ma, Hui Liu, Liuli Zhu, Yi Xie, Chuanqi Ren, Xiaorong Mo, Xiaoying Liu, Chen Liang, Gang Deng, Shuangquan Yao and Chengrong Qin
Int. J. Mol. Sci. 2024, 25(23), 12542; https://doi.org/10.3390/ijms252312542 - 22 Nov 2024
Viewed by 724
Abstract
The thermal washing of oily sludge using sodium persulfate (SD) assisted by sodium lignosulfonate surfactant has been demonstrated to be an effective method for oily sludge remediation. To further explore the underlying mechanisms of this process, a systematic study was conducted by simulating [...] Read more.
The thermal washing of oily sludge using sodium persulfate (SD) assisted by sodium lignosulfonate surfactant has been demonstrated to be an effective method for oily sludge remediation. To further explore the underlying mechanisms of this process, a systematic study was conducted by simulating oily sludge systems consisting of saturated hydrocarbons (SaH), aromatics hydrocarbons (ArH), resins (Res), and asphaltenes (Asp). The effects of reaction conditions, such as pH, sodium lignosulfonate alkyl (LSA) concentration, SD concentration, and washing temperature, were analyzed. Furthermore, the oxidative kinetic mechanism during the reaction process was investigated. The results demonstrated that neither petroleum hydrocarbons nor SD underwent significant chemical transformations when exposed to LSA, while SD exhibited a marked oxidative degradation effect on all four types of hydrocarbons. Oxidation kinetics indicated that sodium hydroxide played a catalytic role, with SD being the main oxidant and particularly efficient in degrading Asp and Res. Meanwhile, LSA contributed to the removal of hydrocarbons by reducing the surface tension of the solution, enhancing solubilization. This study not only elucidates the central role of SD in the thermal washing process but also provides a solid theoretical foundation for the practical application of this technology in oily sludge treatment. Full article
(This article belongs to the Section Physical Chemistry and Chemical Physics)
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15 pages, 4196 KiB  
Article
Sequestration of Dyes from Water into Poly(α-Olefins) Using Polyisobutylene Sequestering Agents
by Neil Rosenfeld, Mara P. Alonso, Courtney Humphries and David E. Bergbreiter
Technologies 2024, 12(8), 138; https://doi.org/10.3390/technologies12080138 - 20 Aug 2024
Viewed by 2645
Abstract
Trace concentrations of dyes are often present in textile wastewater streams and present a serious environmental problem. Thus, these dyes must be removed from wastewater either by degradation or sequestration prior to discharge of the wastewater into the environment. Existing processes to remove [...] Read more.
Trace concentrations of dyes are often present in textile wastewater streams and present a serious environmental problem. Thus, these dyes must be removed from wastewater either by degradation or sequestration prior to discharge of the wastewater into the environment. Existing processes to remove these wastewater contaminants include the use of solid sorbents to sequester dyes or the use of biochemical or chemical methods of dye degradation. However, these processes typically generate their own waste products, are not necessarily rapid because of the low dye concentration, and often use expensive or non-recyclable sequestrants or reagents. This paper describes a simple, recyclable, liquid–liquid extraction scheme where ionic dyes can be sequestered into poly(α-olefin) (PAO) solvent systems. The partitioning of anionic and cationic dyes from water into PAOs is facilitated by ionic PAO-phase anchored sequestering agents that are readily prepared from commercially available vinyl-terminated polyisobutylene (PIB). This is accomplished by a sequence of reactions involving hydroboration/oxidation, conversion of an alcohol into an iodide, and conversion of the resulting primary alkyl iodide into a cationic nitrogen derivative. The products of this synthetic sequence are cationic nitrogen iodide salts which serve as anionic sequestrants that are soluble in PAO. These studies showed that the resulting series of cationic PIB-bound cationic sequestering agents facilitated efficient extraction of anionic, azo, phthalein, and sulfonephthalein dyes from water into a hydrocarbon PAO phase. Since the hydrocarbon PAO phase is completely immiscible with water and the PIB derivatives are also insoluble in water, neither the sequestration solvent nor the sequestrants contaminate wastewater. The effectiveness and efficiency of these sequestrations were assayed by UV–visible spectroscopy. These spectroscopic studies showed that extraction efficiencies were in most cases >99%. These studies also involved procedures that allowed for the regeneration and recycling of these PAO sequestration systems. This allowed us to recycle the PAO solvent system for at least 10 sequential batch extractions where we sequestered sodium salts of methyl red and 4′,5′-dichlorofluorescein dyes from water with extraction efficiencies of >99%. These studies also showed that a PIB-bound derivative of the sodium salt of 1,1,1-trifluoromethylpentane-2,4-dione could be prepared from a PIB-bound carboxylic acid ester by a Claisen-like reaction and that the sodium salt of this β-diketone could be used to sequester cationic dyes from water. This PIB-bound anion rapidly and efficiently extracted >99% of methylene blue, malachite green, and safranine O from water based on UV–visible and 1H NMR spectroscopic assays. Full article
(This article belongs to the Section Environmental Technology)
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18 pages, 2860 KiB  
Article
Initial Litter Chemistry and UV Radiation Drive Chemical Divergence in Litter during Decomposition
by Bei Yao, Xiangshi Kong, Kai Tian, Xiaoyi Zeng, Wenshuo Lu, Lu Pang, Shucun Sun and Xingjun Tian
Microorganisms 2024, 12(8), 1535; https://doi.org/10.3390/microorganisms12081535 - 27 Jul 2024
Cited by 1 | Viewed by 1202
Abstract
Litter’s chemical complexity influences carbon (C) cycling during its decomposition. However, the chemical and microbial mechanisms underlying the divergence or convergence of chemical complexity under UV radiation remain poorly understood. Here, we conducted a 397-day field experiment using 13C cross-polarization magic-angle spinning [...] Read more.
Litter’s chemical complexity influences carbon (C) cycling during its decomposition. However, the chemical and microbial mechanisms underlying the divergence or convergence of chemical complexity under UV radiation remain poorly understood. Here, we conducted a 397-day field experiment using 13C cross-polarization magic-angle spinning nuclear magnetic resonance (13C-CPMAS NMR) to investigate the interactions among the initial chemistry, microbial communities, and UV radiation during decomposition. Our study found that the initial concentrations of O-substituted aromatic C, di-O-alkyl C, and O-alkyl C in Deschampsia caespitosa were higher than those in Kobresia tibetica. Litter’s chemical composition exhibited divergent patterns based on the initial chemistry, UV radiation, and decay time. Specifically, D. caespitosa consistently displayed higher concentrations of di-O-alkyl C and O-alkyl C compared to K. tibetica, regardless of the UV exposure and decay time. Additionally, litter’s chemical complexity was positively correlated with changes in the extracellular enzyme activities, particularly those involved in lignin, cellulose, and hemicellulose degradation, which accounted for 9%, 20%, and 4% of the variation in litter’s chemical complexity, respectively. These findings highlighted the role of distinct microbial communities in decomposing different C components through catabolism, leading to chemical divergence in litter. During the early decomposition stages, oligotrophic Planctomycetes and Acidobacteria metabolized O-alkyl C and di-O-alkyl C under UV-blocking conditions. In contrast, copiotrophic Actinobacteria and Chytridiomycota utilized these components under UV radiation exposure, reflecting their ability to thrive under UV stress conditions due to their rapid growth strategies in environments rich in labile C. Our study revealed that the inherent differences in the initial O-alkyl C and di-O-alkyl C contributed to the chemical divergence, while UV radiation further influenced this divergence by shifting the microbial community composition from oligotrophic to copiotrophic species. Thus, differences in the initial litter chemistry, microbial community, and UV radiation affected the quantity and quality of plant-derived C during decomposition. Full article
(This article belongs to the Section Microbial Biotechnology)
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20 pages, 8247 KiB  
Article
Fabrication of Polycaprolactone-Based Polyurethanes with Enhanced Thermal Stability
by Jasna V. Džunuzović, Ivan S. Stefanović, Enis S. Džunuzović, Tijana S. Kovač, Dušan P. Malenov, Andrea Basagni and Carla Marega
Polymers 2024, 16(13), 1812; https://doi.org/10.3390/polym16131812 - 26 Jun 2024
Cited by 5 | Viewed by 2255
Abstract
The benefit of being acquainted with thermal properties, especially the thermal stability of polyurethanes (PU), and simplified methods for their improvement is manifold. Considering this, the effect of embedding different amounts of unmodified and surface-modified TiO2 nanoparticles (NPs) within PU, based on [...] Read more.
The benefit of being acquainted with thermal properties, especially the thermal stability of polyurethanes (PU), and simplified methods for their improvement is manifold. Considering this, the effect of embedding different amounts of unmodified and surface-modified TiO2 nanoparticles (NPs) within PU, based on polycaprolactone (PCL) and Boltorn® aliphatic hyperbranched polyester, on PU properties was investigated. Results obtained via scanning electron microscopy, swelling measurements, mechanical tests and thermogravimetric analysis revealed that TiO2 NPs can be primarily applied to improve the thermal performance of PU. Through surface modification of TiO2 NPs with an amphiphilic gallic acid ester containing a C12 long alkyl chain (lauryl gallate), the impact on thermal stability of PU was greater due to the better dispersion of modified TiO2 NPs in the PU matrix compared to the unmodified ones. Also, the distinct shape of DTG peaks of the composite prepared using modified TiO2 NPs indicates that applied nano-filler is mostly embedded in soft segments of PU, leading to the delay in thermal degradation of PCL, simultaneously improving the overall thermal stability of PU. In order to further explore the thermal degradation process of the prepared composites and prove the dominant role of incorporated TiO2 NPs in the course of thermal stability of PU, various iso-conversional model-free methods were applied. The evaluated apparent activation energy of the thermal degradation reaction at different conversions clearly confirmed the positive impact of TiO2 NPs on the thermal stability and aging resistance of PU. Full article
(This article belongs to the Special Issue Polyurethane Materials for Multifunctional Applications)
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34 pages, 4088 KiB  
Review
Magnetic Iron Oxide Nanomaterials for Lipase Immobilization: Promising Industrial Catalysts for Biodiesel Production
by Farid Hajareh Haghighi, Roya Binaymotlagh, Cleofe Palocci and Laura Chronopoulou
Catalysts 2024, 14(6), 336; https://doi.org/10.3390/catal14060336 - 22 May 2024
Cited by 8 | Viewed by 2414
Abstract
Biodiesel is a mixture of fatty acid alkyl esters (FAAEs) mainly produced via transesterification reactions among triglycerides and short-chain alcohols catalyzed by chemical catalysts (e.g., KOH, NaOH). Lipase-assisted enzymatic transesterification has been proposed to overcome the drawbacks of chemical synthesis, such as high [...] Read more.
Biodiesel is a mixture of fatty acid alkyl esters (FAAEs) mainly produced via transesterification reactions among triglycerides and short-chain alcohols catalyzed by chemical catalysts (e.g., KOH, NaOH). Lipase-assisted enzymatic transesterification has been proposed to overcome the drawbacks of chemical synthesis, such as high energy consumption, expensive separation of the catalyst from the reaction mixture and production of large amounts of wastewater during product separation and purification. However, one of the main drawbacks of this process is the enzyme cost. In recent years, nano-immobilized lipases have received extensive attention in the design of robust industrial biocatalysts for biodiesel production. To improve lipase catalytic efficiency, magnetic nanoparticles (MNPs) have attracted growing interest as versatile lipase carriers, owing to their unique properties, such as high surface-to-volume ratio and high enzyme loading capacity, low cost and inertness against chemical and microbial degradation, biocompatibility and eco-friendliness, standard synthetic methods for large-scale production and, most importantly, magnetic properties, which provide the possibility for the immobilized lipase to be easily separated at the end of the process by applying an external magnetic field. For the preparation of such effective magnetic nano-supports, various surface functionalization approaches have been developed to immobilize a broad range of industrially important lipases. Immobilization generally improves lipase chemical-thermal stability in a wide pH and temperature range and may also modify its catalytic performance. Additionally, different lipases can be co-immobilized onto the same nano-carrier, which is a highly effective strategy to enhance biodiesel yield, specifically for those feedstocks containing heterogeneous free fatty acids (FFAs). This review will present an update on the use of magnetic iron oxide nanostructures (MNPs) for lipase immobilization to catalyze transesterification reactions for biodiesel production. The following aspects will be covered: (1) common organic modifiers for magnetic nanoparticle support and (2) recent studies on modified MNPs-lipase catalysts for biodiesel production. Aspects concerning immobilization procedures and surface functionalization of the nano-supports will be highlighted. Additionally, the main features that characterize these nano-biocatalysts, such as enzymatic activity, reusability, resistance to heat and pH, will be discussed. Perspectives and key considerations for optimizing biodiesel production in terms of sustainability are also provided for future studies. Full article
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