Search Results (89)

The slow swelling rate of styrene–butadiene–styrene (SBS) in asphalt prolongs the modification process and increases energy consumption. This study proposes a novel method using benzoyl peroxide (BPO) and benzoyl methane (BPA) to accelerate SBS swelling through a radical initiation–capture mechanism. BPO generates free radicals that relax the SBS network, while BPA captures excess radicals, maintaining system stability. Molecular dynamics simulations based on the COMPASS II force field were used to analyse diffusion, radius of gyration, and solubility parameters, revealing that BPO/BPA improved SBS–asphalt compatibility and increased the diffusion coefficient by 76%. Macroscopic viscosity tests confirmed that the swelling time decreased by 40% and equilibrium viscosity increased by 39% compared with the conventional process. The modified asphalt also exhibited enhanced high- and low-temperature performance and ageing resistance. This simple and efficient synergistic technique provides a promising approach for the rapid preparation of SBS-modified asphalt and offers practical potential for industrial production. Full article

Rubber material with high elasticity and viscoelasticity has become the most widely used universal material, and the study of the aging failure mechanism of rubber has been meaningful research in the polymer materials field. Cis-polyisoprene was employed to analyze the mechanism of oxidative degradation under artificial UV irradiation, and the GQDs/g-C₃N₄ photocatalysis with a 2D layered structure prepared by the method of microwave-assisted polymerization enabled to accelerate the degradation procedure. The results showed that the oxidation of cis-polyisoprene occurred during the irradiation for 3 days and the structure of cis-polyisoprene changed. The α-H of the double bond was attacked by oxygen to form hydroperoxide. Then, aldehydes and ketones generated as the addition reaction of double bonds occurred. The content of the hydrogen of C=C reduced, and the oxidative degradation was dominant at the initial aging stage. The crosslinking reaction was dominant at the final aging stage and the average molecular weight decreased from 15.49 × 10⁴ to 8.78 × 10⁴. The GQDs could promote the charge transfer and the photodegradation efficiency and inhibit the electron–hole recombination. The light capture ability of GQDs was improved after compositing with g-C₃N₄. The free radicals ·O₂²⁻ generated after adding GQDs/g-C₃N₄ nanoparticles, and the molecular weight of cis-polyisoprene decreased to 5.79 × 10⁴, with the photocatalytic efficiency increasing by 20%. This work provided academic bases and reference values for the application of photocatalysts in the field of natural rubber degradation and rubber wastewater treatment. Full article

Four different MIL-68(Al) catalysts were synthesized and characterized by XPS, SEM, TEM, XRD, DLS, Nitrogen adsorption removal, and other methods. An aluminum-based MOF (Metal Organic Framework) (MIL-68(Al))/graphite oxide (GO) composite with TiO₂ showed the largest BET specific area with best adsorption performance. Representation demonstrated that MIL-68(Al) and TiO₂ nanoparticles are uniformly dispersed on the surface of the GO lamellar, and a tight heterojunction structure is formed between them. The MIL-68(Al)/GO/TiO₂ exhibits good pore characteristics, structural morphology, and catalytic performance. Adsorption experiments of methyl orange can reach 99.7% with the effect of MIL-68(Al)/GO/TiO₂ in water for 20 min. Moreover, the pH range can be applied to 1–13 and a high concentration of 200 mg/L methyl orange solution also worked well. In addition, this kind of catalyst can also be used for rhodamine B, methylene blue, congo red, and tetracycline in 20 min with good adsorption. Meanwhile, simple filtration can quickly recover MIL-68(Al)/GO/TiO₂ and effectively reuse it. Free radical capture experiments showed a large number of •OH radicals during the adsorption of MO (Methyl Orange) solution by MIL-68(Al)/GO/TiO₂. Meanwhile, the electrostatic interaction, π-π packing and hydrogen bonding make MIL-68(Al)/GO/TiO₂ have a higher adsorption capacity for MO. Therefore, co-doping optimized the structure of MIL-68(Al), enhancing its stability in strong acids and bases while improving adsorption performance across a broader pH range than previously reported. This work addresses the instability of MIL-68(Al) under extreme conditions, demonstrating its significant potential for wastewater treatment applications. Full article

A novel composite material comprising titanium dioxide and layered double hydroxides (TiO₂/LDHs) was innovatively proposed and prepared using the co-precipitation method to overcome the shortcomings of titanium dioxide, such as low efficiency in separating electron–hole pairs induced by light and a low utilization rate of visible light. This material was used to study the visible-light-driven photocatalytic degradation of methylene blue. The experimental results show that by constructing efficient heterojunction structures through the alignment of interface band energies and regulating the interface charge transfer pathways, the recombination rate of photogenerated electron–hole pairs is significantly reduced, and the photocatalytic activity is greatly enhanced. Among the tested samples, the TiO₂/LDHs composite material with an aluminum-to-titanium molar ratio of 1:1 (AT11) demonstrated the best photocatalytic performance. Within 70 min of simulated sunlight exposure, the degradation rate of methylene blue reached 98.2%, and the optimal concentration of the catalyst was 1 g/L. The photocatalytic process follows a first-order kinetic model. After four cycles of use, the degradation efficiency of methylene blue by the AT11 composite material was 78.93%, demonstrating good stability. The free radical capture experiments indicated that the main active substances for the photocatalytic degradation of methylene blue were h⁺ and ·OH. The constructed TiO₂/LDHs heterostructure system significantly enhanced the photocatalytic performance of TiO₂ materials, which was conducive to the efficient utilization of solar energy. Full article

Protein phosphorylation is one of the most common and important post-translational modifications (PTMs) and is highly involved in various biological processes. Ideal adsorbents with high sensitivity and specificity toward phosphopeptides with large coverage are therefore essential for enrichment and mass spectroscopy-based phosphoproteomics analysis. In this study, a newly designed IMAC adsorbent composite was constructed on the graphene matrix coated with mesoporous silica. The outer functional 3D-network layer was prepared by free radical polymerization of the phosphonate-functionalized vinyl imidazolium salt monomer and subsequent metal immobilization. Due to its unique structural feature and high content of Ti⁴⁺ ions, the resulting phosphonate-immobilized adsorbent composite G@mSiO₂@PPFIL-Ti⁴⁺ exhibits excellent performance in phosphopeptide enrichment with a low detection limit (0.1 fmol, tryptic β-casein digest) and superior selectivity (molar ratio of 1:15,000, digest mixture of β-casein and bovine serum albumin). G@mSiO₂@PPFIL-Ti⁴⁺ displays high tolerance to loading and elution conditions and thus can be reused without a marked decrease in enrichment efficacy. The captured phosphopeptides can be released globally, and mono-/multi-phosphopeptides can be isolated stepwise by gradient elution. When applying this material to enrich phosphopeptides from human lung cell lysates, a total of 3268 unique phosphopeptides were identified, corresponding to 1293 phosphoproteins. Furthermore, 2698 phosphorylated peptides were found to be differentially expressed (p < 0.05) between human lung adenocarcinoma cells (SPC-A1) and human normal epithelial cells (Beas-2B), of which 1592 were upregulated and 1106 were downregulated in the cancer group. These results demonstrate the material’s superior enrichment efficiency in complex biological samples. Full article

In this study, we use coal as a carbon source from Zhangjiamao and doped with different nitrogen sources for co-pyrolysis. Nitrogen-rich tar was successfully prepared, and the content and variety were also increased. From the elemental analysis, the nitrogen content of all the tars was significantly enhanced, among which the nitrogen content of the tars after co-pyrolysis with melamine was enhanced by 5.21%, and the nitrogen content of coke was enhanced by 10.87%. According to the GC/MS results, it was found that the nitrogen compounds in the tar after full pyrolysis were richer and more abundant than those in Py-GC/MS. For the free radical reaction, the reaction process is extremely rapid, and the ¹⁵N substitution product after isotope labeling was successfully captured by adding ¹⁵NH₄Cl for isotope labeling, which can be more intuitively and accurately illustrated from the m/z change. Among them, 26 nitrogen-containing compounds were screened out, which accounted for 66.28% of the content, and they were categorized. It was found that the five-membered nitrogen heterocycles were the most abundant, accounting for 34.88%. In addition, five other nitrogen-containing compounds containing different functional groups and the tar from the co-pyrolysis of tar-rich coal were also analyzed by GC/MS, among which the tar from melamine had the highest content of nitrogen-containing compounds, with 70.48%. Finally, the functional groups of nitrogen-containing compounds were further analyzed by XPS and FTIR, and the results were consistent with those of GC/MS analysis. In this paper, nitrogen-rich tar was prepared by co-pyrolysis of tar-rich coal and nitrogen compounds. This achievement provides a valuable reference for the high-value utilization of coal tar. Full article

Antioxidants, such as stilbenes, anthocyanidins, coumarins, tannins and flavonoids, are often based on oxygen-containing redox systems and tend to feature several hydroxyl groups in their chemical structures. From a synthetic perspective, oxygen atoms are prone to bioisosteric replacement with sulfur and, notably, selenium. The main objective of this narrative literature review is to explore if and how bioisosteric substitution of oxygen with sulfur or selenium can enhance the biological activity of natural products. This replacement boosts the biological activity of the resulting molecules considerably as they now combine the redox and antioxidant properties of the original flavonoids and other natural products with the specific redox behavior of sulfur and selenium. Besides sequestering free radicals and peroxides, they may, for instance, also catalyze the removal of oxidative stressors, capture free metal ions and even provide scope for selenium supplementation. Since these molecules resemble their natural counterparts, they also exhibit considerable selectivity inside the body and a good pharmacokinetic profile. Still, the synthesis of such hybrid molecules integrating sulfur and selenium into flavonoids and other natural products is a challenge and requires innovative synthetic strategies and approaches. Full article

CO₂-responsive polymers have emerged as a significant class of smart materials, distinguished by their ability to reversibly alter their properties upon exposure to CO₂. Due to CO₂’s abundant availability, low cost, non-toxicity, energy efficiency, and excellent biocompatibility, these polymers offer remarkable environmental and practical advantages. This review succinctly explores recent advancements in the synthesis, mechanisms, and applications of CO₂-responsive polymers, emphasizing the pivotal roles of specific acidic and basic functional groups such as carboxylic acids, phenolic groups, amines, amidines, guanidines, and imidazoles. Advanced polymerization techniques including free radical polymerization (FRP), atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT), and nitroxide-mediated polymerization (NMP) are critically evaluated for their precision and flexibility in polymer design. Significant applications in smart separation, carbon capture, drug delivery, desalination, emulsions, tissue engineering, and sensing technologies are discussed comprehensively. Although substantial progress has been made, ongoing challenges include enhancing response speed, durability, sustainability, and economic viability. Future research is recommended to focus on innovative polymer structures, computational modeling, hybrid materials, and greener synthesis methods. This review aims to inspire continued exploration and practical utilization of CO₂-responsive polymers to address pressing environmental and technological needs. Full article

Background: Eugenia involucrata DC., a Cerrado native plant, is recognized for its medicinal properties. However, its bioactive compounds remain inadequately explored. Objectives: This study investigated bioactive compounds from a standardized liquid extract from E. involucrata leaves that can act with antioxidant, cytogenotoxic, cytoprotective, and genoprotective effects. Methods: The phenolic compounds in the standardized liquid extract from E. involucrata leaves were screened by HPLC-DAD. The capture of the free radicals DPPH, ABTS⁺, and the metal reduction power FRAP determined the antioxidant potential. Cytotoxicity was evaluated in RAW 264.7 macrophages (MTT assay), and (anti)cytotoxic and (anti)genotoxic effects were assessed in human lymphocytes using the Trypan blue exclusion method and comet assay, respectively. Results: The extracts present key phenolic compounds, such as ellagic acid, myricitrin, and epicatechin gallate. The standardized extract demonstrated antioxidant capacity, evidenced by its ability to reduce iron and scavenge free radicals. The liquid extract from E. involucrata leaves exhibited cytotoxic effects on RAW 264.7 macrophages at higher concentrations, while demonstrating (anti)cytotoxic activity on human lymphocytes from all tested concentrations. The highest concentration tested of the standardized liquid extract from E. involucrata leaves (250 µg/mL) showed genotoxicity against human lymphocytes compared to the negative control. In contrast, the lowest concentration (62.5 µg/mL) exhibited an antigenotoxic effect on human lymphocytes, reducing the genotoxicity of doxorubicin by approximately 27%. Conclusions: The bioactive compounds in the standardized liquid extract from E. involucrata leaves exhibited antioxidant and antigenotoxic properties, suggesting potential value for nutraceutical and pharmaceutical applications, particularly those related to oxidative stress associated withaging and disease progression. Full article

The removal of polychlorinated dibenzo-p-dioxins (PCDDs) via advanced oxidation processes (AOPs) poses a significant challenge due to their high toxicity and chemical stability. In this study, a series of well-dispersed cobalt nanoparticles supported on carbon nitrides (xCoCNs) was synthesized to activate peroxymonosulfate (PMS) for 2,8-dichlorodibenzo-p-dioxin (2,8-DCDD) degradation under visible light. The catalysts prepared were characterized using SEM, XPS, photoluminescence (PL), and UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS). Among them, 2CoCN with an optimal Co content exhibited the highest photocatalytic efficiency, achieving 90.5% degradation of 2,8-DCDD within 160 min under visible light/persulfate oxidation (Vis+PMS+2CoCN system). Compared with other catalysts, 2CoCN exhibited superior optical performance and a narrower bandgap, enabling efficient excitation under visible light (Vis). Notably, all xCoCNs demonstrated pH adaptability, achieving complete degradation of 2,8-DCDD under neutral conditions (pH = 7) without additional acid/alkali adjustment. Through rigorous free radical capture experiments, it was demonstrated that SO₄^•−, ^•OH and ¹O₂ were the primary reactive oxygen species (ROS) in the Vis+PMS+2CoCN system. The catalyst exhibited excellent reusability, with stable activity retained over five cycles. Based on these findings, degradation pathways and mechanisms of 2,8-DCDD in the 2CoCN+Vis+PMS system were proposed. This study presents an effective approach for PCDD abatement in wastewater treatment applications. Full article

Chronic wound healing remains a major challenge in diabetes management due to prolonged inflammation, autonomic neuropathy, and bacterial infections. In particular, multidrug-resistant bacterial infections are important to the development of diabetic wounds, leading to persistent inflammation and delayed healing. To address this issue, we developed a self-adaptive nanozyme designed to modulate infectious and inflammatory microenvironments by doping Ce and Ag into mesoporous silicon nanomaterials (MSNs). The resulting CA@MSNs exhibited strong bacterial capture capabilities via electrostatic attraction. Additionally, the synergistic effects of Ce and Ag endowed CA@MSNs with peroxidase (POD)-like activity, enabling the generation of reactive oxygen species (ROS) to eradicate bacteria in infectious microenvironments. Notably, CA@MSNs also demonstrated the ability to scavenge a broad spectrum of ROS, including hydroxyl free radicals, hydrogen peroxide, and superoxide radicals, in inflammatory microenvironments. This dual functionality helped mitigate inflammation and promote endothelial cell migration. Consequently, treatment with CA@MSNs significantly reduced inflammation, enhanced fibroblast activation, and facilitated collagen deposition, ultimately accelerating the healing of methicillin-resistant Staphylococcus aureus (MRSA)-infected wounds in diabetic mice. In conclusion, this study presents a promising therapeutic strategy for chronic diabetic wounds, offering a novel approach to overcoming infection-related healing delays. Full article

This study evaluated the antioxidant capacity of the oxidation products of three flavonols using oxygen radical absorbance capacity—fluorescein assay (ORAC-FL), oxygen radical absorbance capacity—pyrogallol red assay (ORAC-PGR), and the cellular antioxidant activity (CAA) assay in human dermal fibroblast (HFF) cells, with 2,2’-azobis(2-amidinopropane) dihydrochloride (AAPH) as a free radical generator under controlled pH and solvent conditions. At pH 2 in a polar aprotic solvent, BZF-OH (benzofuranone-OH) compounds were formed, while methoxylated analogs were obtained at pH 7 in a polar protic solvent. The products generated at pH 2 exhibited significantly higher antioxidant capacities, demonstrating the influence of the reaction environment on modulating antioxidant properties. The antioxidant activity was observed to reflect the combined action of the flavonol precursor and its oxidation products. This led to the proposal of the Gross Antioxidant Capacity (GAC) concept to integrate the contribution of all generated species. Since chemical assays such as ORAC do not fully capture the complexity of biological systems, they should be complemented with cellular approaches for a more accurate evaluation. Additionally, BZF-OH compounds were analyzed as potential cyclooxygenase-2 (COX-2) inhibitors through docking and molecular dynamics simulations, where BZF-Quer-OH showed binding affinities comparable to celecoxib, a selective COX-2 inhibitor. These findings were complemented by an analysis of COX-2 expression in RAW 264.7 cells treated with lipopolysaccharide (LPS), where treatment with the antioxidants significantly inhibited COX-2 expression. In the case of the oxidation products, only the oxidation product of rhamnetin showed a reduction in COX-2 expression compared to the LPS-treated control. Together, these results highlight that flavonol-derived oxidation products not only retain significant antioxidant capacity but may also possess anti-inflammatory properties, opening new perspectives for the development of innovative therapies targeting oxidative stress and chronic inflammation. Full article

Nickel-doped titanium dioxide (NIT) with different nickel contents (0.1–1.0 wt%) was prepared via the sol–gel method, combined with mechanical ball milling. X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV–Vis diffuse reflectance spectroscopy (DRS) were employed to characterize the crystalline structure, morphological characteristics, and optical properties of the samples. The photocatalytic activity was evaluated through the photocatalytic degradation of methylene blue (MB) under visible light and nitric oxide (NO) under simulated sunlight. The XRD results show that all the catalysts retain the anatase phase, confirming that nickel doping does not alter the crystalline structure of TiO₂. NIT catalysts exhibited a plate-like morphology due to the ball milling treatment of the precursors. The DRS analysis revealed that nickel modification induced a redshift in the absorption edge of TiO₂ and enhanced the visible-light absorption. The photocatalytic tests demonstrated that 0.5 wt% NIT and 0.7 wt% NIT exhibited the highest photocatalytic activity for MB degradation, achieving degradation rates of 93.1% and 91.4% after 60 min, respectively. Moreover, 0.7 wt% NIT showed the optimal NO conversion efficiency of 45.4% after 30 min. The improved photocatalytic performance of the sample is attributed to enhanced visible-light absorption, reduced charge recombination, and a high specific surface area. This study provides a facile strategy for synthesizing Ni-doped TiO₂ nanoplates based on the sol–gel method, which is scalable in regard to the industrial production of efficient photocatalysts. Full article

The utilization of the photo catalytic activation of permonosulfate (PMS) for the combined breakdown of pollutants has become a focal point in research. Layered double hydroxides (LDHs) have a unique layered structure which is conducive to the adsorption and diffusion of reactants, and can provide more active sites for photocatalytic reactions. The anions between the layers can be exchanged with a variety of substances so that specific catalytically active species can be introduced as needed. LDHs themselves have certain catalytic activity, which can produce synergistic catalysis between LDHs and the supported photocatalytic active substances, and further improve the degradation effect of antibiotics. In actual wastewater treatment, LDHs as a catalyst carrier have a good application prospect. However, the poor activation effect is attributed to the low separation efficiency of catalyst carriers and insufficient active sites. In this study, a dual active site system consisting of Co and Fe, known as CoFe-LDHs@MoS₂, was developed as a catalyst to facilitate the synergistic degradation of norfloxacin (NOF) by PMS under visible light. The findings demonstrate that the material possesses an effective capacity for the synergistic degradation of NOF. A comprehensive investigation was conducted to assess the impact of different catalysts, PMS dosage, degradation systems (Vis, PMS, or Vis PMS), catalyst dosage, NOF concentration, pH, and cycle times on the degradation performance. The active free radicals, degradation pathways, and intermediate toxicity were elucidated through capture experiments, Electron Paramagnetic Resonance Spectrometer (ESR) analysis, a liquid mass spectrometry (LC-MS) toxicity assessment, and theoretical calculations. This research offers a novel approach for designing catalysts with exposed high activity sites for the effective removal of NOF from environmental water. Full article

A series of commercial silica-supported polyoxometalate ionic liquids ([C_nmim]₃PMo₁₂O₄₀) with different substitutes in the imidazole ring were prepared via a facile ball milling method and employed as catalysts in the oxidative desulfurization of organosulfur compounds. The experimental results demonstrated that the active polyoxometalate center was successfully immobilized with a highly uniform dispersion on the silica. Without any organic solvent as the extractant, sulfur removal with the sample C₁₆PMo/SiO₂-BM reached 99.5% in 30 min under the optimal condition, which was ascribed to the high specific surface area and lipophilicity. In addition, the active site was verified by a free radical trapping experiment and an ESR spin capture experiment. In addition, the oxidative product was confirmed by GC-MS analysis. Full article