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1.
J Colloid Interface Sci ; 674: 416-427, 2024 Jun 24.
Artigo em Inglês | MEDLINE | ID: mdl-38943909

RESUMO

Peroxymonosulfate (PMS) could be activated by either radical path or non-radical path, how to rationally mediate these two routines was an important unresolved issue. This work has introduced a simple way to address this problem via metal atom doping. It was found that Fe-doped nitrogen-rich graphitic carbon nitride (Fe-C3N5) exhibited high activity towards PMS activation for tetracycline degradation, and the degradation rate was 3.14 times higher than that of Co-doped nitrogen-rich graphitic carbon nitride (Co-C3N5). Radical trapping experiment revealed the contributions of reactive species over two catalysts were different. Electron paramagnetic resonance analysis further uncovered the non-radical activation path played a dominated role on Fe-C3N5 surface, while the radical activation path was the main routine on Co-C3N5 surface. Density functional theory calculations, X-ray photoelectron spectroscopy analysis, and electrochemical experiments provided convincing evidence to support these views. This study supplied a novel method to mediate PMS activation path via changing the doped metal atom in g-C3N5 skeleton, and it allowed us to better optimize the PMS activation efficiency.

2.
Chemosphere ; 361: 142518, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38830463

RESUMO

Fe-based metal-organic frameworks (MOFs) have good photocatalytic performance, environmental friendliness, low cost, and abundance. However, their applications are limited by low water stability, particularly in the presence of light irradiation and oxidizing agents. In this study, we present a MIL-53(Fe)-based MOF using 1,4-naphthalene dicarboxylic (1,4-NDC) and 1,4-benzenedicarboxylic (H2BDC) acid co-ligands, denoted MIL-53(Fe)-Nx, where Nx represents the ratio of 1,4-NDC. This MOF exhibits high water stability and good photocatalytic activity because of the hydrophobicity of naphthalene. The removal and mineralization rates for 100 mg/L 2,4-dichlorophenol reached 100% and 22%, respectively, within 60 min. After three cycles of use, the Fe leached into the solution from the catalysts was significantly lower than the maximum permissible limit indicated in the European Union standard. Of note, 1,4-NDC can be used to make a rigid MOF, thereby improving the crystallinity, porosity, and hydrophobicity of the resultant materials. It also significantly reduced the bandgap energy and improved the charge separation efficiency of the catalysts. This study provides a route to enhance the water stability of Fe-based MOFs via a mixed-ligand strategy to expand their applications in pollutant control.


Assuntos
Clorofenóis , Ferro , Estruturas Metalorgânicas , Poluentes Químicos da Água , Estruturas Metalorgânicas/química , Clorofenóis/química , Catálise , Poluentes Químicos da Água/química , Ferro/química , Água/química , Ligantes
3.
Environ Sci Technol ; 58(24): 10852-10862, 2024 Jun 18.
Artigo em Inglês | MEDLINE | ID: mdl-38843408

RESUMO

The Cu(II)/H2O2 system is recognized for its potential to degrade recalcitrant organic contaminants and inactivate microorganisms in wastewater. We investigated its unique dual oxidation strategy involving the selective oxidation of copper-complexing ligands and enhanced oxidation of nonchelated organic compounds. L-Histidine (His) and benzoic acid (BA) served as model compounds for basic biomolecular ligands and recalcitrant organic contaminants, respectively. In the presence of both His and BA, the Cu(II)/H2O2 system rapidly degraded His complexed with copper ions within 30 s; however, BA degraded gradually with a 2.3-fold efficiency compared with that in the absence of His. The primary oxidant responsible was the trivalent copper ion [Cu(III)], not hydroxyl radical (•OH), as evidenced by •OH scavenging, hydroxylated BA isomer comparison with UV/H2O2 (a •OH generating system), electron paramagnetic resonance, and colorimetric Cu(III) detection via periodate complexation. Cu(III) selectively oxidized His owing to its strong chelation with copper ions, even in the presence of excess tert-butyl alcohol. This selectivity extended to other copper-complexing ligands, including L-asparagine and L-aspartic acid. The presence of His facilitated H2O2-mediated Cu(II) reduction and increased Cu(III) production, thereby enhancing the degradation of BA and pharmaceuticals. Thus, the Cu(II)/H2O2 system is a promising option for dual-target oxidation in diverse applications.


Assuntos
Cobre , Histidina , Peróxido de Hidrogênio , Oxirredução , Cobre/química , Histidina/química , Peróxido de Hidrogênio/química , Catálise , Ferro/química , Radical Hidroxila/química , Ácido Benzoico/química
4.
J Colloid Interface Sci ; 674: 9-18, 2024 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-38908062

RESUMO

Disulfiram (DSF) metabolites exhibit antitumor properties when bound to Cu2+. This combination also promotes the generation of reactive oxygen species (ROS), ultimately leading to tumor cell death. In this study, CuO2 served as a carrier for DSF, forming a dual-drug delivery system with Cu2+ and DSF encapsulated in polydopamine (PDA). In the final delivery system, CuO2 (DSF-CuO2@PDA) was hydrolyzed at the tumor site, releasing both Cu2+ and H2O2. Cu2+ reacts with DSF metabolites to form Bis(diethyldithiocarbamate)-Cu (CuET), which triggers a Fenton-like reaction that generates ROS. Chemotherapy and chemodynamic therapy exhibited significant tumor-suppressive capabilities, with an inhibition rate of 61 %. In addition, the DSF-CuO2@PDA complex demonstrated superlative tumor-targeting ability and biocompatibility.

5.
J Colloid Interface Sci ; 674: 279-288, 2024 Jun 24.
Artigo em Inglês | MEDLINE | ID: mdl-38936084

RESUMO

Rational design of coordination environment of Fe-based metal-organic frameworks (Fe-MOFs) is still a challenge in achieving enhanced catalytic activity for Fenten-like advanced oxidation process. Here in, novel porous Fe-MOFs with modulated O-Fe-N coordination was developed by configurating amino terephthalic acid (H2ATA) and pyrazine-dicarboxylic acid (PzDC) (Fe-ATA/PzDC-7:3). PzDC ligands introduce pyridine-N sites to form O-Fe-N coordination with lower binding energy, which affect the local electronic environment of Fe-clusters in Fe-ATA, thus decreased its interfacial H2O2 activation barrier. O-Fe-N coordination also accelerate Fe(II)/Fe(III) cycling of Fe-clusters by triggering the reactive oxidant species mediated Fe(III) reduction. As such, Fe-ATA/PzDC-7:3/H2O2 system exhibited excellent degradation performance for typical antibiotic sulfamethoxazole (SMX), in which the steady-state concentration of hydroxyl radical (OH) was 1.6 times higher than that of unregulated Fe-ATA. Overall, this study highlights the role of O-Fe-N coordination and the electronic environment of Fe-clusters on regulating Fenton-like catalytic performance, and provides a platform for precise engineering of Fe-MOFs.

6.
Angew Chem Int Ed Engl ; : e202407870, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38748475

RESUMO

Converting spent lithium-ion batteries (LIBs) cathode materials into environmental catalysts has drawn more and more attention. Herein, we fabricated a Co3O4-based catalyst from spent LiCoO2 LIBs (Co3O4-LIBs) and found that the role of Al and Cu from current collectors on its performance is nonnegligible. The density functional theory calculations confirmed that the doping of Al and/or Cu upshifts the d-band center of Co. A Fenton-like reaction based on peroxymonosulfate (PMS) activation was adopted to evaluate its activity. Interestingly, Al doping strengthened chemisorption for PMS (from -2.615 eV to -2.623 eV) and shortened Co-O bond length (from 2.540 Å to 2.344 Å) between them, whereas Cu doping reduced interfacial charge-transfer resistance (from 28.347 kΩ to 6.689 kΩ) excepting for the enhancement of the above characteristics. As expected, the degradation activity toward bisphenol A of Co3O4-LIBs (0.523 min-1) was superior to that of Co3O4 prepared from commercial CoC2O4 (0.287 min-1). Simultaneously, the reasons for improved activity were further verified by comparing activity with catalysts doped Al and/or Cu into Co3O4. This work reveals the role of elements from current collectors on the performance of functional materials from spent LIBs, which is beneficial to the sustainable utilization of spent LIBs.

7.
J Colloid Interface Sci ; 670: 297-310, 2024 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-38763026

RESUMO

Fenton/Fenton-like reaction induced chemical dynamic therapy (CDT) has been widely recognized in tumor therapy. Due to the low efficiency of conversion from high-valent metal ions (M(n+1)+) to low-valent ions (Mn+) in the Fenton/Fenton-like catalytic process, enhancing the conversion efficiency safely and effectively would create a great opportunity for the clinical application of CDT. In the study, a universal nanoreactor (NR) consisting of liposome (Lip), tumor cell membrane (CM), and bis(2,4,5-trichloro-6-carboxyphenyl) oxalate (CPPO) is developed to tackle this challenge. The CPPO was first discovered to decompose under weak acidity and H2O2 conditions to generate carboxylic acids (R'COOH) and alcohols (R'OH) with reducibility, which will reduce M(n+1)+ to Mn+ and magnify the effect of CDT. Furthermore, glucose oxidase (GOx) was introduced to decompose glucose in tumor and generate H2O2 and glucose acid, which promote the degradation of CPPO, further strengthening the efficiency of CDT, leading to a butterfly effect. This demonstrated that the butterfly effect triggered by NR and GOx encourages Fenton/Fenton-like reactions of Fe3O4 and MoS2, thereby enhancing the tumor inhibition effect. The strategy of combining GOx and CPPO to strengthen the Fenton/Fenton-like reaction is a universal strategy, which provides a new and interesting perspective for CPPO in the application of CDT, reflecting the exquisite integration of Fenton chemistry and catalytic medicine.


Assuntos
Peróxido de Hidrogênio , Peróxido de Hidrogênio/química , Humanos , Ferro/química , Lipossomos/química , Glucose Oxidase/química , Glucose Oxidase/metabolismo , Animais , Propriedades de Superfície , Antineoplásicos/química , Antineoplásicos/farmacologia , Oxalatos/química , Camundongos , Tamanho da Partícula , Sobrevivência Celular/efeitos dos fármacos
8.
Small ; : e2401147, 2024 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-38770990

RESUMO

Cuproptosis, a recently discovered copper-dependent cell death, presents significant potential for the development of copper-based nanoparticles to induce cuproptosis in cancer therapy. Herein, a unique ternary heterojunction, denoted as HACT, composed of core-shell Au@Cu2O nanocubes with surface-deposited Titanium Dioxide quantum dots and modified with hyaluronic acid is introduced. Compared to core-shell AC NCs, the TiO2/Au@Cu2O exhibits improved energy structure optimization, successfully separating electron-hole pairs for redox use. This optimization results in a more rapid generation of singlet oxygen and hydroxyl radicals triggering oxidative stress under ultrasound radiation. Furthermore, the HACT NCs initiate cuproptosis by Fenton-like reaction and acidic environment, leading to the sequential release of cupric and cuprous ions. This accumulation of copper induces the aggregation of lipoylated proteins and reduces iron-sulfur proteins, ultimately initiating cuproptosis. More importantly, HACT NCs show a tendency to selectively target cancer cells, thereby granting them a degree of biosecurity. This report introduces a ternary heterojunction capable of triggering both cuproptosis and oxidative stress-related combination therapy in a stimulus-responsive manner. It can energize efforts to develop effective melanoma treatment strategies using Cu-based nanoparticles through rational design.

9.
J Hazard Mater ; 471: 134422, 2024 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-38677118

RESUMO

Electron transfer pathways have been verified as overriding regimes when peroxydisulfate (PDS) was activated by porous carbon. The incorporation of graphitic structure into carbon matrix was favorable to the rapid electron transfer, but excessive graphitization would deteriorate the specific surface area (SSA), weakening the catalytic performance. The reasonable trade-off between SSA and graphitization degree was necessary and challenging for the preparation of efficient carbon based PS-activators. Herein, a series of graphitic porous carbon with discrepant SSA and graphitic structure were fabricated. The incorporation of graphitization tracks into ultra-thin edges on porous carbon film was verified by multifarious structural characterization. After trade-off, the optimum catalyst exhibited superior catalytic performance with degradation rate constant (kobs) exceeding that of ungraphitized precursor by up to 16.0 times. Mechanistic investigations substantiated that the sufficient SSA of catalyst provided favorable conditions for its affinity towards PDS and sulfadiazine (SDZ), resulting in the formation of PDS* complexes and SDZ adsorption, while the appropriate graphitization degree ensured the reinforced electron transfer rate, which collectively accelerated SDZ oxidation through electron-transfer pathway. The multivariate linear regression model linking kobs to SSA and graphitization degree was established providing basis to construct efficient catalysts for PDS activation.

10.
Chemosphere ; 358: 142132, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38670505

RESUMO

The escalation of industrial activities has escalated the production of pharmaceutical and dyeing effluents, raising significant environmental issues. In this investigation, a hybrid approach of Fenton-like reactions and adsorption was used for deep treatment of these effluents, focusing on effects of variables like hydrogen peroxide concentration, catalyst type, pH, reaction duration, temperature, and adsorbent quantity on treatment effectiveness, and the efficacy of acid-modified attapulgite (AMATP) and ferric iron (Fe(III))-loaded AMATP (Fe(III)-AMATP) was examined. Optimal operational conditions were determined, and the possibility of reusing the catalysts was explored. Employing Fe3O4 as a heterogeneous catalyst and AMATP for adsorption, CODCr was reduced by 78.38-79.14%, total nitrogen by 71.53-77.43%, and phosphorus by 97.74-98.10% in pharmaceutical effluents. Similarly, for dyeing effluents, Fe(III)-AMATP achieved 79.87-80.94% CODCr, 68.59-70.93% total nitrogen, and 79.31-83.33% phosphorus reduction. Regeneration experiments revealed that Fe3O4 maintained 59.48% efficiency over three cycles, and Fe(III)-AMATP maintained 62.47% efficiency over four cycles. This work offers an economical, hybrid approach for effective pharmaceutical and dyeing effluent treatment, with broad application potential.


Assuntos
Compostos Férricos , Peróxido de Hidrogênio , Resíduos Industriais , Compostos de Magnésio , Compostos de Silício , Eliminação de Resíduos Líquidos , Poluentes Químicos da Água , Eliminação de Resíduos Líquidos/métodos , Poluentes Químicos da Água/química , Compostos Férricos/química , Adsorção , Compostos de Silício/química , Compostos de Magnésio/química , Peróxido de Hidrogênio/química , Catálise , Ferro/química , Fósforo/química , Nitrogênio/química , Corantes/química , Concentração de Íons de Hidrogênio , Purificação da Água/métodos
11.
Biochemistry (Mosc) ; 89(Suppl 1): S112-S126, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38621747

RESUMO

The review considers the problem of hydrogen peroxide decomposition and hydroxyl radical formation in the presence of iron in vivo and in vitro. Analysis of the literature data allows us to conclude that, under physiological conditions, transport of iron, carried out with the help of carrier proteins, minimizes the possibility of appearance of free iron ions in cytoplasm of the cell. Under pathological conditions, when the process of transferring an iron ion from a donor protein to an acceptor protein can be disrupted due to modifications of the carrier proteins, iron ions can enter cytosol. However, at pH values close to neutral, which is typical for cytosol, iron ions are converted into water-insoluble hydroxides. This makes it impossible to decompose hydrogen peroxide according to the mechanism of the classical Fenton reaction. A similar situation is observed in vitro, since buffers with pH close to neutral are used to simulate free radical oxidation. At the same time, iron hydroxides are able to catalyze decomposition of hydrogen peroxide with formation of a hydroxyl radical. Decomposition of hydrogen peroxide with iron hydroxides is called Fenton-like reaction. Studying the features of Fenton-like reaction in biological systems is the subject of future research.


Assuntos
Peróxido de Hidrogênio , Radical Hidroxila , Radical Hidroxila/química , Ferro/química , Hidróxidos , Oxirredução , Proteínas de Transporte
12.
ACS Appl Mater Interfaces ; 16(15): 18534-18550, 2024 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-38574189

RESUMO

The metastasis and recurrence of cancer are related to immunosuppression and hypoxia in the tumor microenvironment. Activating immune activity and improving the hypoxic environment face essential challenges. This paper reports on a multifunctional nanomaterial, HSCCMBC, that induces immunogenic cell death through powerful photodynamic therapy/chemodynamic therapy synergistic antitumor effects. The tumor microenvironment changed from the immunosuppressive type to immune type, activated the immune activity of the system, decomposed hydrogen peroxide to generate oxygen based on Fenton-like reaction, and effectively increased the level of intracellular O2 with the assistance of 3-bromopyruvate, a cell respiratory inhibitor. The structure and composition of HSCCMBC were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, infrared spectroscopy, etc. Oxygen probe RDPP was used to investigate the oxygen level inside and outside the cell, and hydroxyl radical probe tetramethylbenzidine was used to investigate the Fenton-like reaction ability. The immunofluorescence method investigated the expression of various immune markers and hypoxia-inducing factors in vitro and in vivo after treatment. In vitro and in vivo experiments indicate that HSCCMBC is an excellent antitumor agent and is expected to be a candidate drug for antitumor immunotherapy.


Assuntos
Nanopartículas , Neoplasias , Humanos , Dióxido de Silício/farmacologia , Cobre/química , Carbono/farmacologia , Morte Celular Imunogênica , Neoplasias/tratamento farmacológico , Oxigênio/química , Hipóxia , Linhagem Celular Tumoral , Peróxido de Hidrogênio/química , Microambiente Tumoral , Nanopartículas/química
13.
Adv Mater ; : e2403965, 2024 Apr 24.
Artigo em Inglês | MEDLINE | ID: mdl-38655917

RESUMO

State-of-the-art Fenton-like reactions are crucial in advanced oxidation processes (AOPs) for water purification. This review explores the latest advancements in heterogeneous metal-based catalysts within AOPs, covering nanoparticles (NPs), single-atom catalysts (SACs), and ultra-small atom clusters. A distinct connection between the physical properties of these catalysts, such as size, degree of unsaturation, electronic structure, and oxidation state, and their impacts on catalytic behavior and efficacy in Fenton-like reactions. In-depth comparative analysis of metal NPs and SACs is conducted focusing on how particle size variations and metal-support interactions affect oxidation species and pathways. The review highlights the cutting-edge characterization techniques and theoretical calculations, indispensable for deciphering the complex electronic and structural characteristics of active sites in downsized metal particles. Additionally, the review underscores innovative strategies for immobilizing these catalysts onto membrane surfaces, offering a solution to the inherent challenges of powdered catalysts. Recent advances in pilot-scale or engineering applications of Fenton-like-based devices are also summarized for the first time. The paper concludes by charting new research directions, emphasizing advanced catalyst design, precise identification of reactive oxygen species, and in-depth mechanistic studies. These efforts aim to enhance the application potential of nanotechnology-based AOPs in real-world wastewater treatment.

14.
Environ Sci Pollut Res Int ; 31(19): 28525-28537, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38558348

RESUMO

Herein, novel catalysts of Fe-containing zeolite-A (Fe/zeolite-A) were synthesized by exchanging iron ions into zeolite-A framework, and short-chain organic acids (SCOAs) were employed as chelating agents. Reactive Brilliant Blue KN-R (KN-R) was used as a model pollutant to evaluate the performance of these catalysts based on the heterogeneous Fenton reaction. The results showed that Fe-OA/3A, which applied zeolite-3A as the supporter and oxalic as the chelating agent, presented the most prominent KN-R decolorization efficiency. Under the initial pH of 2.5, 0.4 mM KN-R could be totally decolorized within 20 min. However, the mineralization efficiency of KN-R was only 58.2%. Therefore, anthraquinone dyes were introduced to modify zeolite-3A. As a result, the mineralization efficiency of KN-R was elevated to 92.7% when using Alizarin Violet (AV) as the modifier. Moreover, the modified catalysts exhibited excellent stability, the KN-R decolorization efficiency could be maintained above 95.0% within 20 min after operating for nine cycles. The mechanism revealed that the Fe(II)/Fe(III) cycle was accelerated by AV-modified catalyst thus prompting the KN-R decolorization in Fenton-like system. These findings provide new insights for preparing catalysts with excellent activity and stability for dye wastewater treatment.


Assuntos
Ferro , Zeolitas , Zeolitas/química , Ferro/química , Corantes/química , Poluentes Químicos da Água/química , Catálise , Antraquinonas/química , Benzenossulfonatos/química , Peróxido de Hidrogênio/química
15.
ACS Appl Mater Interfaces ; 16(14): 17242-17252, 2024 Apr 10.
Artigo em Inglês | MEDLINE | ID: mdl-38556729

RESUMO

Protective autophagy and DNA damage repair lead to tumor radio-resistance. Some hypoxic tumors exhibit a low radiation energy absorption coefficient in radiation therapy. High doses of X-rays may lead to side effects in the surrounding normal tissues. In order to overcome the radio-resistance and improve the efficacy of radiotherapy based on the characteristics of the tumor microenvironment, the development of radiosensitizers has attracted much attention. In this study, a Janus ACSP nanoparticle (NP) was developed for chemodynamic therapy and radiosensitization. The reactive oxygen species generated by the Fenton-like reaction regulated the distribution of cell cycles from a radioresistant phase to a radio-sensitive phase. The high-Z element, Au, enhanced the production of hydroxyl radicals (•OH) under X-ray radiation, promoting DNA damage and cell apoptosis. The NP delayed DNA damage repair by interfering with certain proteins involved in the DNA repair signaling pathway. In vivo experiments demonstrated that the combination of the copper-ion-based Fenton-like reaction and low-dose X-ray radiation enhanced the effectiveness of radiotherapy, providing a novel approach for synergistic chemodynamic and radiosensitization therapy. This study provides valuable insights and strategies for the development and application of NPs in cancer treatment.


Assuntos
Nanopartículas , Neoplasias , Radiossensibilizantes , Humanos , Neoplasias/tratamento farmacológico , Radiossensibilizantes/farmacologia , Radiossensibilizantes/uso terapêutico , Apoptose , Linhagem Celular Tumoral , Microambiente Tumoral , Peróxido de Hidrogênio
16.
Angew Chem Int Ed Engl ; 63(26): e202402669, 2024 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-38637296

RESUMO

Singlet oxygen (1O2) is an essential reactive species responsible for selective oxidation of organic matter, especially in Fenton-like processes. However, due to the great limitations in synthesizing catalysts with well-defined active sites, the controllable production and practical application of 1O2 remain challenging. Herein, guided by theoretical simulations, a series of boron nitride-based single-atom catalysts (BvBN/M, M=Co, Fe, Cu, Ni and Mn) were synthesized to regulate 1O2 generation by activating peroxymonosulfate (PMS). All the fabricated BvBN/M catalysts with explicit M-N3 sites promoted the self-decomposition of the two PMS molecules to generate 1O2 with high selectivity, where BvBN/Co possessed moderate adsorption energy and d-band center exhibited superior catalytic activity. As an outcome, the BvBN/Co-PMS system coupled with membrane filtration technology could continuously transform aromatic alcohols to aldehydes with nearly 100 % selectivity and conversion rate under mild conditions, suggesting the potential of this novel catalytic system for green organic synthesis.

17.
J Nanobiotechnology ; 22(1): 117, 2024 Mar 16.
Artigo em Inglês | MEDLINE | ID: mdl-38493145

RESUMO

Reactive oxygen species (ROS) has emerged as potent therapeutic agents for biofilm-associated bacterial infections. Chemodynamic therapy (CDT), involving the generation of high-energy ROS, displays great potential in the therapy of bacterial infections. However, challenges such as insufficient hydrogen peroxide (H2O2) and over-expressed glutathione (GSH) levels within the microenvironment of bacterial biofilms severely limit the antibacterial efficacy of CDT. Herein, we have developed a multifunctional nanoplatform (CuS@CaO2@Dex) by integrating copper sulfide (CuS) and calcium peroxide (CaO2) into dextran (Dex)-coated nanoparticles. This innovative platform enhanced ROS generation for highly efficient biofilm elimination by simultaneously supplying H2O2 and depleting GSH. The Dex-coating facilitated the penetrability of CuS@CaO2@Dex into biofilms, while CaO2 generated a substantial amount of H2O2 in the acidic biofilm microenvironment. CuS, through a Fenton-like reaction, catalyzed the conversion of self-supplied H2O2 into hydroxyl radicals (•OH) and consumed the overexpressed GSH. Additionally, the incorporation of near-infrared II (NIR II) laser irradiation enhanced the photothermal properties of CuS, improving the catalytic efficiency of the Fenton-like reaction for enhanced antibacterial effects. In vivo experiments have demonstrated that CuS@CaO2@Dex exhibited remarkable antibacterial and antibiofilm efficacy, exceptional wound healing capabilities, and notable biosafety. In summary, the Dex-coated nanoplatform proposed in this study, with its self-sterilization capability through ROS, holds significant potential for future biomedical applications.


Assuntos
Infecções Bacterianas , Staphylococcus aureus Resistente à Meticilina , Neoplasias , Humanos , Peróxido de Hidrogênio/farmacologia , Espécies Reativas de Oxigênio , Antibacterianos/farmacologia , Biofilmes , Glutationa , Linhagem Celular Tumoral , Microambiente Tumoral
18.
Environ Pollut ; 348: 123825, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38513946

RESUMO

Carbon-driven advanced oxidations show great potential in water purification, but regulating structures and properties of carbon-based catalysts to achieve ultrafast Fenton-like reactions remains challenging. Herein, a biomorphic diatomite-based catalyst (BD-C) with Si-O doping was prepared using natural diatomite as silicon source and porous template. The results showed that the metal-free BD-C catalyst exhibited ultrafast oxidation performances (0.95-2.58 min-1) towards a variety of pollutants in PMS-based Fenton-like reaction, with the Fenton-like activity of metal-free catalyst comparable to metal-based catalysts or even single-atom catalysts. Pollutants (e.g., CP, BPA, TC, and PCM) with electron-donating groups exhibited extremely low PMS decomposition with overwhelmed electron transfer process (ETP), while high PMS consumption was induced by the addition of electron-withdrawing pollutants (e.g., MNZ and ATZ), which was dominated by radical oxidation. The BD-C/PMS system also showed a high ability to resist the environmental interference. In-depth theoretical investigations demonstrated that the coordination of Si-O can lower the potential barrier of PMS activation for accelerating the generation of radicals, and also promote the electron transfer from pollutants to the BD-C/PMS complexes. In addition, BD-C was deposited onto a polytetrafluoroethylene membrane (PTFEM) with 100% of pollutants removal over 10 h, thereby revealing the promising prospects of utilizing BD-C for practical applications.


Assuntos
Carbono , Terra de Diatomáceas , Poluentes Ambientais , Oxirredução , Transporte de Elétrons , Peróxidos
19.
Environ Pollut ; 345: 123509, 2024 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-38325512

RESUMO

Coal fly ash (CFA), an industrial solid waste, can be utilized to synthesize Zeolite Socony Mobil-5 (ZSM-5) by incorporating an external silica source. In this study, a series of ZSM-5 zeolites were synthesized using rice husk ash (RHA) as the primary silica source and CFA as the primary aluminum source under controlled hydrothermal reaction conditions, and the growth mechanism of ZSM-5 was investigated. The process of ZSM-5 growth was featured by the transformation of hyperpoly silico-aluminate in CFA and RHA into monomers. These monomers formed crystal nuclei connected in a five-membered ring structure under the influence of Tetrapropyl ammonium hydroxide (TPAOH). The surplus monomeric silica-aluminate grew on the nucleus surface due to the addition of the silica source within RHA (RHA-SiO2), ultimately resulting in the development of ZSM-5 zeolite. Characterization results demonstrated that RHA-SiO2 exhibited favorable physical and chemical properties during the ZSM-5 synthesis, with a crystallinity of 99.03%, a specific surface area of 321.19 m2/g, a weight loss of only 3.06% at 800 °C and a total acidity of 0.65 mmol/g. To evaluate the catalytic performance of ZSM-5, Fe/Cu-modified ZSM-5 was developed and used as the catalyst for the degradation of tetracycline (TC) in Fenton-like oxidation. The results indicated that Fe/Cu-ZSM-5 exhibited excellent activity and stability as the catalyst for TC degradation and mineralization. The maximum TC degradation rate reached 99.02% in 10 min and the TOC removal could be up to 69.32% in 2 h. Characterization results indicated that the Fe/Cu ions redox cycle accelerated the generation of active species (1O2 and ˙OH) in Fenton-like systems. The ZSM-5 zeolite synthesized from solid waste demonstrated superb stability and catalytic activity, leading to the effective removal of TC. Since real wastewater generally contains various pollutants, future research efforts should focused on multi-pollutant treatment.


Assuntos
Oryza , Zeolitas , Cinza de Carvão/química , Zeolitas/química , Oryza/química , Resíduos Sólidos , Dióxido de Silício/química , Oxirredução , Tetraciclina , Antibacterianos , Carvão Mineral
20.
J Hazard Mater ; 467: 133752, 2024 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-38350320

RESUMO

A remarkably efficient and affordable Fe/Cu bimetallic catalyst featuring a substantial light energy utilization and compatibility with a sizable substrate was developed for Fenton-like reactions aimed at pollutant control. Specifically, a novel strategy was employed to synthesize high-density metal sites (Fe:Cu ≈ 3:1) robustly embedded on polyethylene/polyethylene terephthalate nonwoven fabric (PE/PET NWF) via radiation-induced graft polymerization (RIGP) and subsequent chemical modification, labeled as Fe/Cu-PPAO. Its high effectiveness was demonstrated by degrading 50 mg/L of tetracycline hydrochloride within 30 min in the presence of H2O2 under simulate sunlight irradiation. It was investigated that amidoxime groups regulated the optical gaps and HOMO-LUMO gaps of metal ions to enable the absorption of a broader spectrum light while the Cu2+ facilitated the transfer of electrons between the bimetal ions to achieve an improved reaction path. Furthermore, X-ray absorption fine structure (XAFS) and density functional theory (DFT) calculations further revealed its special complex state and delicate electronic structure between bimetal ions and amidoxime groups. Our study offers a new strategy to synthesize high-density bimetallic sites catalyst for environmental remediation and pushes forward insight into understanding the catalytic mechanism of bimetallic Fenton-like catalysts.

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