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1.
Proc Natl Acad Sci U S A ; 121(9): e2317394121, 2024 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-38377212

RESUMO

Effectively managing sewage sludge from Fenton reactions in an eco-friendly way is vital for Fenton technology's viability in pollution treatment. This study focuses on sewage sludge across various treatment stages, including generation, concentration, dehydration, and landfill, and employs chemical composite MoS2 to facilitate green resource utilization of all types of sludge. MoS2, with exposed Mo4+ and low-coordination sulfur, enhances iron cycling and creates an acidic microenvironment on the sludge surface. The MoS2-modified iron sludge exhibits outstanding (>95%) phenol and pollutant degradation in hydrogen peroxide and peroxymonosulfate-based Fenton systems, unlike unmodified sludge. This modified sludge maintains excellent Fenton activity in various water conditions and with multiple anions, allowing extended phenol degradation for over 14 d. Notably, the generated chemical oxygen demand (COD) in sludge modification process can be efficiently eliminated through the Fenton reaction, ensuring effluent COD compliance and enabling eco-friendly sewage sludge resource utilization.

2.
Nano Lett ; 2024 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-39392201

RESUMO

Chemodynamic therapy (CDT) is an innovative and burgeoning strategy that utilizes Fenton-Fenton-like chemistry and specific microenvironments to produce highly toxic hydroxyl radicals (•OH), with numerous methods emerging to refine this approach. Herein, we report a coordination compound, Fe-norepinephrine nanoparticles (Fe-NE NPs), via a one-pot synthesis. The Fe-NE NPs are based on ferrous ions (Fe2+) and norepinephrine, which are capable of efficient Fe2+/Fe3+ delivery. Once internalized by tumor cells, the released Fe2+/Fe3+ exerts the Fenton reaction to specifically produce toxic •OH. Moreover, the internal photothermal conversion ability of Fe-NE NPs allows us to simultaneously introduce light to trigger local heat generation and then largely improve the Fenton reaction efficiency, which enables a synergetic photothermal and chemodynamic therapy to realize satisfactory in vivo antitumor efficiency. This proof-of-concept work offers a promising approach to developing nanomaterials and refining strategies for enhanced CDT against tumors.

3.
Small ; 20(6): e2305974, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-37771197

RESUMO

Iron oxide nanoparticles (IONPs) have garnered significant attention as a promising platform for reactive oxygen species (ROS)-dependent disease treatment, owing to their remarkable biocompatibility and Fenton catalytic activity. However, the low catalytic activity of IONPs is a major hurdle in their clinical translation. To overcome this challenge, IONPs of different compositions are examined for their Fenton reaction under pharmacologically relevant conditions. The results show that wüstite (FeO) nanoparticles exhibit higher catalytic activity than magnetite (Fe3 O4 ) or maghemite (γ-Fe2 O3 ) of matched size and coating, despite having a similar surface oxidation state. Further analyses suggest that the high catalytic activity of wüstite nanoparticles can be attributed to the presence of internal low-valence iron (Fe0 and Fe2+ ), which accelerates the recycling of surface Fe3+ to Fe2+ through intraparticle electron transport. Additionally, ultrasmall wüstite nanoparticles are generated by tuning the thermodecomposition-based nanocrystal synthesis, resulting in a Fenton reaction rate 5.3 times higher than that of ferumoxytol, an FDA-approved IONP. Compared with ferumoxytol, wüstite nanoparticles substantially increase the level of intracellular ROS in mouse mammary carcinoma cells. This study presents a novel mechanism and pivotal improvement for the development of highly efficient ROS-inducing nanozymes, thereby expanding the horizons for their therapeutic applications.


Assuntos
Óxido Ferroso-Férrico , Nanopartículas , Camundongos , Animais , Transporte de Elétrons , Espécies Reativas de Oxigênio , Compostos Férricos/química , Compostos Ferrosos
4.
Small ; : e2311244, 2024 Jun 19.
Artigo em Inglês | MEDLINE | ID: mdl-38898764

RESUMO

Radiofrequency ablation (RFA) is one of the most common minimally invasive techniques for the treatment of solid tumors, but residual malignant tissues or small satellite lesions after insufficient RFA (iRFA) are difficult to remove, often leading to metastasis and recurrence. Here, Fe-TPZ nanoparticles are designed by metal ion and (TPZ) ligand complexation for synergistic enhancement of RFA residual tumor therapy. Fe-TPZ nanoparticles are cleaved in the acidic microenvironment of the tumor to generate Fe2+ and TPZ. TPZ, an anoxia-dependent drug, is activated in residual tumors and generates free radicals to cause tumor cell death. Elevated Fe2+ undergoes a redox reaction with glutathione (GSH), inducing a strong Fenton effect and promoting the production of the highly toxic hydroxyl radical (•OH). In addition, the ROS/GSH imbalance induced by this treatment promotes immunogenic cell death (ICD), which triggers the release of damage-associated molecular patterns, macrophage polarization, and lymphocyte infiltration, thus triggering a systemic antitumor immune response and noteworthy prevention of tumor metastasis. Overall, this integrated treatment program driven by multiple microenvironment-dependent pathways overcomes the limitations of the RFA monotherapy approach and thus improves tumor prognosis. Furthermore, these findings aim to provide new research ideas for regulating the tumor immune microenvironment.

5.
Chemistry ; 30(24): e202304337, 2024 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-38373023

RESUMO

The Fenton reaction refers to the reaction in which ferrous ions (Fe2+) produce hydroxyl radicals and other reactive oxidizing substances by decomposing hydrogen peroxide (H2O2). This paper reviews the mechanism, application system, and materials employed in the Fenton reaction including conventional homogeneous and non-homogeneous Fenton reactions as well as photo-, electrically-, ultrasonically-, and piezoelectrically-triggered Fenton reactions, and summarizes the applications in the degradation of soil oil pollutions, landfill leachate, textile wastewater, and antibiotics from a practical point of view. The mineralization paths of typical pollutant are elucidated with relevant case studies. The paper concludes with a summary and outlook of the further development of Fenton-like reactions.

6.
Environ Sci Technol ; 58(25): 11063-11073, 2024 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-38869036

RESUMO

Rhizosphere iron plaques derived from Fe-based nanomaterials (NMs) are a promising tool for sustainable agriculture. However, the requirement for flooded conditions to generate iron plaque limits the scope of the NM application. In this study, we achieved in situ Fenton oxidation of a highly chlorinated persistent organic pollutant (2,2',4,5,5'-pentachlorobiphenyl, PCB101) through iron plaque mediated by the interaction between α-Fe2O3 NMs and plant-rhizobacteria symbionts under dryland conditions. Mechanistically, the coexistence of α-Fe2O3 NMs and Pseudomonas chlororaphis JD37 stimulated alfalfa roots to secrete acidic and reductive agents as well as H2O2, which together mediated the rhizosphere Fenton reaction and converted α-Fe2O3 NMs into iron plaque rich in Fe(II)-silicate. Further verifications reproduced the Fenton reaction in vitro using α-Fe2O3 NMs and rhizosphere compounds, confirming the critical role of •OH in the oxidative degradation of PCB101. Significant reductions in PCB101 content by 18.6%, 42.9%, and 23.2% were respectively found in stem, leaf, and soil after a 120-d treatment, proving the effectiveness of this NMs-plant-rhizobacteria technique for simultaneously safe crop production and soil remediation. These findings can help expand the potential applications of nanobio interaction and its mediated iron plaque generation for both agricultural practice and soil remediation.


Assuntos
Ferro , Poluentes do Solo , Ferro/metabolismo , Poluentes do Solo/metabolismo , Nanoestruturas/química , Compostos Férricos , Solo/química , Rizosfera
7.
Environ Res ; 258: 119419, 2024 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-38879107

RESUMO

Nano-zerovalent iron (nZVI) is a promising material for the removal of both organic and inorganic pollutants from contaminated water. This study investigates the potential of a novel composite of nZVI on a polymer-derived supporting ceramic (nZVI-PDC) synthesized via the liquid-phase reduction method for the simultaneous adsorption and Fenton-type reduction of bromate anion (BrO3-) in water. The nZVI nanoparticles were effectively anchored onto the PDC by impregnating high-yield carbon in a ferrous sulfate solution. The PDC facilitated the uniform dispersion of nZVI nanoparticles due to its multiple active sites distributed within mesocarbon cavities. The developed nZVI-PDC composite exhibited a high specific surface area of 837 m2 g-1 and an ordered mesoporous structure with a pore volume of 0.37 cm3 g-1. As an adsorbent, the nZVI-PDC composite exhibited a maximum adsorption capacity (qe) of 842 mg g-1 and a partition coefficient (KH) of 10.2 mg g-1 µM-1, as calculated by the pseudo-second-order model. As a catalyst, the composite demonstrated a reaction kinetic rate of 43.5 µmol g-1 h-1 within 6 h at pH 4, using a dosage of 60 mg L-1 nZVI-PDC and a concentration of 0.8 mmol L-1 H2O2. Comparatively, PDC exhibited a qe of 408 mg g-1, KH of 1.67 mg g-1 µM-1, and a reaction rate of 20.8 µmol g-1 h-1, while nZVI showed a qe of 456 mg g-1, KH of 2.30 mg g-1 µM-1, and a reaction rate of 27.2 µmol g-1 h-1. The modelling indicated that the nZVI-PDC composite followed pseudo-second-order kinetics. The remarkable removal efficiency of the nZVI-PDC composite was attributed to the synergistic effects between PDC and nZVI, where PDC facilitated charge transfer, promoting Fe2+ generation and the Fe3+/Fe2+ cycle. Overall, this work introduces a promising adsorption technology for the efficient removal of BrO3- from contaminated aqueous solutions, highlighting the significant potential of the nZVI-PDC composite in water purification applications.


Assuntos
Bromatos , Cerâmica , Ferro , Poluentes Químicos da Água , Ferro/química , Adsorção , Poluentes Químicos da Água/química , Cerâmica/química , Bromatos/química , Purificação da Água/métodos , Peróxido de Hidrogênio/química , Polímeros/química , Oxirredução , Nanopartículas Metálicas/química
8.
Environ Res ; 262(Pt 1): 119883, 2024 Aug 29.
Artigo em Inglês | MEDLINE | ID: mdl-39214488

RESUMO

Favipiravir (FAV) is a widely utilized antiviral drug effective against various viruses, including SARS-CoV-2, influenza, and RNA viruses. This article aims to introduce a novel approach, known as Linear-Paired Electrocatalytic Degradation (LPED), as an efficient technique for the electrocatalytic degradation of emerging pollutants. LPED involves simultaneously utilizing a carbon-Felt/Co-PbO2 anode and a carbon-felt/Co/Fe-MOF-74 cathode, working together to degrade and mineralize FAV. The prepared anode and cathode characteristics were analyzed using XPS, SEM, EDX mapping, XRD, LSV, and CV analyses. A rotatable central composite design-based quadratic model was employed to optimize FAV degradation, yielding statistically desirable results. Under optimized conditions (pH = 5, current density = 4.2 mA/cm2, FAV concentration = 0.4 mM), individual processes of cathodic electro-Fenton and anodic oxidation with a CF/Co-PbO2 anode achieved degradation rates of 58.9% and 89.5% after 120 min, respectively. In contrast, using the LPED strategy resulted in a remarkable degradation efficiency of 98.4%. Furthermore, a cyclic voltammetric study of FAV on a glassy carbon electrode was conducted to gather additional electrochemical insights and rectify previously published data regarding redox behavior, pH-dependent properties, and adsorption activities. The research also offers a new understanding of the LPED mechanism of FAV at the surfaces of both CF/Co-PbO2 and CF/Co/Fe-MOF-74 electrodes, utilizing data from cyclic voltammetry and LC-MS techniques. The conceptual strategy of LPED is generalizable in order to the synergism of anodic oxidation and cathodic electro-Fenton for the degradation of other toxic and resistant pollutants.

9.
J Nanobiotechnology ; 22(1): 98, 2024 Mar 09.
Artigo em Inglês | MEDLINE | ID: mdl-38461231

RESUMO

Chemodynamic therapy (CDT) based on intracellular Fenton reaction to produce highly cytotoxic reactive oxygen species (ROS) has played an essential role in tumor therapy. However, this therapy still needs to be improved by weakly acidic pH and over-expression of glutathione (GSH) in tumor microenvironment (TEM), which hinders its future application. Herein, we reported a multifunctional bimetallic composite nanoparticle MnO2@GA-Fe@CAI based on a metal polyphenol network (MPN) structure, which could reduce intracellular pH and endogenous GSH by remodeling tumor microenvironment to improve Fenton activity. MnO2 nanoparticles were prepared first and MnO2@GA-Fe nanoparticles with Fe3+ as central ion and gallic acid (GA) as surface ligands were prepared by the chelation reaction. Then, carbonic anhydrase inhibitor (CAI) was coupled with GA to form MnO2@GA-Fe@CAI. The properties of the bimetallic composite nanoparticles were studied, and the results showed that CAI could reduce intracellular pH. At the same time, MnO2 could deplete intracellular GSH and produce Mn2+ via redox reactions, which re-established the TME with low pH and GSH. In addition, GA reduced Fe3+ to Fe2+. Mn2+ and Fe2+ catalyzed the endogenous H2O2 to produce high-lever ROS to kill tumor cells. Compared with MnO2, MnO2@GA-Fe@CAI could reduce the tumor weight and volume for the xenograft MDA-MB-231 tumor-bearing mice and the final tumor inhibition rate of 58.09 ± 5.77%, showing the improved therapeutic effect as well as the biological safety. Therefore, this study achieved the high-efficiency CDT effect catalyzed by bimetallic through reshaping the tumor microenvironment.


Assuntos
Nanopartículas , Neoplasias , Neoplasias de Mama Triplo Negativas , Humanos , Animais , Camundongos , Peróxido de Hidrogênio , Compostos de Manganês/farmacologia , Espécies Reativas de Oxigênio , Óxidos , Ácido Gálico , Glutationa , Concentração de Íons de Hidrogênio , Linhagem Celular Tumoral , Microambiente Tumoral
10.
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
11.
Mikrochim Acta ; 191(9): 511, 2024 08 05.
Artigo em Inglês | MEDLINE | ID: mdl-39103612

RESUMO

A sequential dual-locked luminescent copper nanoclusters (CuNCs) probe was designed and synthesized for the specific imaging and selective killing of tumor cells. This nanoprobe was prepared by first forming a Fe3+-coupled tannic acid (TA)-stabilized CuNCs (CuNCs-FeIII), which is in quenching state due to the electron transfer between CuNCs and Fe3+, and then coating a protectable layer of hyaluronic acid (HA) on the surface of CuNCs-FeIII to form the final dual-locked nanoprobe (CuNCs-FeIII@HA). When the nanoprobe of CuNCs-FeIII@HA target enter the tumor cells through CD44-HA receptor, HAase will first digest the HA layer of the nanoprobes, and then, GSH over-expressed in tumor cells will reduce Fe3+ to Fe2+, thus restoring the fluorescence emission of CuNCs and at the same time killing the tumor cells with the hydroxyl free radicals (∙OH) produced by the Fenton reaction between Fe2+ and H2O2. This sequential dual-locked luminescent nanoprobe of CuNCs-FeIII@HA has been successfully used for the specific imaging and selective killing of tumor cells.


Assuntos
Cobre , Cobre/química , Humanos , Nanopartículas Metálicas/química , Ácido Hialurônico/química , Taninos/química , Imagem Óptica , Corantes Fluorescentes/química , Sobrevivência Celular/efeitos dos fármacos , Substâncias Luminescentes/química , Substâncias Luminescentes/síntese química , Linhagem Celular Tumoral , Radical Hidroxila/química , Antineoplásicos/farmacologia , Antineoplásicos/química , Peróxido de Hidrogênio/química
12.
Mikrochim Acta ; 191(11): 647, 2024 10 05.
Artigo em Inglês | MEDLINE | ID: mdl-39367939

RESUMO

Hydrogen peroxide-based Fenton reaction can effectively degrade many small-molecule fluorescent dyes, leading to notable alterations in fluorescence signals. Additionally, the two-dimensional black phosphorus/platinum nanocomposite (BP/Pt) demonstrates exceptional catalase (CAT) characteristics. Based on these, a colorimetric-fluorescence dual-mode signal output pattern based on BP/Pt-Fenton reaction-rhodamine B tandem reaction system is reported. The physical adsorption property of the BP/Pt nanozymes was utilized to couple with antibodies, thus constructing a novel dual-mode nanozyme-based immuno-sensing assay (NISA). By using the migratory antibiotic enrofloxacin (ENR) as the target, the NISA provided highly sensitive detection with the detection limits of 0.058 ng/mL for colorimetric-mode and 0.025 ng/mL for fluorescence-mode and achieved accurate quantitative detection in environmental water and crucian carp samples. This work provides an innovative design for monitoring antibiotics in the environment and broadens the idea for the application of nanozymes and Fenton systems in immunosensing assays.


Assuntos
Antibacterianos , Catalase , Enrofloxacina , Peróxido de Hidrogênio , Ferro , Limite de Detecção , Fósforo , Platina , Enrofloxacina/análise , Platina/química , Imunoensaio/métodos , Animais , Peróxido de Hidrogênio/química , Catalase/química , Ferro/química , Fósforo/química , Antibacterianos/análise , Antibacterianos/química , Rodaminas/química , Carpas , Nanocompostos/química , Colorimetria/métodos , Poluentes Químicos da Água/análise , Corantes Fluorescentes/química , Anticorpos Imobilizados/imunologia
13.
Nano Lett ; 23(14): 6323-6329, 2023 Jul 26.
Artigo em Inglês | MEDLINE | ID: mdl-37459426

RESUMO

There remains continued interest in improving the advanced water oxidation process [e.g., ultraviolet (UV)/hydrogen peroxide (H2O2)] for more efficient and environmentally friendly wastewater treatment. Here, we report the design, fabrication, and performance of graphene oxide (GO, on top)/nickel-doped iron oxyhydroxide (Ni:FeOOH, shell)/silicon nanowires (SiNWs, core) as a new multifunctional photocatalyst for the degradation of common pollutants like polystyrene and methylene blue through enhancing the hydroxyl radical (•OH) production rate of the UV/H2O2 system. The photocatalyst combines the advantages of a large surface area and light absorption characteristics of SiNWs with heterogeneous photo-Fenton active Ni:FeOOH and photocatalytically active/charge separator GO. In addition, the built-in electric field of GO/Ni:FeOOH/SiNWs facilitates the charge separation of electrons to GO and holes to Ni:FeOOH, thus boosting the photocatalytic performance. Our photocatalyst increases the •OH yield by 5.7 times compared with that of a blank H2O2 solution sample and also extends the light absorption spectrum to include visible light irradiation.

14.
Nano Lett ; 23(20): 9563-9570, 2023 10 25.
Artigo em Inglês | MEDLINE | ID: mdl-37819937

RESUMO

Traditional disposable personal protective equipment (PPE) only blocks pathogenic bacteria by mechanical filtration, with the risk of recontamination and transmission remaining. Herein, inspired by phenolic-enabled nanotechnology (PEN), we proposed engineered polyphenol coatings by plant-derived aromatic aldehydes and metal involvement, denoted as FQM, to obtain the desired photocatalysis-self-Fenton antibacterial performance. Experiments and theoretical analysis proved the dual mechanism of Fe-induced enhancement: (1) tuning of molecular structure realized improved optical properties; (2) Fe(III)/Fe(II) triggered photocatalytic cascade self-Fenton reaction. Mechanism study reveals FQM killing bacteria by direct-contact ROS attack and gene regulation. Further, the FQM was developed as the ideal antibacterial coating on different fabrics (cloth cotton, polyester, and N95 mask), killing more than 93% of bacteria after 5 cycles of use. Such photocatalysis-self-Fenton coatings based on engineered polyphenols endowed with desirable safety, sustainability, and efficient antibacterial features are promising solutions to meet the challenges of the currently available PPE.


Assuntos
Compostos Férricos , Polifenóis , Polifenóis/farmacologia , Polifenóis/química , Têxteis , Antibacterianos/farmacologia , Antibacterianos/química
15.
Int J Mol Sci ; 25(17)2024 Aug 25.
Artigo em Inglês | MEDLINE | ID: mdl-39273160

RESUMO

Alzheimer's disease (AD) is a multifaceted neurodegenerative disorder characterized by cognitive decline and neuronal loss, representing a most challenging health issue. We present a computational analysis of transcriptomic data of AD tissues vs. healthy controls, focused on the elucidation of functional roles played by long non-coding RNAs (lncRNAs) throughout the AD progression. We first assembled our own lncRNA transcripts from the raw RNA-Seq data generated from 527 samples of the dorsolateral prefrontal cortex, resulting in the identification of 31,574 novel lncRNA genes. Based on co-expression analyses between mRNAs and lncRNAs, a co-expression network was constructed. Maximal subnetworks with dense connections were identified as functional clusters. Pathway enrichment analyses were conducted over mRNAs and lncRNAs in each cluster, which served as the basis for the inference of functional roles played by lncRNAs involved in each of the key steps in an AD development model that we have previously built based on transcriptomic data of protein-encoding genes. Detailed information is presented about the functional roles of lncRNAs in activities related to stress response, reprogrammed metabolism, cell polarity, and development. Our analyses also revealed that lncRNAs have the discerning power to distinguish between AD samples of each stage and healthy controls. This study represents the first of its kind.


Assuntos
Doença de Alzheimer , Redes Reguladoras de Genes , RNA Longo não Codificante , Doença de Alzheimer/genética , Doença de Alzheimer/metabolismo , RNA Longo não Codificante/genética , Humanos , Transcriptoma , Perfilação da Expressão Gênica , RNA Mensageiro/genética , RNA Mensageiro/metabolismo , Regulação da Expressão Gênica , Biologia Computacional/métodos
16.
Int J Mol Sci ; 25(9)2024 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-38731973

RESUMO

Wilson disease is a genetic disorder of the liver characterized by excess accumulation of copper, which is found ubiquitously on earth and normally enters the human body in small amounts via the food chain. Many interesting disease details were published on the mechanistic steps, such as the generation of reactive oxygen species (ROS) and cuproptosis causing a copper dependent cell death. In the liver of patients with Wilson disease, also, increased iron deposits were found that may lead to iron-related ferroptosis responsible for phospholipid peroxidation within membranes of subcellular organelles. All topics are covered in this review article, in addition to the diagnostic and therapeutic issues of Wilson disease. Excess Cu2+ primarily leads to the generation of reactive oxygen species (ROS), as evidenced by early experimental studies exemplified with the detection of hydroxyl radical formation using the electron spin resonance (ESR) spin-trapping method. The generation of ROS products follows the principles of the Haber-Weiss reaction and the subsequent Fenton reaction leading to copper-related cuproptosis, and is thereby closely connected with ROS. Copper accumulation in the liver is due to impaired biliary excretion of copper caused by the inheritable malfunctioning or missing ATP7B protein. As a result, disturbed cellular homeostasis of copper prevails within the liver. Released from the liver cells due to limited storage capacity, the toxic copper enters the circulation and arrives at other organs, causing local accumulation and cell injury. This explains why copper injures not only the liver, but also the brain, kidneys, eyes, heart, muscles, and bones, explaining the multifaceted clinical features of Wilson disease. Among these are depression, psychosis, dysarthria, ataxia, writing problems, dysphagia, renal tubular dysfunction, Kayser-Fleischer corneal rings, cardiomyopathy, cardiac arrhythmias, rhabdomyolysis, osteoporosis, osteomalacia, arthritis, and arthralgia. In addition, Coombs-negative hemolytic anemia is a key feature of Wilson disease with undetectable serum haptoglobin. The modified Leipzig Scoring System helps diagnose Wilson disease. Patients with Wilson disease are well-treated first-line with copper chelators like D-penicillamine that facilitate the removal of circulating copper bound to albumin and increase in urinary copper excretion. Early chelation therapy improves prognosis. Liver transplantation is an option viewed as ultima ratio in end-stage liver disease with untreatable complications or acute liver failure. Liver transplantation finally may thus be a life-saving approach and curative treatment of the disease by replacing the hepatic gene mutation. In conclusion, Wilson disease is a multifaceted genetic disease representing a molecular and clinical challenge.


Assuntos
Cobre , Ferroptose , Degeneração Hepatolenticular , Ferro , Humanos , Degeneração Hepatolenticular/metabolismo , Degeneração Hepatolenticular/patologia , Cobre/metabolismo , Ferro/metabolismo , Espécies Reativas de Oxigênio/metabolismo , Fígado/metabolismo , Fígado/patologia , Animais
17.
Int J Mol Sci ; 25(5)2024 Feb 25.
Artigo em Inglês | MEDLINE | ID: mdl-38473913

RESUMO

Hemochromatosis represents clinically one of the most important genetic storage diseases of the liver caused by iron overload, which is to be differentiated from hepatic iron overload due to excessive iron release from erythrocytes in patients with genetic hemolytic disorders. This disorder is under recent mechanistic discussion regarding ferroptosis, reactive oxygen species (ROS), the gut microbiome, and alcohol abuse as a risk factor, which are all topics of this review article. Triggered by released intracellular free iron from ferritin via the autophagic process of ferritinophagy, ferroptosis is involved in hemochromatosis as a specific form of iron-dependent regulated cell death. This develops in the course of mitochondrial injury associated with additional iron accumulation, followed by excessive production of ROS and lipid peroxidation. A low fecal iron content during therapeutic iron depletion reduces colonic inflammation and oxidative stress. In clinical terms, iron is an essential trace element required for human health. Humans cannot synthesize iron and must take it up from iron-containing foods and beverages. Under physiological conditions, healthy individuals allow for iron homeostasis by restricting the extent of intestinal iron depending on realistic demand, avoiding uptake of iron in excess. For this condition, the human body has no chance to adequately compensate through removal. In patients with hemochromatosis, the molecular finetuning of intestinal iron uptake is set off due to mutations in the high-FE2+ (HFE) genes that lead to a lack of hepcidin or resistance on the part of ferroportin to hepcidin binding. This is the major mechanism for the increased iron stores in the body. Hepcidin is a liver-derived peptide, which impairs the release of iron from enterocytes and macrophages by interacting with ferroportin. As a result, iron accumulates in various organs including the liver, which is severely injured and causes the clinically important hemochromatosis. This diagnosis is difficult to establish due to uncharacteristic features. Among these are asthenia, joint pain, arthritis, chondrocalcinosis, diabetes mellitus, hypopituitarism, hypogonadotropic hypogonadism, and cardiopathy. Diagnosis is initially suspected by increased serum levels of ferritin, a non-specific parameter also elevated in inflammatory diseases that must be excluded to be on the safer diagnostic side. Diagnosis is facilitated if ferritin is combined with elevated fasting transferrin saturation, genetic testing, and family screening. Various diagnostic attempts were published as algorithms. However, none of these were based on evidence or quantitative results derived from scored key features as opposed to other known complex diseases. Among these are autoimmune hepatitis (AIH) or drug-induced liver injury (DILI). For both diseases, the scored diagnostic algorithms are used in line with artificial intelligence (AI) principles to ascertain the diagnosis. The first-line therapy of hemochromatosis involves regular and life-long phlebotomy to remove iron from the blood, which improves the prognosis and may prevent the development of end-stage liver disease such as cirrhosis and hepatocellular carcinoma. Liver transplantation is rarely performed, confined to acute liver failure. In conclusion, ferroptosis, ROS, the gut microbiome, and concomitant alcohol abuse play a major contributing role in the development and clinical course of genetic hemochromatosis, which requires early diagnosis and therapy initiation through phlebotomy as a first-line treatment.


Assuntos
Alcoolismo , Ferroptose , Microbioma Gastrointestinal , Hemocromatose , Sobrecarga de Ferro , Neoplasias Hepáticas , Humanos , Hemocromatose/genética , Hepcidinas/metabolismo , Espécies Reativas de Oxigênio/metabolismo , Alcoolismo/complicações , Inteligência Artificial , Fatores de Confusão Epidemiológicos , Antígenos de Histocompatibilidade Classe I/genética , Proteína da Hemocromatose/metabolismo , Proteínas de Membrana/metabolismo , Ferro/metabolismo , Sobrecarga de Ferro/genética , Ferritinas , Etanol , Neoplasias Hepáticas/complicações
18.
J Environ Manage ; 366: 121868, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-39032257

RESUMO

The Fenton reaction is recognized as an effective technique for degrading persistent organic pollutants, such as the emerging pollutant trimethoprim (TMP). Recently, due to the excellent reducibility of active hydrogen ([H]), Pd-H2 has been preferred for Fenton-like reactions and the specific H2 activation of Pd-based catalysts. Herein, a heterogeneous Fenton catalyst named the hydrogen-accelerated oxygen reduction Fenton (MHORF@UiO-66(Zr)) system was prepared through the strategy of building ships in the bottle. The [H] has been used for the acceleration of the reduction of Fe(III) and self-generate H2O2. The systematic characterization demonstrated that the nano Pd0 particle was highly dispersed into the UiO-66(Zr). The results found that 20 mg L-1 of TMP was thoroughly degraded within 90 min in the MHORF@UiO-66(Zr) system under conditions of initial pH 3, 30 mL min-1 H2, 2 g L-1 Pd@UiO-66(Zr) and 25 µM Fe2+. The hydroxyl radical as well as the singlet oxygen were evidenced to be the main reactive oxygen species by scavenging experiments and electron spin resonance. In addition, both reducing Fe(III) and self-generating H2O2 could be achieved due to the strong metal-support interaction (SMSI) between the nano Pd0 particles and UiO-66(Zr) confirmed by the correlation results of XPS and calculation of density functional theory. Finally, the working mechanism of the MHORF@UiO-66(Zr) system and the possible degradation pathway of the TMP have been proposed. The novel system exhibited excellent reusability and stability after six cyclic reaction processes.


Assuntos
Peróxido de Hidrogênio , Trimetoprima , Peróxido de Hidrogênio/química , Trimetoprima/química , Catálise , Ferro/química , Paládio/química , Oxirredução
19.
J Environ Sci (China) ; 143: 1-11, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-38644008

RESUMO

Potential health risks related to environmental endocrine disruptors (EEDs) have aroused research hotspots at the forefront of water treatment technologies. Herein, nitrogen-doped titanium dioxide/schwertmannite nanocomposites (N-TiO2/SCH) have been successfully developed as heterogeneous catalysts for the degradation of typical EEDs via photo-Fenton processes. Due to the sustainable Fe(III)/Fe(II) conversion induced by photoelectrons, as-prepared N-TiO2/SCH nanocomposites exhibit much enhanced efficiency for the degradation of bisphenol A (BPA; ca. 100% within 60 min under visible irradiation) in a wide pH range of 3.0-7.8, which is significantly higher than that of the pristine schwertmannite (ca. 74.5%) or N-TiO2 (ca. 10.8%). In this photo-Fenton system, the efficient degradation of BPA is mainly attributed to the oxidation by hydroxyl radical (•OH) and singlet oxygen (1O2). Moreover, the possible catalytic mechanisms and reaction pathway of BPA degradation are systematically investigated based on analytical and photoelectrochemical analyses. This work not only provides a feasible means for the development of novel heterogeneous photo-Fenton catalysts, but also lays a theoretical foundation for the potential application of mineral-based materials in wastewater treatment.


Assuntos
Compostos Benzidrílicos , Compostos de Ferro , Nanocompostos , Nitrogênio , Fenóis , Titânio , Poluentes Químicos da Água , Titânio/química , Compostos Benzidrílicos/química , Fenóis/química , Nanocompostos/química , Poluentes Químicos da Água/química , Nitrogênio/química , Catálise , Ferro/química , Peróxido de Hidrogênio/química , Disruptores Endócrinos/química , Purificação da Água/métodos
20.
Angew Chem Int Ed Engl ; : e202413633, 2024 Sep 23.
Artigo em Inglês | MEDLINE | ID: mdl-39312192

RESUMO

We have developed a new type of nanoparticles with potent antitumor activity photoactivatable via the combination of molecular photoswitching of spiropyran (SP) and enzymatic reaction of glucose oxidase (GOx). As two key processes involved therein, Fe(III)-to-Fe(II) photoreduction in Fe(III) metal-organic frameworks (MOFs) brings about the release of free Fe2+/Fe3+ while the photoswitching of SP to merocyanine (MC) unlocks the enzymatic activity of GOx that was pre-passivated by SP. The release of free Fe3+ boosts its hydrolysis and therefore enables the acidification of microenvironment, which is further reinforced by one of the products of the GOx-mediated glucose oxidation reaction, gluconic acid (GlcA). Based on the generation of Fe2+ and acidic milieu together with another product of the oxidation reaction, hydrogen peroxide (H2O2), these two processes jointly present triple enabling factors for generating lethal hydroxyl radicals (•OH) species via Fenton reactions and therefore oxidative stress capable of inhibiting tumor. The antitumor potency of such nanoparticle is verified in tumor-bearing model mice in vivo, proclaiming its potential as a potent and safe agent based on the unique mechanism of optically manipulating enzyme activity for synergistic antitumor therapeutics with high spatial precision, enhanced efficacy and minimized side effects.

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