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1.
J Environ Sci (China) ; 149: 288-300, 2025 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-39181643

RESUMO

Structural regulation of Pd-based electrocatalytic hydrodechlorination (EHDC) catalyst for constructing high-efficient cathode materials with low noble metal content and high atom utilization is crucial but still challenging. Herein, a support electron inductive effect of Pd-Mn/Ni foam catalyst was proposed via in-situ Mn doping to optimize the electronic structure of the Ni foam (NF), which can inductive regulation of Pd for improving the EHDC performance. The mass activity and current efficiency of Pd-Mn/NF catalyst are 2.91 and 1.34 times superior to that of Pd/NF with 2,4-dichlorophenol as model compound, respectively. The Mn-doped interlayer optimized the electronic structure of Pd by bringing the d-state closer to the Fermi level than Pd on the NF surface, which optimizied the binding of EHDC intermediates. Additionally, the Mn-doped interlayer acted as a promoter for generating H* and accelerating the EHDC reaction. This work presents a simple and effective regulation strategy for constructing high-efficient cathode catalyst for the EHDC of chlorinated organic compounds.


Assuntos
Manganês , Níquel , Paládio , Catálise , Paládio/química , Manganês/química , Níquel/química , Técnicas Eletroquímicas/métodos , Eletrodos , Clorofenóis/química , Halogenação
2.
Rev Neurol ; 79(6): 161-173, 2024 Sep 16.
Artigo em Espanhol | MEDLINE | ID: mdl-39267402

RESUMO

This review, conducted by the Andalusian Epilepsy Society, provides an update on recent advances in the treatment of drug-resistant epilepsy, focusing on three new anti-seizure drugs: cenobamate, fenfluramine and cannabidiol. These emerging drugs offer new therapeutic alternatives for patients with drug-resistant focal epilepsy, Dravet syndrome, and Lennox-Gastaut syndrome. The primary objective of this review is to provide healthcare professionals with an up-to-date overview of the efficacy, safety and potential clinical applications of these treatments, backed by the latest evidence. In addition to reviewing the available clinical evidence, the document addresses essential practical considerations for the implementation of these drugs in routine clinical practice, including aspects such as their dosage, drug interactions, and management of their side-effects. With this review, the Andalusian Epilepsy Society aims to contribute to improving the care for and quality of life of patients with drug-resistant epilepsy and their families.


TITLE: Avances y orientaciones en el tratamiento de la epilepsia farmacorresistente: revisión de los nuevos fármacos cenobamato, fenfluramina y cannabidiol por la Sociedad Andaluza de Epilepsia.Esta revisión, realizada por la Sociedad Andaluza de Epilepsia, proporciona una actualización sobre los avances recientes en el tratamiento de la epilepsia farmacorresistente y se enfoca en tres nuevos medicamentos anticrisis: cenobamato, fenfluramina y cannabidiol. Estos fármacos emergentes ofrecen nuevas opciones terapéuticas para pacientes con epilepsia focal farmacorresistente y síndromes como el de Dravet y el de Lennox-Gastaut. El objetivo principal de esta revisión es brindar a los profesionales de la salud un panorama actualizado sobre la eficacia, la seguridad y las posibles aplicaciones clínicas de estos tratamientos, respaldado por la evidencia más reciente. Además de revisar la evidencia clínica disponible, el documento aborda consideraciones prácticas esenciales para la implementación de estos fármacos en la práctica clínica diaria, incluyendo aspectos como la posología, la identificación de interacciones farmacológicas y la gestión de efectos secundarios. A través de esta revisión, la Sociedad Andaluza de Epilepsia trata de contribuir a mejorar la atención y la calidad de vida de los pacientes con epilepsia farmacorresistente y sus familias.


Assuntos
Anticonvulsivantes , Canabidiol , Carbamatos , Epilepsia Resistente a Medicamentos , Fenfluramina , Canabidiol/uso terapêutico , Humanos , Anticonvulsivantes/uso terapêutico , Epilepsia Resistente a Medicamentos/tratamento farmacológico , Carbamatos/uso terapêutico , Fenfluramina/uso terapêutico , Epilepsias Mioclônicas/tratamento farmacológico , Síndrome de Lennox-Gastaut/tratamento farmacológico , Guias de Prática Clínica como Assunto , Clorofenóis , Tetrazóis
3.
CNS Drugs ; 38(9): 733-742, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39096467

RESUMO

BACKGROUND AND OBJECTIVES: Cenobamate (CNB) is a new antiseizure medication (ASM) to treat drug-resistant, focal-onset seizures. Data on its use in early therapy lines are not yet available, and clinicians frequently consider CNB to be a later ASM drug choice. We investigated the efficacy and safety of CNB as an early adjunctive treatment in drug-resistant, focal-onset seizures. METHODS: The study population were patients with drug-resistant, focal-onset seizures who were initiated with CNB after they did not respond to two or three lifetime ASMs, including all prior and concomitant ASMs. These patients were matched (1:2) by sex, age, and seizure frequency to controls who were initiated with any ASM other than CNB. All participants participated in the Mainz Epilepsy Registry. We evaluated the retention rate after 12 months of CNB and after each new adjunctive ASM in the control group. In addition, seizure freedom and the response rate (reduction of seizure frequency by ≥ 50% from baseline) after 12 months were estimated. RESULTS: We included 231 patients aged 44.4 ± 15.8 years. Of these, 33.3% (n = 77) were on CNB, 19.0% (n = 44) on valproate (VPA), 17.3% (n = 40) on lacosamide (LCS), 16.4% (n = 38) on levetiracetam (LEV), and 13.9% (n = 32) on topiramate (TPM). The highest retention rate after 12 months since the beginning of the early adjunctive therapy was observed on CNB (92.0%), compared with LCS (80.0%), LEV (73.3%), VPA (68.2%), or TPM (62.5%) (p < 0.05). Seizure freedom and response rate were also the best on CNB (19.5% and 71.4%, respectively) compared with other ASMs (8.3% and 52.5%, respectively; p < 0.05). No significant differences in adverse events between CNB and other ASMs were observed. CONCLUSIONS: Our study provides evidence that CNB is an effective ASM with a good safety profile in the early therapy lines of drug-resistant, focal-onset seizures. This data should support medical decision making in the management of patients with refractory epilepsy. CLINICAL TRIAL ID: NCT05267405.


Assuntos
Anticonvulsivantes , Carbamatos , Clorofenóis , Epilepsia Resistente a Medicamentos , Quimioterapia Combinada , Convulsões , Humanos , Masculino , Anticonvulsivantes/administração & dosagem , Anticonvulsivantes/uso terapêutico , Anticonvulsivantes/efeitos adversos , Feminino , Adulto , Carbamatos/uso terapêutico , Carbamatos/efeitos adversos , Carbamatos/administração & dosagem , Pessoa de Meia-Idade , Estudos de Coortes , Epilepsia Resistente a Medicamentos/tratamento farmacológico , Convulsões/tratamento farmacológico , Clorofenóis/administração & dosagem , Clorofenóis/efeitos adversos , Clorofenóis/uso terapêutico , Resultado do Tratamento , Tetrazóis/administração & dosagem , Tetrazóis/uso terapêutico , Tetrazóis/efeitos adversos , Ácido Valproico/uso terapêutico , Ácido Valproico/administração & dosagem , Ácido Valproico/efeitos adversos
4.
Water Res ; 263: 122158, 2024 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-39088882

RESUMO

This study investigated the expediated transformation of halophenols in the presence of nitrite (NO2-) under slightly acidic conditions in ice, whereas such transformation was negligible in liquid water at 4 °C. We proposed that this phenomenon was attributed to the freeze-concentration effect, incurring a pH drop and the aggregation of NO2- and halophenols within the liquid-like grain boundary layer amid ice crystals. Within this micro-environment, NO2- underwent protonation to generate reactive nitrous acid (HNO2) and nitrosonium ions (NO+) that facilitate the nitration and oxidation of halophenols. When 10 µÐœ halophenol was treated by freezing in the presence of 5 µÐœ NO2-, the total yields of nitrated products reached 2.4 µÐœ and 1.4 µÐœ within 12 h for 2-chlorophenol (2CP) and 2-bromophenol (2BP), respectively. NO+ drove oxidative coupling reactions, generating hydroxyl polyhalogenated diphenyl ethers (OH-PBDEs) and hydroxyl polyhalogenated diphenyls via C-O or C-C coupling. These two pathways were intricately intertwined. The presence of natural organic matter (NOM) mitigated the formation of nitrated products and completely suppressed the coupling products. This study offers valuable insights into the fate of halophenols in ice and suggests potential pathways for the formation of nitrophenolic compounds and OH-PBDEs in natural cold environments. These findings also open up a new avenue in environmental chemistry research.


Assuntos
Gelo , Nitritos , Fenóis , Nitritos/química , Fenóis/química , Congelamento , Oxirredução , Clorofenóis/química , Concentração de Íons de Hidrogênio
5.
Water Res ; 265: 122260, 2024 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-39167969

RESUMO

The design of bioelectrochemical system based on the principle of niche construction, offers a prospective pathway for achieving efficient and thorough biodechlorination in groundwater. This study designed a single-chamber microbial electrolysis cell, with porous three-dimensional (3D) electrodes introduced, to accelerate the niche construction process of functional communities. This approach allowed the growth of various bacteria capable of simultaneously degrading 2,4-dichlorophenol (DCP) and its refractory intermediates, 4-chlorophenol (4CP). The 3D-electrodes provided abundant attachment sites for diverse microbes with a high initial Shannon index (3.4), and along the degradation progress, functional bacteria (Hydrogenoanaerobacterium and Rhodococcus erythropolis for DCP-degrading, Sphingobacterium hotanense for 4CP-degrading and Delftia tsuruhatensis for phenol-degrading) constructed their niches. Applying an external voltage (0.6 V) further increased the selective pressure and niche construction pace, as well as provided 'micro-oxidation' site on the electrode surface, thereby achieving the degradation of 4CP and mineralization of phenol. The porous electrodes could also adsorb contaminants and narrow their interaction distance with microbes, which benefited the degradation efficiency. Thus a 10-fold increase in the overall mineralization of DCP was achieved. This study constructed a novel bioelectrochemical system for achieving efficient and thorough biodechlorination, which was suitable for in situ bioremediation of groundwater.


Assuntos
Biodegradação Ambiental , Eletrodos , Clorofenóis/metabolismo , Bactérias/metabolismo , Água Subterrânea/química , Poluentes Químicos da Água/metabolismo , Purificação da Água/métodos
6.
Cochrane Database Syst Rev ; 8: CD014941, 2024 08 01.
Artigo em Inglês | MEDLINE | ID: mdl-39087564

RESUMO

BACKGROUND: Although most people with epilepsy achieve complete seizure cessation, approximately one-third of those with the condition continue experiencing seizures despite the use of antiseizure medications (ASMs) given as monotherapy or polytherapy. In this review, we summarised the evidence from randomised controlled trials (RCTs) about cenobamate as an add-on treatment for focal epilepsy uncontrolled by one or more concomitant ASMs. OBJECTIVES: To assess the efficacy and tolerability of add-on oral cenobamate for the treatment of drug-resistant focal-onset seizures, defined as seizures persisting despite treatment with one or more ASMs. SEARCH METHODS: We searched the Cochrane Register of Studies (CRS Web) and MEDLINE Ovid (September 2022). In addition, we contacted the manufacturer of cenobamate and experts in the field to enquire after any ongoing or unpublished studies. SELECTION CRITERIA: RCTs comparing add-on cenobamate to placebo or another ASM in people with focal epilepsy uncontrolled by one or more concomitant ASMs. DATA COLLECTION AND ANALYSIS: Two review authors independently selected trials for inclusion, extracted data, performed risk of bias assessment, and assessed the certainty of the evidence using the GRADE approach. Our primary outcomes were at least a 50% reduction in total seizure frequency, seizure freedom, and the occurrence of adverse events. We used an intention-to-treat approach for our primary analyses. For each outcome we estimated summary risk ratios (RRs) with their 95% confidence intervals (CIs). We summarised the estimates of effects and certainty of the evidence for each outcome in a summary of findings table. MAIN RESULTS: We included two studies (659 adult participants, 442 allocated to cenobamate and 217 to placebo). The overall RR for at least a 50% reduction in seizure frequency for add-on cenobamate at any dose compared to placebo was 2.17 (52% versus 24%, 95% CI 1.66 to 2.84; 2 studies, 605 participants; moderate-certainty evidence). The RR for seizure freedom for add-on cenobamate at any dose compared to placebo was 4.45 (16% versus 5%, 95% CI 2.25 to 8.78; 2 studies, 605 participants; moderate-certainty evidence). The RR for the occurrence of adverse events for add-on cenobamate at any dose compared to placebo was 1.14 (77% versus 67%, 95% CI 1.02 to 1.27; 2 studies, 659 participants; moderate-certainty evidence). We judged the two included RCTs as at low or unclear risk of bias. Both studies were sponsored by the drug company that produces cenobamate. AUTHORS' CONCLUSIONS: Add-on cenobamate is probably better than placebo in reducing the frequency of seizures by at least 50% and in achieving seizure freedom in adults with focal epilepsy uncontrolled by one or more concomitant ASMs (moderate level of certainty). Its use is probably associated with an increased risk of adverse events (moderate level of certainty). Further prospective, controlled trials are required to evaluate the efficacy and tolerability of add-on cenobamate compared to other ASMs. The efficacy and tolerability of cenobamate as adjunctive treatment for focal epilepsy in children should be further investigated. Finally, the long-term efficacy and tolerability of add-on cenobamate treatment in people with other epilepsy types (e.g. generalised epilepsy) or specific epilepsy syndromes, as well as its use as monotherapy, require additional study.


Assuntos
Anticonvulsivantes , Carbamatos , Clorofenóis , Epilepsia Resistente a Medicamentos , Quimioterapia Combinada , Epilepsias Parciais , Ensaios Clínicos Controlados Aleatórios como Assunto , Humanos , Anticonvulsivantes/uso terapêutico , Anticonvulsivantes/efeitos adversos , Epilepsia Resistente a Medicamentos/tratamento farmacológico , Epilepsias Parciais/tratamento farmacológico , Carbamatos/uso terapêutico , Carbamatos/efeitos adversos , Clorofenóis/uso terapêutico , Clorofenóis/efeitos adversos , Adulto , Viés , Compostos de Benzil/uso terapêutico , Compostos de Benzil/efeitos adversos , Tetrazóis
7.
Environ Sci Pollut Res Int ; 31(39): 51934-51953, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-39134794

RESUMO

Chlorophenols are one of the major organic pollutants responsible for the contamination of water bodies. This study explores the application of Ni-Zn/CeO2 nanocomposites, synthesized via the aqueous co-precipitation method, as effective adsorbents for the 4-chlorophenol removal from aqueous solutions. The nanocomposites' chemical and structural characteristics were assessed using different physical characterization methods, viz. X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, zeta potential, using a Box-Behnken design within response surface methodology, optimal conditions of pH 3, temperature 20 °C, contact time 120 min, adsorbent dosage 0.05 g, and 4-chlorophenol concentration 50 ppm are identified. Among the nanocomposites tested, NZC 20:10:70, with 20% Ni and 10% Zn, achieves enhanced performance, removing 99.1% of 4-chlorophenol within 2 h. Adsorption kinetics follow the pseudo-second-order model and equilibrium data fit the Freundlich isotherm. Thermodynamic analysis indicates an exothermic and spontaneous process. The adsorption capacity of NZC 20:10:70 shows significant enhancement, growing from 19.85 mg/g at 10 ppm to 96.33 mg/g at 50 ppm initial concentration. Physical characterization confirms NZC 20:10:70's superior properties, including a high surface area of 118.471 m2/g. Evaluating economic viability, NZC 20:10:70 demonstrates robust reusability, retaining 85% efficiency over eight regeneration cycles. These results highlight NZC 20:10:70 as a promising adsorbent for effective and sustainable chlorophenol removal in water treatment.


Assuntos
Clorofenóis , Nanocompostos , Poluentes Químicos da Água , Zinco , Clorofenóis/química , Nanocompostos/química , Adsorção , Poluentes Químicos da Água/química , Zinco/química , Níquel/química , Cinética , Cério/química , Purificação da Água/métodos
8.
J Hazard Mater ; 478: 135427, 2024 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-39116741

RESUMO

Microbial metabolism is an important driving force for the elimination of 4-chlorophenoxyacetic acid residues in the environment. The α-Ketoglutarate-dependent dioxygenase (TfdA) or 2,4-D oxygenase (CadAB) catalyzes the cleavage of the aryl ether bond of 4-chlorophenoxyacetic acid to 4-chlorophenol, which is one of the important pathways for the initial metabolism of 4-chlorophenoxyacetic acid by microorganisms. However, strain Cupriavidus sp. DL-D2 could utilize 4-chlorophenoxyacetic acid but not 4-chlorophenol for growth. This scarcely studied degradation pathway may involve novel enzymes that has not yet been characterized. Here, a gene cluster (designated cpd) responsible for the catabolism of 4-chlorophenoxyacetic acid in strain DL-D2 was cloned and identified, and the dioxygenase CpdA/CpdB responsible for the initial degradation of 4-chlorophenoxyacetic acid was successfully expressed, which could catalyze the conversion of 4-chlorphenoxyacetic acid to 4-chlorocatechol. Then, an aromatic cleavage enzyme CpdC further converts 4-chlorocatechol into 3-chloromuconate. The results of substrate degradation experiments showed that CpdA/CpdB could also degrade 3-chlorophenoxyacetic acid and phenoxyacetic acid, and homologous cpd gene clusters were widely discovered in microbial genomes. Our findings revealed a novel degradation mechanism of 4-chlorophenoxyacetic acid at the molecular level.


Assuntos
Cupriavidus , Dioxigenases , Herbicidas , Dioxigenases/metabolismo , Dioxigenases/genética , Cupriavidus/metabolismo , Cupriavidus/genética , Cupriavidus/enzimologia , Herbicidas/metabolismo , Herbicidas/química , Família Multigênica , Clorofenóis/metabolismo , Biodegradação Ambiental , Proteínas de Bactérias/metabolismo , Proteínas de Bactérias/genética , Ácido 2,4-Diclorofenoxiacético/análogos & derivados
9.
Epilepsy Behav ; 158: 109898, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39002273

RESUMO

GABA modulators such as phenobarbital (PB) and sodium channel blockers such as phenytoin (PHT) have long been the mainstay of pharmacotherapy for the epilepsies. In the context of neonatal seizures, both PB and PHT display incomplete clinical efficacy. Moreover, in animal models, neonatal exposure to these medications result in neurodegeneration raising concerns about safety. Cenobamate, a more recently approved medication, displays unique pharmacology as it is both a positive allosteric modulator of GABA-A receptors, and a voltage-gated sodium channel blocker. While cenobamate is approved for adult use, its efficacy and safety profile against neonatal seizures is poorly understood. To address this gap, we assessed the efficacy and safety of cenobamate in immature rodents. Postnatal day (P)7 rat pups were pretreated with cenobamate and challenged with the chemoconvulsant pentylenetetrazole (PTZ) to screen for anti-seizure effects. In a separate experiment, P7 rats were treated with cenobamate, and brains were processed to assess induction of cell death. Cenobamate displays dose-dependent anti-seizure efficacy in neonatal rats. Unlike PHB and PHT, it does not induce neurotoxicity in P7 rats. Thus, cenobamate may be effective at treating neonatal seizures while avoiding unwanted neurotoxic side effects such as cell death.


Assuntos
Animais Recém-Nascidos , Anticonvulsivantes , Carbamatos , Morte Celular , Modelos Animais de Doenças , Relação Dose-Resposta a Droga , Ratos Sprague-Dawley , Convulsões , Animais , Convulsões/induzido quimicamente , Convulsões/tratamento farmacológico , Anticonvulsivantes/farmacologia , Ratos , Morte Celular/efeitos dos fármacos , Carbamatos/farmacologia , Carbamatos/uso terapêutico , Clorofenóis/farmacologia , Pentilenotetrazol/toxicidade , Masculino , Feminino , Convulsivantes/toxicidade , Encéfalo/efeitos dos fármacos , Tetrazóis
10.
J Chromatogr A ; 1731: 465196, 2024 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-39047444

RESUMO

Magnetic multi-template molecularly imprinted polymers (M-mt-MIPs) were successfully synthesized by surface imprinting and multi-template imprinting strategy, using polydopamine coated magnetic multi-walled carbon nanotubes as supporting materials, five typical chlorophenols (CPs) as templates, methacrylic acid as functional monomer and ethylene glycol dimethacrylate as cross-linker. Compared to non-imprinted polymers (NIPs), the as-prepared M-mt-MIPs showed high adsorption capacity (32.58‒80.63 mg g-1), rapid mass transfer and specific selectivity for the five targeted CPs, which were applied as magnetic solid-phase extraction (MSPE) adsorbents. Parameters affecting MSPE efficiency were detailed investigated, such as adsorbents dosage, sample pH, extraction time, type and volume of desorption solvent and salt effect. Combined with HPLC-DAD, a simple, rapid and sensitive method was established, showing good linearity (2‒200 µg L-1), low limits of detection (0.32‒0.49 µg L-1), and high enrichment factors (35.2‒108). The developed M-mt-MIPs-MSPE-HPLC method was applied to enrich and determine CPs in tannery wastewater, wet-blue and crust leather, and satisfactory spiking recoveries were attained in the range of 73.95‒109.7% with relative standard deviations (RSDs) of 2.13-8.48%. This study provided a new alternative material and method to rapid simultaneously extract and analyze low concentration of typical CPs in complicated matrices.


Assuntos
Clorofenóis , Polímeros Molecularmente Impressos , Extração em Fase Sólida , Cromatografia Líquida de Alta Pressão/métodos , Clorofenóis/análise , Clorofenóis/isolamento & purificação , Polímeros Molecularmente Impressos/química , Extração em Fase Sólida/métodos , Adsorção , Limite de Detecção , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/isolamento & purificação , Poluentes Químicos da Água/química , Impressão Molecular/métodos , Nanotubos de Carbono/química , Águas Residuárias/química , Polímeros/química , Indóis
11.
Talanta ; 278: 126503, 2024 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-38963976

RESUMO

Triclosan (TCS), triclocarban (TCC), and chlorophenols (CPs) are broad-spectrum antibacterials widely used in dermatological and oral hygiene products, which could induce severe liver and intestine injuries. Hence, it is essential to establish a rapid and sensitive method to monitor TCS, TCC, and CPs in various organisms. In this work, fluorine-functionalized covalent organic framework (COF-F) was prepared by using 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tri-aniline and 2,3,5,6-tetrafluoroterephthalaldehyde as two building units and employed as a solid phase microextraction (SPME) probe for the extraction of TCS, TCC and CPs. The COF-F possessed excellent hydrophobicity, a large specific surface area (1354.3 m2 g-1) and high uniform porosity (3.2 nm), which facilitated high selectivity and adsorption properties towards TCS, TCC, and CPs. Therefore, the as-prepared COF-F-SPME in combination with electrospray ionization mass spectrometry has been developed to provide fast and ultrasensitive detection of TCS, TCC, and CPs in biological samples. The established method demonstrated satisfactory linear ranges (0.01-100.00 µg L-1) and low limits of detection (0.003-0.040 µg L-1) for TCS, TCC and CPs. The developed method could be successfully applied to detect TCS, TCC and CPs in the liver and kidney tissues of mice, demonstrating the potential for the detection of chlorinated aromatic pollutants in the biological samples.


Assuntos
Carbanilidas , Clorofenóis , Microextração em Fase Sólida , Espectrometria de Massas por Ionização por Electrospray , Triclosan , Animais , Microextração em Fase Sólida/métodos , Triclosan/análise , Triclosan/química , Carbanilidas/análise , Camundongos , Clorofenóis/análise , Espectrometria de Massas por Ionização por Electrospray/métodos , Flúor/química , Estruturas Metalorgânicas/química , Limite de Detecção , Masculino
12.
Environ Sci Pollut Res Int ; 31(35): 47836-47850, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-39007977

RESUMO

This current study explored the effect of pyrite on the treatment of chlorophenolic compounds (CP) by Fenton process with micron-sized zero-valent iron (ZVI) as the catalyst. The experiments were conducted in batch reactors with 100 mg L-1 CP, 0-0.02 M H2O2, and variable pyrite and ZVI doses (0-1 g L-1). Our findings show that while the reactor with 1 g L-1 ZVI as the only catalyst achieved only 10% CP removal efficiency due to rapid ZVI surface passivation and ZVI particle aggregation, the CP removal efficiency increased with increasing pyrite dose and reached 100% within couple of minutes in reactors with 0.8 g L-1 pyrite and 0.2 g L-1 ZVI. The CP removal was mainly driven by the oxidative treatment of CPs with some strong radicals such as hydroxyl radicals (•OH) while the adsorption onto the catalyst surface was only responsible for 10 to 25% of CP removals, depending on the type of CP studied. The positive impact of pyrite on CP removal by the ZVI/H2O2 system could be attributed to the ability of pyrite to (1) create an acidic environment for optimum Fenton process, (2) provide support material for ZVI to minimize ZVI particle agglomeration, and (3) stimulate iron redox cycling for improved surface site generation. Following oxidative Fenton treatment, the degradation intermediate products of CPs, including some aromatic compounds (benzoquinone, hydroquinone, etc.) and organic acids (e.g., acetic acid), became more biodegradable in comparison to their mother compounds. Overall, the treatment systems with a mixture of ZVI and pyrite as catalyst materials could offer a suitable cost-effective technology for the treatment of wastewater containing biologically non- or low-degradable toxic compounds such as chlorophenols.


Assuntos
Clorofenóis , Peróxido de Hidrogênio , Ferro , Ferro/química , Peróxido de Hidrogênio/química , Clorofenóis/química , Concentração de Íons de Hidrogênio , Sulfetos/química , Catálise , Biodegradação Ambiental , Poluentes Químicos da Água/química , Oxirredução
13.
Water Res ; 262: 122090, 2024 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-39032340

RESUMO

Ammonia monooxygenase (AMO)-mediated cometabolism of organic pollutants has been widely observed in biological nitrogen removal process. However, its molecular mechanism remains unclear, hindering its practical application. Furthermore, conventional nitrification systems encounter significant challenges such as air pollution and the loss of ammonia-oxidizing bacteria, when dealing with wastewater containing volatile organic pollutants. This study developed a nitrifying membrane-aerated biofilm reactor (MABR) to enhance the biodegradation of volatile 4-chlorophenol (4-CP). Results showed that 4-CP was primarily removed via Nitrosomonas nitrosa-mediated cometabolism in the presence of NH4+-N, supported by the increased nicotinamide adenine dinucleotide (NADH) and adenosine triphosphate (ATP) content, AMO activity and the related genes abundance. Hydroquinone, detected for the first time and produced via oxidative dechlorination, as well as 4-chlorocatechol was primary transformation products of 4-CP. Nitrosomonas nitrosa AMO structural model was constructed for the first time using homology modeling. Molecular dynamics simulation suggested that the ortho-carbon in the benzene ring of 4-CP was more prone to metabolismcompared to the ipso-carbon. Density functional theory calculation revealed that 4-CP was metabolized by AMO via H-abstraction-OH-rebound reaction, with a significantly higher rebound barrier at the ipso-carbon (16.37 kcal·mol-1) as compared to the ortho-carbon (6.7 kcal·mol-1). This study fills the knowledge gap on the molecular mechanism of AMO-mediated cometabolism of organic pollutants, providing practical and theoretical foundations for improving volatile organic pollutants removal through nitrifying MABR.


Assuntos
Biofilmes , Biotransformação , Clorofenóis , Simulação de Dinâmica Molecular , Nitrificação , Clorofenóis/metabolismo , Oxirredutases/metabolismo , Biodegradação Ambiental
14.
Chemosphere ; 363: 142824, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-38996980

RESUMO

The disposal and resource utilization of sewage sludge (SS) have always been significant challenges for environmental protection. This study employed straightforward pyrolysis to prepare iron-containing sludge biochar (SBC) used as a catalyst and to recover bio-oil used as fuel energy. The results indicated that SBC-700 could effectively activate persulfate (PS) to remove 97.2% of 2,4-dichlorophenol (2,4-DCP) within 60 min. Benefiting from the appropriate iron content, oxygen-containing functional groups and defective structures provide abundant active sites. Meanwhile, SBC-700 exhibits good stability and reusability in cyclic tests and can be easily recovered by magnetic separation. The role of non-radicals is emphasized in the SBC-700/PS system, and in particular, single linear oxygen (1O2) is proposed to be the dominant reactive oxygen. The bio-oil, a byproduct of pyrolysis, exhibits a higher heating value (HHV) of about 30 MJ/kg, with H/C and O/C ratios comparable to those of biodiesel. The energy recovery rate of the SS pyrolysis system was calculated at 80.5% with a lower input cost. In conclusion, this investigation offers a low-energy consumption and sustainable strategy for the resource utilization of SS while simultaneously degrading contaminants.


Assuntos
Carvão Vegetal , Clorofenóis , Pirólise , Esgotos , Sulfatos , Carvão Vegetal/química , Esgotos/química , Clorofenóis/química , Sulfatos/química , Biocombustíveis/análise , Eliminação de Resíduos Líquidos/métodos , Poluentes Químicos da Água/química , Catálise , Ferro/química , Óleos de Plantas , Polifenóis
15.
J Hazard Mater ; 476: 135063, 2024 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-38954853

RESUMO

Ball-milled plastic char supported nano zero-valent iron (nZVI@BMPC) and their application combined with anaerobic sludge for microbial dechlorination of 2,4,6-trichlorophenol (2,4,6-TCP) were investigated. The XRD and FTIR analysis proved composition of zero valent states of iron, and the BET and SEM analysis showed that nZVI was uniformly distributed on the surface of BMPC. Successive addition of 1000 mg/L sodium lactate and nZVI@BMPC enhanced the acclamation of anaerobic sludge and resulted in the degradation of 4-CP within 80 days. The acclimated consortium with nZVI@BMPC completely degraded 2,4,6-TCP into CH4 and CO2, and the key dechlorination route was through 4-CP dechlorinaion and mineralization. The degradation rate of 2,4,6-TCP with nZVI@BMPC was 0.22/d, greater than that without nZVI@BMPC. The dechlorination efficiency was enhanced in the Fe2+/Fe3+ system controlled by nZVI@BMPC and iron-reducing bacteria. Metagenomic analysis result showed that the dominant de-chlorinators were Chloroflexi sp., Desulfovibrio, and Pseudomonas, which could directly degrade 2,4,6-TCP to 4-CP, especially, Chloroflexi bacterium could concurrently be used to mineralize 4-CP. The relative abundance of the functional genes cprA, acoA, acoB, and tfdB increased significantly in the presence of the nZVI@BMPC. This study provides a new strategy can be a good alternative for possible application in groundwater remediation.


Assuntos
Biodegradação Ambiental , Clorofenóis , Ferro , Esgotos , Clorofenóis/química , Clorofenóis/metabolismo , Esgotos/microbiologia , Ferro/química , Anaerobiose , Poluentes Químicos da Água/química , Poluentes Químicos da Água/metabolismo , Bactérias/metabolismo , Nanopartículas Metálicas/química
16.
J Environ Manage ; 366: 121805, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-39018859

RESUMO

Sulfurized nanoscale zero-valent iron supported on biochar (BC-SNZVI) has been successfully synthesized for 2,4,6-trichlorophenol (2,4,6-TCP) removal, while was only effectively under acidic conditions. To obtain highly efficient removal of 2,4,6-TCP within a broader pH range, weak static magnetic fields (WMF) was applied in BC-SNZVI/2,4,6-TCP aqueous systems. Results showed 30 mT WMF supported the most extensive 2,4,6-TCP removal, and 87.4% of 2,4,6-TCP (initial concentration of 30 mg/L) was removed by 0.5 g/L BC-SNZVI at neutral pH (pH = 6.8) within 180 min, which was increased by 54.4% compared to that without WMF. The observed rate constant (Kobs) under 30 mT WMF was 2.1-fold greater than that without WMF. Although three typical anions (NO3- (0.5-10.0 mM), H2PO4- (0.05-0.5 mM), and HCO3- (0.5-5.0 mM)) still inhibited 2,4,6-TCP removal, WMF could efficiently alleviate the inhibitory effects. Moreover, 73.1% of 2,4,6-TCP was successfully removed by BC-SNZVI under WMF in natural water. WMF remarkably boosted the dechlorination of 2,4,6-TCP, increasing the 2,4,6-TCP dechlorination efficiency from 45.2% (in the absence of WMF) to 83.8% (in the presence of WMF) by the end of 300 min. And the complete dechlorination product phenol appeared within 10 min. Force analysis confirmed the magnetic field gradient force (FB) moved paramagnetic Fe2+ at the SNZVI surface along the direction perpendicular to the external applied field, promoting the mass-transfer controlled SNZVI corrosion. Corrosion resistance analysis revealed WMF promoted the electron-transfer controlled SNZVI corrosion by decreasing its self-corrosion potential (Ecorr). With the introduction of sulfur, the magnitude of FB doubled and the Ecorr decreased comparing with NZVI. Our findings provide a facile and viable strategy for treating chlorinated phenols at neutral pH.


Assuntos
Carvão Vegetal , Clorofenóis , Ferro , Carvão Vegetal/química , Ferro/química , Clorofenóis/química , Concentração de Íons de Hidrogênio , Poluentes Químicos da Água/química , Campos Magnéticos
17.
Bioresour Technol ; 406: 131085, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38977038

RESUMO

In this work, an effort has been made to enhance the efficacy of biological process for the effective degradation of 2, 4-dichlorophenol (2, 4-DCP) from wastewater. The polyurethane foam was modified with Fe3O4 nanoparticles and combined with polyvinyl alcohol, sodium alginate, and bacterial consortium for biodegradation of 2, 4-DCP in a packed bed biofilm reactor. The maximum removal efficiency of 2, 4-DCP chemical oxygen demand, and total organic carbon were found to be 92.51 ± 0.83 %, 86.85 ± 1.32, and 91.78 ± 1.24 %, respectively, in 4 days and 100 mg L-1 of 2, 4-DCP concentration at an influent loading rate of 2 mg L-1h-1 and hydraulic retention time of 50 h. Packed bed biofilm reactor was effective for up to four cycles to remove 2, 4-DCP. Growth inhibition kinetics were evaluated using the Edward model, yielding maximum growth rate of 0.45 day-1, inhibition constant of 110.6 mg L-1, and saturation constant of 62.3 mg L-1.


Assuntos
Biodegradação Ambiental , Biofilmes , Reatores Biológicos , Clorofenóis , Poliuretanos , Poliuretanos/química , Biofilmes/efeitos dos fármacos , Cinética , Poluentes Químicos da Água , Animais
18.
Environ Sci Technol ; 58(29): 13131-13144, 2024 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-38986049

RESUMO

Pd-based electrodes are recognized to facilitate effective electrochemical hydrodechlorination (EHDC) as a result of their superior capacity for atomic hydrogen (H*) generation. However, challenges such as electrode stability, feasibility of treating complex matrices, and high cost associated with electrode synthesis hinder the application of Pd-based electrodes for EHDC. In this work, we investigated the feasibility of degrading 2,4-dichlorophenol (2,4-DCP) by EHDC employing Pd-loaded activated carbon particles, prepared via a simple wet-impregnation method, as a flow cathode (FC) suspension. Compared to other Pd-based EHDC studies, a much lower Pd loading (0.02-0.08 mg cm-2) was used. Because of the excellent mass transfer in the FC system, almost 100% 2,4-DCP was hydrodechlorinated to phenol within 1 h. The FC system also showed excellent performance in treating complex water matrices (including hardness ion-containing wastewater and various other chlorinated organics such as 2,4-dichlorobenzoic acid and trichloroacetic acid) with a relatively low energy consumption (0.26-1.56 kW h m-3 mg-1 of 2,4-DCP compared to 0.32-7.61 kW h m-3 mg-1 of 2,4-DCP reported by other studies). The FC synthesized here was stable over 36 h of continuous operation, indicating its potential suitability for real-world applications. Employing experimental investigations and mathematical modeling, we further show that hydrodechlorination of 2,4-DCP occurs via interaction with H*, with no role of direct electron transfer and/or HO•-mediated processes in the removal of 2,4-DCP.


Assuntos
Eletrodos , Filtração , Poluentes Químicos da Água/química , Purificação da Água/métodos , Águas Residuárias/química , Clorofenóis/química , Técnicas Eletroquímicas
19.
J Expo Sci Environ Epidemiol ; 34(4): 637-646, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38890543

RESUMO

BACKGROUND: Emerging studies suggest that endocrine disrupting chemicals (EDCs) in personal care and other consumer products are linked with various adverse health effects, including respiratory and reproductive effects. Despite Black persons using more personal care products than other demographic groups and having a high asthma burden, little is known regarding their consumer product use patterns and associated EDC exposures. OBJECTIVE: To examine the association between recent exposure to select EDCs with specific consumer products and behaviors in a cohort of 110 predominantly Black children with asthma, ages 8-17 years, living in Baltimore City, Maryland. METHODS: We quantified concentrations of bisphenol A (BPA), bisphenol S (BPS), bisphenol F, two dichlorophenols, four parabens, triclosan, benzophenone-3, and triclocarban in spot urine samples. Questionnaires were used to capture recent (last 24-h) consumer product use and behaviors. Associations between EDCs and consumer product uses/behaviors were assessed using multivariable linear regression, adjusting for age, gender, race/ethnicity, and caregiver income level. Effect estimates were expressed as geometric mean ratios of biomarker concentrations of product-users vs non-users. RESULTS: Increased concentrations to select EDCs were associated with recent use of air freshener (ratios; BPA: 1.9, 95%CI 1.4-2; BPS 1.7, 95%CI 1-2.97; propyl paraben: 3.0, 95%CI 1.6-5.6), scented candles (methyl paraben: 2.6, 95%CI 1.1-6.1), and scented carpet powder (2,5-dichlorophenol: 2.8, 95%CI 1.2-6.3). Additionally, consuming canned food was associated with some increased biomarker concentrations (ratios: BPA: 1.7, 95%CI 1.2-2.4; BPS: 2.1, 95% CI: 1.2-3.6). SIGNIFICANCE: These findings add to the body of evidence suggesting that recent use of select consumer products in Black children contributes to exposure of chemicals of concern and could potentially inform exposure mitigation interventions. Findings have broad potential health implications for pediatric populations and Black children who may face exposure and health disparities. IMPACT: Little is known about how children's personal care product use and consumer behaviors affect their exposures to endocrine disrupting chemicals (EDCs). This is particularly true for Black children who often experience a disparate exposure burden to many EDCs. This is a significant knowledge gap among children that are uniquely vulnerable to EDCs as they undergo critical windows of growth and development. Our findings show associations between consumer products and EDC exposures in predominantly Black children in low-income settings. Identifying EDC exposure determinants has broad health implications as many of these chemicals have been associated with adverse health risks.


Assuntos
Asma , Compostos Benzidrílicos , Cosméticos , Disruptores Endócrinos , Exposição Ambiental , Parabenos , Fenóis , Humanos , Criança , Disruptores Endócrinos/urina , Masculino , Adolescente , Feminino , Fenóis/urina , Baltimore/epidemiologia , Parabenos/análise , Exposição Ambiental/análise , Compostos Benzidrílicos/urina , Triclosan/urina , Benzofenonas/urina , Carbanilidas/urina , População Urbana/estatística & dados numéricos , Negro ou Afro-Americano/estatística & dados numéricos , Clorofenóis/urina , Inquéritos e Questionários , Poluentes Ambientais/urina , Sulfonas
20.
Epilepsia Open ; 9(4): 1502-1514, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38861254

RESUMO

OBJECTIVE: In Europe, cenobamate has been approved for use as an adjunctive therapy in adult patients with epilepsy (PWE) with focal-onset seizures (FOS) who have not responded satisfactorily to treatment with at least two antiseizure medications (ASMs). Pivotal trials and real-world observational studies have demonstrated a high efficacy of cenobamate, even in very difficult-to-treat epilepsies. Our aim was to investigate the efficacy of add-on cenobamate in adult PWE who were prospectively monitored. We compared these results with those previously obtained for add-on lacosamide, perampanel, and brivaracetam therapy. METHODS: Patients were enrolled from the CENKORK study, which is a prospective, non-interventional, open-label, monocenter cohort study of adult PWE experiencing FOS. The titration of cenobamate was performed according to the guidelines outlined in the summary of product characteristics. The primary outcome measure was the retention rate at 6 months and 1 year. In addition, we assessed seizure-free rates, the proportion of patients achieving at least a 50% seizure reduction, adverse events, and the reasons for treatment discontinuation. These outcome measures were compared with historical controls treated with adjunctive lacosamide, perampanel, or brivaracetam at our center. RESULTS: Between June 2021 and 2022, 172 PWE with ongoing FOS were included. 22 cases were lost to follow-up, leaving 150 cases for the 1-year assessment. The retention rates at 6 months and 1 year were 88.7% and 80%, respectively. Seizure freedom was achieved in 14% of patients at both the 6-month and 1-year marks, while the ≥50% responder rates were 50% and 61%, respectively. The 6-month retention rate was significantly higher in cenobamate than in other ASMs (p < 0.001 for each comparator). Adverse events were significantly more common with perampanel (p < 0.001). SIGNIFICANCE: Add-on cenobamate proved to be particularly efficacious compared to our experience with other recently introduced ASMs. PLAIN LANGUAGE SUMMARY: This observational study was carried out in 172 adult patients with difficult-to-treat epilepsy who were treated with adjunctive cenobamate. After 1 year, the data of 150 patients could be analyzed. Seizure freedom, in the preceding 3 months, was achieved in 14%. The rate of PWE continuing cenobamate was 80%. In our hands, cenobamate showed promising efficacy and tolerability even when compared to other recently introduced antiseizure medications.


Assuntos
Anticonvulsivantes , Carbamatos , Epilepsia Resistente a Medicamentos , Quimioterapia Combinada , Lacosamida , Nitrilas , Piridonas , Humanos , Lacosamida/uso terapêutico , Anticonvulsivantes/uso terapêutico , Masculino , Feminino , Adulto , Pessoa de Meia-Idade , Carbamatos/uso terapêutico , Piridonas/uso terapêutico , Estudos Prospectivos , Nitrilas/uso terapêutico , Epilepsia Resistente a Medicamentos/tratamento farmacológico , Resultado do Tratamento , Adulto Jovem , Pirrolidinonas/uso terapêutico , Idoso , Estudos de Coortes , Clorofenóis , Tetrazóis
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