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1.
Nature ; 630(8016): 381-386, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38811733

RESUMO

Lignocellulose is mainly composed of hydrophobic lignin and hydrophilic polysaccharide polymers, contributing to an indispensable carbon resource for green biorefineries1,2. When chemically treated, lignin is compromised owing to detrimental intra- and intermolecular crosslinking that hampers downstream process3,4. The current valorization paradigms aim to avoid the formation of new C-C bonds, referred to as condensation, by blocking or stabilizing the vulnerable moieties of lignin5-7. Although there have been efforts to enhance biomass utilization through the incorporation of phenolic additives8,9, exploiting lignin's proclivity towards condensation remains unproven for valorizing both lignin and carbohydrates to high-value products. Here we leverage the proclivity by directing the C-C bond formation in a catalytic arylation pathway using lignin-derived phenols with high nucleophilicity. The selectively condensed lignin, isolated in near-quantitative yields while preserving its prominent cleavable ß-ether units, can be unlocked in a tandem catalytic process involving aryl migration and transfer hydrogenation. Lignin in wood is thereby converted to benign bisphenols (34-48 wt%) that represent performance-advantaged replacements for their fossil-based counterparts. Delignified pulp from cellulose and xylose from xylan are co-produced for textile fibres and renewable chemicals. This condensation-driven strategy represents a key advancement complementary to other promising monophenol-oriented approaches targeting valuable platform chemicals and materials, thereby contributing to holistic biomass valorization.


Assuntos
Compostos Benzidrílicos , Biomassa , Fracionamento Químico , Lignina , Fenóis , Compostos Benzidrílicos/química , Compostos Benzidrílicos/metabolismo , Catálise , Celulose/química , Celulose/metabolismo , Fracionamento Químico/métodos , Hidrogenação , Lignina/química , Lignina/metabolismo , Fenóis/química , Fenóis/metabolismo , Madeira/química , Xilanos/química , Xilanos/metabolismo , Xilose/química , Xilose/metabolismo , Combustíveis Fósseis , Têxteis
2.
Proc Natl Acad Sci U S A ; 119(32): e2116289119, 2022 08 09.
Artigo em Inglês | MEDLINE | ID: mdl-35917342

RESUMO

Glioblastoma (GBM) is an aggressive malignant primary brain tumor with limited therapeutic options. We show that the angiotensin II (AngII) type 2 receptor (AT2R) is a therapeutic target for GBM and that AngII, endogenously produced in GBM cells, promotes proliferation through AT2R. We repurposed EMA401, an AT2R antagonist originally developed as a peripherally restricted analgesic, for GBM and showed that it inhibits the proliferation of AT2R-expressing GBM spheroids and blocks their invasiveness and angiogenic capacity. The crystal structure of AT2R bound to EMA401 was determined and revealed the receptor to be in an active-like conformation with helix-VIII blocking G-protein or ß-arrestin recruitment. The architecture and interactions of EMA401 in AT2R differ drastically from complexes of AT2R with other relevant compounds. To enhance central nervous system (CNS) penetration of EMA401, we exploited the crystal structure to design an angiopep-2-tethered EMA401 derivative, A3E. A3E exhibited enhanced CNS penetration, leading to reduced tumor volume, inhibition of proliferation, and increased levels of apoptosis in an orthotopic xenograft model of GBM.


Assuntos
Bloqueadores do Receptor Tipo 2 de Angiotensina II , Compostos Benzidrílicos , Neoplasias Encefálicas , Reposicionamento de Medicamentos , Glioblastoma , Isoquinolinas , Receptor Tipo 2 de Angiotensina , Analgésicos/farmacologia , Angiotensina II/química , Angiotensina II/farmacologia , Bloqueadores do Receptor Tipo 2 de Angiotensina II/uso terapêutico , Apoptose , Compostos Benzidrílicos/química , Compostos Benzidrílicos/farmacologia , Compostos Benzidrílicos/uso terapêutico , Neoplasias Encefálicas/tratamento farmacológico , Glioblastoma/tratamento farmacológico , Humanos , Isoquinolinas/química , Isoquinolinas/farmacologia , Isoquinolinas/uso terapêutico , Conformação Proteica em alfa-Hélice , Receptor Tipo 2 de Angiotensina/química , Receptor Tipo 2 de Angiotensina/metabolismo , Carga Tumoral/efeitos dos fármacos
3.
Anal Bioanal Chem ; 416(15): 3519-3532, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38656365

RESUMO

The masking of specific effects in in vitro assays by cytotoxicity is a commonly known phenomenon. This may result in a partial or complete loss of effect signals. For common in vitro assays, approaches for identifying and quantifying cytotoxic masking are partly available. However, a quantification of cytotoxicity-affected signals is not possible. As an alternative, planar bioassays that combine high-performance thin layer chromatography with in vitro assays, such as the planar yeast estrogen screen (p-YES), might allow for a quantification of cytotoxically affected signals. Affected signals form a typical ring structure with a supressed or completely lacking centre that results in a double peak chromatogram. This study investigates whether these double peaks can be used for fitting a peak function to extrapolate the theoretical, unaffected signals. The precision of the modelling was evaluated for four individual peak functions, using 42 ideal, undistorted peaks from estrogenic model compounds in the p-YES. Modelled ED50-values from bisphenol A (BPA) experiments with cytotoxically disturbed signals were 13 times higher than for the apparent data without compensation for cytotoxicity (320 ± 63 ng versus 24 ± 17 ng). This finding has a high relevance for the modelling of mixture effects according to concentration addition that requires unaffected, complete dose-response relationships. Finally, we applied the approach to results of a p-YES assay on leachate samples of an elastomer material used in water engineering. In summary, the fitting approach enables the quantitative evaluation of cytotoxically affected signals in planar in vitro assays and also has applications for other fields of chemical analysis like distorted chromatography signals.


Assuntos
Bioensaio , Bioensaio/métodos , Cromatografia em Camada Fina/métodos , Fenóis/toxicidade , Fenóis/análise , Fenóis/química , Compostos Benzidrílicos/toxicidade , Compostos Benzidrílicos/análise , Compostos Benzidrílicos/química , Estrogênios/análise , Estrogênios/toxicidade
4.
Environ Res ; 255: 119192, 2024 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-38777299

RESUMO

The present study evaluates the adsorption efficiency of low-cost carbonaceous adsorbents as fly ash (FA), saw dust biochar (SDB) (untreated and alkali - treated), live/dead pulverized white rot fungus Hypocrea lixii biomass encapsulated in sodium alginate (SA) against the commercially available activated carbon (AC) and graphene oxide (GO) SA beads for removal of benzene phenol derivatives - Bisphenol A (BPA)/triclosan (TCS). Amongst bi - and tri - composites SA beads, tri-composite beads comprising of untreated flyash - dead fungal biomass - sodium alginate (UFA - DB - SA) showed at par results with commercial composite beads. The tri - composite beads with point zero charge (Ppzc) of 6.2 was characterized using FTIR, XRD, surface area BET and SEM-EDX. The batch adsorption using tri - composite beads revealed removal of 93% BPA with adsorption capacity of 16.6 mg/g (pH 6) and 83.72% TCS with adsorption capacity of 14.23 mg/g (pH 5), respectively at 50 ppm initial concentration with 6 % adsorbent dose in 5 h. Freundlich isotherm favoring multilayered adsorption provided a better fit with r2 of 0.9674 for BPA and 0.9605 for TCS respectively. Intraparticle diffusion model showed adsorption of BPA/TCS molecules to follow pseudo - second order kinetics with boundary layer diffusion governed by first step of fast adsorption and intraparticle diffusion within pores by second slow adsorption step. Thermodynamic parameters (ΔH°, ΔS°, ΔG°) revealed adsorption process as exothermic, orderly and spontaneous. Methanol showed better desorbing efficiency leading to five cycles reusability. The phytotoxicity assay revealed increased germination rate of mung bean (Vigna radiata) seeds, sprinkled with post adsorbed treated water (0 h, 5 h and 7 h) initially spiked with 50 ppm BPA/TCS. Overall, UFA - DB - SA tri - composite beads provides a cost effective and eco - friendly matrix for effective removal of hydrophobic recalcitrant compounds.


Assuntos
Alginatos , Compostos Benzidrílicos , Fenóis , Adsorção , Fenóis/química , Alginatos/química , Compostos Benzidrílicos/química , Grafite/química , Poluentes Químicos da Água/química , Carvão Vegetal/química , Hypocrea/química , Cinza de Carvão/química
5.
Environ Res ; 252(Pt 3): 119015, 2024 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-38692423

RESUMO

Carbon material modification and defect engineering are indispensable for bolstering the photocatalytic effectiveness of bismuth halide oxide (BiOX). In this study, a novel porous and defect-rich Ar-CB-2 photocatalyst was synthesized for emerging pollutants degradation. Leveraging the interfacial coupling effect of multi-walled carbon nanotubes (MWCNTs), we expanded the absorption spectrum of BiOI nanosheets and significantly suppressed the recombination of charge carriers. Introducing defects via Argon (Ar) plasma-etching further bolstered the adsorption efficacy and electron transfer properties of photocatalyst. In comparison to the pristine BiOI and CB-2, the Ar-CB-2 photocatalyst demonstrated superior photodegradation efficiency, with the first-order reaction rates for the photodegradation of tetracycline (TC) and bisphenol A (BPA) increasing by 2.83 and 4.53 times, respectively. Further probe experiments revealed that the steady-state concentrations of ·O2- and 1O2 in the Ar-CB-2/light system were enhanced by a factor of 1.67 and 1.28 compared to CB-2/light system. This result confirmed that the porous and defect-rich structure of Ar-CB-2 inhibited electron-hole recombination and boosted photocatalyst-oxygen interaction, swiftly transforming O2 into active oxygen species, thus accelerating their production. Furthermore, the possible degradation pathways for TC and BPA in the Ar-CB-2/light system were predicted. Overall, these findings offered a groundbreaking approach to the development of highly effective photocatalysts, capable of swiftly breaking down emerging pollutants.


Assuntos
Argônio , Compostos Benzidrílicos , Bismuto , Nanotubos de Carbono , Fenóis , Fotólise , Bismuto/química , Nanotubos de Carbono/química , Catálise , Porosidade , Fenóis/química , Compostos Benzidrílicos/química , Argônio/química , Tetraciclina/química , Poluentes Químicos da Água/química , Poluentes Ambientais/química , Processos Fotoquímicos , Gases em Plasma/química
6.
Environ Res ; 249: 118093, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38237759

RESUMO

Plastic pollution has become a major environmental problem because it does not break down and poses risks to ecosystems and human health. This study focuses on the environmentally friendly synthesis of ZnO nanocubes using an extract from Ceropegia omissa H. Huber plant leaves. The primary goal is to investigate the viability of these nanocubes as visible-light photocatalysts for the degradation of bisphenol A (BPA). The synthesized ZnO nanocubes have a highly crystalline structure and a bandgap of 3.1 eV, making them suitable for effective visible-light photocatalysis. FTIR analysis, which demonstrates that the pertinent functional groups are present, demonstrates the chemical bonding and reducing processes that take place in the plant extract. The XPS method also studies zinc metals, oxygen valencies, and binding energies. Under visible light irradiation, ZnO nanocubes degrade BPA by 86% in 30 min. This plant-extract-based green synthesis method provides a long-term replacement for traditional procedures, and visible light photocatalysis has advantages over ultraviolet light. The study's results show that ZnO nanocubes may be good for the environment and can work well as visible light photocatalysts to break down organic pollutants. This adds to what is known about using nanoparticles to clean up the environment. As a result, this study highlights the potential of using environmentally friendly ZnO nanocubes as a long-lasting and efficient method of reducing organic pollutant contamination in aquatic environments.


Assuntos
Compostos Benzidrílicos , Luz , Fenóis , Extratos Vegetais , Poluentes Químicos da Água , Óxido de Zinco , Óxido de Zinco/química , Compostos Benzidrílicos/química , Fenóis/química , Fenóis/análise , Extratos Vegetais/química , Poluentes Químicos da Água/química , Catálise , Química Verde/métodos , Fotólise
7.
Environ Res ; 249: 118427, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38325780

RESUMO

Porous organic polymers (POPs) present superior adsorption performance to steroid endocrine disruptors. However, the effective recovery and high cost have been a big limitation for their large-scale applications. Herein, magnetic azo-linked porous polymers (Fe3O4@SiO2/ALP-p) were designed and prepared in a green synthesis approach using low-price materials from phloroglucinol and pararosaniline via a diazo-coupling reaction under standard temperature and pressure conditions, which embedded with Fe3O4@SiO2 nanoparticles to form three-dimensional interlayer network structure with flexible-rigid interweaving. The saturated adsorption capacity to bisphenol-A (BPA) was 485.09 mg/g at 298 K, which increased by 1.4 times compared with ALP-p of relatively smaller mass density. This enhanced adsorption was ascribed to increment from surface adsorption and pore filling with 2.3 times of specific surface area and 2.6 times of pore volume, although the total organic functional groups decreased with Fe3O4@SiO2 amendment. Also, the adsorption rate increased by about 1.1 and 1.5-fold due to enhancement in the initial stage of surface adsorption and subsequent stage pore diffusion, respectively. Moreover, this adsorbent could be used in broad pH (3.0-7.0) and salinity adaptability (<0.5 mol/L). The loss of adsorption capacity and magnetic recovery were lower than 1.1% and 0.8% in each operation cycle because of the flexible-rigid interweave. This excellent performance was contributed by synergistic effects from physisorption and chemisorption, such as pore filling, electrostatic attraction, π-π stacking, hydrogen bonding, and hydrophobic interaction. This study offered a cost-effective, high-performing, and ecologically friendly material along with a green preparation method.


Assuntos
Compostos Benzidrílicos , Fenóis , Polímeros , Poluentes Químicos da Água , Adsorção , Fenóis/química , Poluentes Químicos da Água/química , Porosidade , Polímeros/química , Compostos Benzidrílicos/química , Química Verde/métodos , Compostos Azo/química , Reciclagem/métodos , Purificação da Água/métodos
8.
Environ Res ; 251(Pt 2): 118718, 2024 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-38490623

RESUMO

Bisphenol A (BPA) degradation efficiency by bacteria or by metal-organic-frameworks (MOFs) catalyzed persulfate (PMS) oxidation have been studied intensively. However, their synergistic effect on BPA degradation was less reported. In this study, we combined previously synthesized CNT-hemin/Mn-MOF with an BPA degrading bacteria SQ-2 to form a composite (SQ-2@MOFs). CNT-hemin/Mn-MOF in the composite catalyzed little PMS to promote the degradation efficiency of SQ-2 on BPA. Results indicated SQ-2@MOFs significantly accelerated BPA degradation rate than SQ-2 alone. Furthermore, SQ-2@MOFs composite was successfully immobilized in hydrogel to achieve better degradation performance. Immobilized SQ-2@MOFs could almost completely degrade 1-20 mg/L BPA within 24 h and completely degrade 5 mg/L BPA at pH 4-8. Besides, degradation byproducts also reduced by immobilized SQ-2@MOFs, which promoted the cleaner biodegradation of BPA. Metabolomics and multiple chemical characterization results revealed the interconnection mechanism between CNT-hemin/Mn-MOFs, SQ-2 and hydrogel. CNT-hemin/Mn-MOF helped SQ-2 degrade BPA into more biodegradable products, promoted electron transfer, and augmented BPA degradation ability of SQ-2 itself. SQ-2 enabled the surface electronegativity of SQ-2@MOFs more suitable for BPA contact. Meanwhile, SQ-2 avoided the loss of Fe and Mn of CNT-hemin/Mn-MOF. Hydrogel augmented the above synergistic effect. This study provided new perspective for the development of biodegradation materials through interdisciplinary integration.


Assuntos
Compostos Benzidrílicos , Biodegradação Ambiental , Hidrogéis , Estruturas Metalorgânicas , Fenóis , Compostos Benzidrílicos/química , Compostos Benzidrílicos/metabolismo , Fenóis/química , Fenóis/metabolismo , Hidrogéis/química , Estruturas Metalorgânicas/química , Poluentes Químicos da Água/química , Poluentes Químicos da Água/metabolismo , Bactérias/metabolismo
9.
Ecotoxicol Environ Saf ; 272: 116065, 2024 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-38330872

RESUMO

Bisphenol A (BPA) and its substitute bisphenol S (BPS) are desirable materials widely used in manufacturing plastic products but can pose carcinogenic risks to humans. A new conductive iron-based metal-organic framework (Fe-HHTP)-modified pencil graphite electrode (PGE) for electrochemically sensing BPA and BPS was prepared and fully characterized by SEM, TEM, FT-IR, XRD, and XPS. Results showed that the optimal conditions for preparing Fe-HHTP/PGE were a pH of 6.5, a Fe-HHTP concentration of 2 mg·mL-1, a deposition potential of 0 V, and a deposition time of 100 s. The Fe-HHTP/PGE prepared under such conditions harbored a significant electrocatalytic activity with a detection limit of 0.8 nM for BPA and 1.7 nM for BPS (S/N = 3). Correspondingly, the electrochemical response current was linearly correlated to BPA and BPS, ranging from 0.01 to 100 µM. Fe-HHTP/PGE also obtained satisfactory recoveries by 93.8-102.1% and 96.0-101.3% for detecting BPA and BPS in plastic food packaging samples. Our work has provided a novel electrochemical tool to simultaneously detect BPA and BPS in food packaging samples and environmental matrixes.


Assuntos
Grafite , Estruturas Metalorgânicas , Fenóis , Humanos , Grafite/química , Espectroscopia de Infravermelho com Transformada de Fourier , Compostos Benzidrílicos/química , Eletrodos
10.
J Environ Manage ; 362: 121342, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38830282

RESUMO

In this study, Ag/Bi2O3/Bi5O7I with s-scheme heterostructures were successfully synthesized in situ by nano-silver modification of CUA-17 and halogenated hydrolysis.The growth rate of Bi2O3 crystals was effectively controlled by adjusting the doping amount of Ag, resulting in the formation of a facet-coupling heterojunctions. Through the investigation of the microstructure and compositional of catalysts, it has been confirmed that an intimate facet coupling between the Bi2O3 (120) facet and the Bi5O7I (312) facet, which provides robust support for charge transfer. Under visible light irradiation, the AgBOI.3 heterojunction photocatalyst exhibited an outstanding degradation rate of 98.2% for Bisphenol A (BPA) with excellent stability. Further characterization using optical, electrochemical, impedance spectroscopy, and electron spin resonance techniques revealed significantly enhanced efficiency in photogenerated charge separation and transfer, and confirming the s-scheme structure of the photocatalyst. Density functional theory calculations was employed to elucidate the mechanism of BPA degradation and the degradation pathway of BPA was investigated by LC-MS. Finally, the toxicity of the degradation intermediates was evaluated using T.E.S.T software.


Assuntos
Compostos Benzidrílicos , Bismuto , Fenóis , Prata , Fenóis/química , Compostos Benzidrílicos/química , Bismuto/química , Catálise , Prata/química
11.
J Environ Manage ; 358: 120846, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38599079

RESUMO

Recently, the Fenton-like reaction using peroxymonosulfate (PMS) has been acknowledged as a potential method for breaking down organic pollutants. In this study, we successfully synthesized a highly efficient and stable single atom molybdenum (Mo) catalyst dispersed on nitrogen-doped carbon (Mo-NC-0.1). This catalyst was then utilized for the first time to activate PMS and degrade bisphenol A (BPA). The Mo-NC-0.1/PMS system demonstrated the ability to completely degrade BPA within just 20 min. Scavenging tests and density functional theory (DFT) calculations have demonstrated that the primary reactive oxygen species was singlet oxygen (1O2) produced by Mo-N4 sites. The self-cycling of Mo facilitated PMS activation and the transition from a free radical activation pathway to a non-radical pathway mediated by 1O2. Simultaneously, the nearby pyridinic N served as adsorption sites to immobilize BPA and PMS molecules. The exceptionally high catalytic activity of Mo-NC-0.1 derived from its unique Mo-N coordination, which markedly reduced the distance for 1O2 to migrate to the BPA molecules. The Mo-NC-0.1/PMS system effectively reduced the acute toxicity of BPA and exhibited excellent cycling stability with minimal leaching. This study presented a new catalyst with high selectivity for 1O2 generation and provided valuable insights for the application of single atom catalysts in PMS-based AOPs.


Assuntos
Molibdênio , Oxigênio Singlete , Catálise , Molibdênio/química , Oxigênio Singlete/química , Nitrogênio/química , Compostos Benzidrílicos/química , Fenóis/química , Peróxidos/química
12.
Molecules ; 29(11)2024 May 27.
Artigo em Inglês | MEDLINE | ID: mdl-38893397

RESUMO

A specific feature of mushrooms (including those of the genus Pleurotus) is their natural ability to absorb and accumulate many chemical substances present in their immediate environment, which makes them an excellent natural sorption material. Hence, fruiting bodies of mushrooms have been recognized for years as excellent indicators of the environment, reflecting its current state. Nevertheless, mushrooms can accumulate both health-promoting substances, such as bioelements, and toxic substances, such as heavy metals and organic compounds, including bisphenol A® (BPA). This organic chemical compound in the phenol group, although it has been withdrawn in the EU since 2010, is widely present in the environment around us. In the present experiment, we aimed to determine the effect of adding BPA to liquid media for in vitro cultures of Pleurotus spp. The biomass increases were determined. Moreover, the degrees of adsorption and desorption of BPA from the obtained freeze-dried biomass in two different environments (neutral and acidic) were determined as a function of time. This is the first study to determine the bioavailability of adsorbed BPA in obtained biomass by extracting the mycelium into artificial digestive juices in a model digestive system. BPA was added to the liquid Oddoux medium in the following amounts: 0.01, 0.5, and 0.5 g/250 mL of medium. The amounts of adsorbed and desorbed BPA were determined by flow injection analysis (FIA) with amperometric detection. The addition of BPA to the substrate reduced the biomass growth in each of the discussed cases. BPA adsorption by the mycelium occurred at over 90% and depended on the morphology of the mushroom (structure, surface development, and pore size). BPA desorption depended on the pH of the environment and the desorption time. Mushrooms are an excellent natural remedial material, but BPA is extracted into artificial digestive juices; therefore, consuming mushrooms from industrialized areas may have health consequences for our bodies.


Assuntos
Compostos Benzidrílicos , Biomassa , Fenóis , Pleurotus , Fenóis/química , Fenóis/metabolismo , Pleurotus/metabolismo , Pleurotus/química , Pleurotus/crescimento & desenvolvimento , Compostos Benzidrílicos/química , Compostos Benzidrílicos/metabolismo , Adsorção , Análise de Injeção de Fluxo
13.
Environ Monit Assess ; 196(5): 492, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38691228

RESUMO

Bisphenol A (BPA) is an essential and extensively utilized chemical compound with significant environmental and public health risks. This review critically assesses the current water purification techniques for BPA removal, emphasizing the efficacy of adsorption technology. Within this context, we probe into the synthesis of magnetic biochar (MBC) using co-precipitation, hydrothermal carbonization, mechanical ball milling, and impregnation pyrolysis as widely applied techniques. Our analysis scrutinizes the strengths and drawbacks of these techniques, with pyrolytic temperature emerging as a critical variable influencing the physicochemical properties and performance of MBC. We explored various modification techniques including oxidation, acid and alkaline modifications, element doping, surface functional modification, nanomaterial loading, and biological alteration, to overcome the drawbacks of pristine MBC, which typically exhibits reduced adsorption performance due to its magnetic medium. These modifications enhance the physicochemical properties of MBC, enabling it to efficiently adsorb contaminants from water. MBC is efficient in the removal of BPA from water. Magnetite and maghemite iron oxides are commonly used in MBC production, with MBC demonstrating effective BPA removal fitting well with Freundlich and Langmuir models. Notably, the pseudo-second-order model accurately describes BPA removal kinetics. Key adsorption mechanisms include pore filling, electrostatic attraction, hydrophobic interactions, hydrogen bonding, π-π interactions, and electron transfer surface interactions. This review provides valuable insights into BPA removal from water using MBC and suggests future research directions for real-world water purification applications.


Assuntos
Compostos Benzidrílicos , Carvão Vegetal , Fenóis , Águas Residuárias , Poluentes Químicos da Água , Purificação da Água , Carvão Vegetal/química , Compostos Benzidrílicos/química , Compostos Benzidrílicos/análise , Fenóis/análise , Fenóis/química , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/química , Purificação da Água/métodos , Adsorção , Águas Residuárias/química , Eliminação de Resíduos Líquidos/métodos
14.
J Environ Sci (China) ; 139: 569-588, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38105077

RESUMO

Environmental pollution, such as water contamination, is a critical issue that must be absolutely addressed. Here, three different morphologies of tungsten-based photocatalysts (WO3 nanorods, WO3/WS2 nanobricks, WO3/WS2 nanorods) are made using a simple hydrothermal method by changing the solvents (H2O, DMF, aqueous HCl solution). The as-prepared nanocatalysts have excellent thermal stability, large porosity, and high hydrophilicity. The results show all materials have good photocatalytic activity in aqueous media, with WO3/WS2 nanorods (NRs) having the best activity in the photodegradation of bisphenol A (BPA) under visible-light irradiation. This may originate from increased migration of charge carriers and effective prevention of electron‒hole recombination in WO3/WS2 NRs, whereby this photocatalyst is able to generate more reactive •OH and •O2- species, leading to greater photocatalytic activity. About 99.6% of BPA is photodegraded within 60 min when using 1.5 g/L WO3/WS2 NRs and 5.0 mg/L BPA at pH 7.0. Additionally, the optimal conditions (pH, catalyst dosage, initial BPA concentration) for WO3/WS2 NRs are also elaborately investigated. These rod-like heterostructures are expressed as potential catalysts with excellent photostability, efficient reusability, and highly active effectivity in different types of water. In particular, the removal efficiency of BPA by WO3/WS2 NRs reduces by only 1.5% after five recycling runs and even reaches 89.1% in contaminated lake water. This study provides promising insights for the nearly complete removal of BPA from wastewater or different water resources, which is advantageous to various applications in environmental remediation.


Assuntos
Luz , Tungstênio , Tungstênio/química , Compostos Benzidrílicos/química , Água , Catálise
15.
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
16.
Toxicol Appl Pharmacol ; 466: 116477, 2023 05 01.
Artigo em Inglês | MEDLINE | ID: mdl-36940861

RESUMO

Many studies suggest that the potential impact of bisphenol S (BPS) as an endocrine disruptor is comparable to that of bisphenol A (BPA). However, in vitro-to-in vivo and from animal to human extrapolations require knowledge of the plasma free fraction of the active endocrine compounds. The present study aimed to characterise BPA and BPS binding to plasma proteins both in humans and different animal species. The plasma protein binding of BPA and BPS was assessed by equilibrium dialysis in plasma from adult female mice, rats, monkeys, early and late pregnant women as well as paired cord blood, early and late pregnant sheep and foetal sheep. The fraction of free BPA was independent of plasma concentrations and ranged between 4% and 7% in adults. This fraction was 2 to 3.5 times lower than that of BPS in all species except sheep, ranging from 3% to 20%. Plasma binding of BPA and BPS was not affected by the stage of pregnancy, BPA and BPS free fractions representing about 4% and 9% during early and late human pregnancy, respectively. These fractions were lower than the free fractions of BPA (7%) and BPS (12%) in cord blood. Our results suggest that similarly to BPA, BPS is extensively bound to proteins, mainly albumin. The higher fraction of free BPS compared to BPA may have implications for human exposure assessment since BPS free plasma concentrations are expected to be 2 to 3.5 times higher than that of BPA for similar plasma concentration.


Assuntos
Compostos Benzidrílicos , Fenóis , Adulto , Gravidez , Humanos , Feminino , Ratos , Animais , Camundongos , Ovinos , Compostos Benzidrílicos/química , Proteínas Sanguíneas , Feto
17.
Immunity ; 40(4): 477-89, 2014 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-24745332

RESUMO

We identified three retinoid-related orphan receptor gamma t (RORγt)-specific inhibitors that suppress T helper 17 (Th17) cell responses, including Th17-cell-mediated autoimmune disease. We systemically characterized RORγt binding in the presence and absence of drugs with corresponding whole-genome transcriptome sequencing. RORγt acts as a direct activator of Th17 cell signature genes and a direct repressor of signature genes from other T cell lineages; its strongest transcriptional effects are on cis-regulatory sites containing the RORα binding motif. RORγt is central in a densely interconnected regulatory network that shapes the balance of T cell differentiation. Here, the three inhibitors modulated the RORγt-dependent transcriptional network to varying extents and through distinct mechanisms. Whereas one inhibitor displaced RORγt from its target loci, the other two inhibitors affected transcription predominantly without removing DNA binding. Our work illustrates the power of a system-scale analysis of transcriptional regulation to characterize potential therapeutic compounds that inhibit pathogenic Th17 cells and suppress autoimmunity.


Assuntos
Benzenoacetamidas/farmacologia , Compostos Benzidrílicos/farmacologia , Digoxina/farmacologia , Encefalomielite Autoimune Experimental/tratamento farmacológico , Redes Reguladoras de Genes/efeitos dos fármacos , Compostos Heterocíclicos de 4 ou mais Anéis/farmacologia , Esclerose Múltipla/tratamento farmacológico , Membro 3 do Grupo F da Subfamília 1 de Receptores Nucleares/antagonistas & inibidores , Subpopulações de Linfócitos T/efeitos dos fármacos , Células Th17/efeitos dos fármacos , Androstenóis/química , Animais , Benzenoacetamidas/química , Compostos Benzidrílicos/química , Diferenciação Celular/efeitos dos fármacos , Linhagem Celular Tumoral , Linhagem da Célula/efeitos dos fármacos , Citocinas/metabolismo , Digoxina/química , Encefalomielite Autoimune Experimental/imunologia , Compostos Heterocíclicos de 4 ou mais Anéis/química , Humanos , Camundongos , Camundongos Endogâmicos C57BL , Camundongos Knockout , Esclerose Múltipla/imunologia , Glicoproteína Mielina-Oligodendrócito/imunologia , Membro 3 do Grupo F da Subfamília 1 de Receptores Nucleares/genética , Fragmentos de Peptídeos/imunologia , Ligação Proteica/efeitos dos fármacos , Relação Estrutura-Atividade , Biologia de Sistemas , Subpopulações de Linfócitos T/imunologia , Células Th17/imunologia , Transcrição Gênica/efeitos dos fármacos , Ativação Transcricional/efeitos dos fármacos
18.
Environ Res ; 235: 116487, 2023 10 15.
Artigo em Inglês | MEDLINE | ID: mdl-37419196

RESUMO

Bisphenols and Perfluoroalkyls are chemical compounds widely used in industry known to be endocrine disruptors (EDs). Once ingested through contaminated aliments, they mimic the activity of endogenous hormones leading to a broad spectrum of diseases. Due to the extensive use of plastic in human life, particular attention should be paid to antenatal exposure to Bisphenols and Perfluoroalkyls since they cross the placental barrier and accumulates in developing embryo. Here we investigated the effects of Bisphenol-A (BPA), Bisphenol-S (BPS), perfluorooctane-sulfonate (PFOS) and perfluorooctanoic-acid (PFOA), alone or combined, on human-induced pluripotent stem cells (hiPSCs) that share several biological features with the stem cells of blastocysts. Our data show that these EDs affect hiPSC inducing a great mitotoxicity and dramatic changes in genes involved in the maintenance of pluripotency, germline specification, and epigenetic regulation. We also evidenced that these chemicals, when combined, may have additive, synergistic but also negative effects. All these data suggest that antenatal exposure to these EDs may affect the integrity of stem cells in the developing embryos, interfering with critical stages of early human development that might be determinant for fertility. The observation that the effects of exposure to a combination of these chemicals are not easily foreseeable further highlights the need for wider awareness of the complexity of the EDs effects on human health and of the social and economic burden attributable to these compounds.


Assuntos
Disruptores Endócrinos , Fluorocarbonos , Infertilidade , Humanos , Feminino , Gravidez , Epigênese Genética , Placenta , Fertilidade , Compostos Benzidrílicos/toxicidade , Compostos Benzidrílicos/química , Fluorocarbonos/toxicidade , Disruptores Endócrinos/toxicidade
19.
Proc Natl Acad Sci U S A ; 117(47): 29677-29683, 2020 11 24.
Artigo em Inglês | MEDLINE | ID: mdl-33168711

RESUMO

Yeast prions provide self-templating protein-based mechanisms of inheritance whose conformational changes lead to the acquisition of diverse new phenotypes. The best studied of these is the prion domain (NM) of Sup35, which forms an amyloid that can adopt several distinct conformations (strains) that confer distinct phenotypes when introduced into cells that do not carry the prion. Classic dyes, such as thioflavin T and Congo red, exhibit large increases in fluorescence when bound to amyloids, but these dyes are not sensitive to local structural differences that distinguish amyloid strains. Here we describe the use of Michler's hydrol blue (MHB) to investigate fibrils formed by the weak and strong prion fibrils of Sup35NM and find that MHB differentiates between these two polymorphs. Quantum mechanical time-dependent density functional theory (TDDFT) calculations indicate that the fluorescence properties of amyloid-bound MHB can be correlated to the change of binding site polarity and that a tyrosine to phenylalanine substitution at a binding site could be detected. Through the use of site-specific mutants, we demonstrate that MHB is a site-specific environmentally sensitive probe that can provide structural details about amyloid fibrils and their polymorphs.


Assuntos
Compostos de Anilina/química , Compostos Benzidrílicos/química , Príons/química , Amiloide/química , Sítios de Ligação , Vermelho Congo/química , Fluorescência , Proteínas Fúngicas/química , Fatores de Terminação de Peptídeos/química , Domínios Proteicos , Leveduras/química
20.
Int J Mol Sci ; 24(3)2023 Feb 02.
Artigo em Inglês | MEDLINE | ID: mdl-36769204

RESUMO

Bisphenol A (4,4-isopropylidenediphenol, BPA) is an organic compound widely used, e.g., in the production of epoxy resins, plastics, and thermal receipt papers. Unfortunately, bisphenol A has negative effects on human health, which has prompted the search for an effective method of its removal. One of the most promising methods of its elimination is photocatalytic removal. The aim of this study was to design an effective method for the photocatalytic removal of bisphenol A using, for the first time, hierarchical zeolites and ruthenium ion-modified diatom biosilica, and silver as photocatalysts and optimization of the reaction conditions: temperature, pH, and composition of the reaction mixture as well as the electromagnetic wavelength. Additionally, for the first time, the electromagnetic wavelength that would be most suitable for the study was selected. All materials used were initially characterized by XRD and low-temperature nitrogen adsorption/desorption isotherms. Ruthenium ion-modified biosilica proved to be the most effective catalyst for bisphenol A removal, which occurred at a rate higher than 99%.


Assuntos
Diatomáceas , Rutênio , Poluentes Químicos da Água , Zeolitas , Humanos , Zeolitas/química , Poluentes Químicos da Água/química , Compostos Benzidrílicos/química
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