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1.
Nature ; 589(7842): 396-401, 2021 01.
Artigo em Inglês | MEDLINE | ID: mdl-33473229

RESUMO

The water-gas shift (WGS) reaction is an industrially important source of pure hydrogen (H2) at the expense of carbon monoxide and water1,2. This reaction is of interest for fuel-cell applications, but requires WGS catalysts that are durable and highly active at low temperatures3. Here we demonstrate that the structure (Pt1-Ptn)/α-MoC, where isolated platinum atoms (Pt1) and subnanometre platinum clusters (Ptn) are stabilized on α-molybdenum carbide (α-MoC), catalyses the WGS reaction even at 313 kelvin, with a hydrogen-production pathway involving direct carbon monoxide dissociation identified. We find that it is critical to crowd the α-MoC surface with Pt1 and Ptn species, which prevents oxidation of the support that would cause catalyst deactivation, as seen with gold/α-MoC (ref. 4), and gives our system high stability and a high metal-normalized turnover number of 4,300,000 moles of hydrogen per mole of platinum. We anticipate that the strategy demonstrated here will be pivotal for the design of highly active and stable catalysts for effective activation of important molecules such as water and carbon monoxide for energy production.

2.
Ecotoxicol Environ Saf ; 282: 116708, 2024 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-39018736

RESUMO

Previous studies reported that hemoprotein CYP450 catalyzed triclosan coupling is an "uncommon" metabolic pathway that may enhance toxicity, raising concerns about its environmental and health impacts. Hemoglobin, a notable hemoprotein, can catalyze endogenous phenolic amino acid tyrosine coupling reactions. Our study explored the feasibility of these coupling reactions for exogenous phenolic pollutants in plasma. Both hemoglobin and hemin were found to catalyze triclosan coupling in the presence of H2O2. This resulted in the formation of five diTCS-2 H, two diTCS-Cl-3 H, and twelve triTCS-4 H in phosphate buffer, with a total of nineteen triclosan coupling products monitored using LC-QTOF. In plasma, five diTCS-2 H, two diTCS-Cl-3 H, and two triTCS-4 H were detected in hemoglobin-catalyzed reactions. Hemin showed a weaker catalytic effect on triclosan transformation compared to hemoglobin, likely due to hemin dimerization and oxidative degradation by H2O2, which limits its catalytic efficiency. Triclosan transformation in the human plasma-like medium still occurs with high H2O2, despite the presence of antioxidant proteins that typically inhibit such transformations. In plasma, free H2O2 was depleted within 40 minutes when 800 µM H2O2 was added, suggesting a rapid consumption of H2O2 in these reactions. Antioxidative species, or hemoglobin/hemin scavengers such as bovine serum albumin, may inhibit but not completely terminate the triclosan coupling reactions. Previous studies reported that diTCS-2 H showed higher hydrophobicity and greater endocrine-disrupting effects compared to triclosan, which further underscores the potential health risks. This study indicates that hemoglobin and heme in human plasma might significantly contribute to phenolic coupling reactions, potentially increasing health risks.

3.
Anal Chem ; 95(39): 14573-14581, 2023 10 03.
Artigo em Inglês | MEDLINE | ID: mdl-37729469

RESUMO

Discrimination and quantification of amino acid (AA) enantiomers are particularly important for diagnosing and treating diseases. Recently, dual-mode probes have gained a lot of research interest because they can catch more detecting information compared with the single-mode probes. Thus, it is of great significance to develop a dual-mode sensor realizing AA enantiomer discrimination conveniently and efficiently. In this work, carbon dot L-TCDs were prepared by N-methyl-1,2-benzenediamine dihydrochloride (OTD) and l-tryptophan. With the assistance of H2O2, L-TCDs show an excellent discrimination performance for enantiomers of glutamine (Gln) and valine (Val) in both fluorescent and colorimetric modes. The fluorescence enantioselectivity of Gln (FD/FL) and Val (FL/FD) is 5.29 and 4.13, respectively, and the colorimetric enantioselectivity of Gln (ID/IL) and Val (IL/ID) is 13.26 and 3.42, individually. The chiral recognition mechanism of L-TCDs was systematically studied. L-TCDs can be etched by H2O2, and the participation of AA enantiomers results in different amounts of the released OTD, which provides fluorescent and colorimetric signals for identifying and quantifying the enantiomers of Gln and Val. This work provides a more convenient and flexible dual-mode sensing strategy for discriminating AA enantiomers, which is expected to be of great value in facile and high-throughput chiral recognition.


Assuntos
Glutamina , Valina , Colorimetria/métodos , Carbono/química , Peróxido de Hidrogênio , Aminoácidos , Corantes
4.
Environ Geochem Health ; 45(6): 2963-2983, 2023 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-36123510

RESUMO

Heavy metal concentrations (Al, V, Mn, Fe, Co, Ni, Cu, Zn, and Pb) and the magnetic properties of soil and sediment samples in/around an electrolytic manganese metal (EMM) industrial estate in northern China were investigated. Potential enrichment of Mn, Zn, and Pb was found in/around the core area of the EMM industrial estate; however, the pollution load index (PLI) values did not indicate severely polluted levels. For adults, all hazard index (HI) values of noncarcinogenic risks in the soil samples were below the safe level of 1.00. For children, none of the HI values exceeded the safe level, except Mn (HI = 1.23) in one industrial estate sample. The particle size of magnetic materials was mostly in the range of stable single-domain, and coarser ferrimagnetic phases enhanced the magnetic parameters in the industrial estate soils. Highly positive correlations were found between magnetic parameters, heavy metal concentrations, and PLI values, demonstrating that the magnetic parameters are an efficient proxy for assessing heavy metal contamination. Enrichment of Mn, Zn, and Pb was mainly derived from the EMM industry. The data showed that the EMM industrial estate under cleaner production had limited adverse impacts on the adjacent environment from the perspective of heavy metal contamination.


Assuntos
Monitoramento Ambiental , Metais Pesados , Poluentes do Solo , China , Chumbo , Fenômenos Magnéticos , Manganês , Metais Pesados/análise , Medição de Risco , Solo/química , Poluentes do Solo/toxicidade , Poluentes do Solo/análise
5.
Ecotoxicol Environ Saf ; 236: 113446, 2022 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-35366563

RESUMO

The ecological risks of nonylphenol (NP) and tetrabromobisphenol A (TBBPA) have received continued attention owing to their large consumption, frequently detection, adverse effects on the reproductive fitness, and lack of risk assessment technical systems. The geometric mean of the median concentrations of NP in the 22 surface waters was 0.278 µg/L, and TBBPA in the seven surface waters was 0.014 µg/L in China. The species sensitivity distribution (SSD) models were augmented by extrapolated reproductive toxicity data of native species to reduce uncertainty. The SSD models and the hazardous concentrations for 5% of species exhibited good robustness and reliability using the bootstrap method and minimum sample size determination. The acute and reproductive predicted no-effect concentrations (PNECs) were derived as 9.88 and 0.187 µg/L for NP, and 56.6 and 0.0878 µg/L for TBBPA, respectively. The risk quotients indicated that 11 of 22 locations for NP, and 3 of 7 locations for TBBPA were at high ecological risk levels based on the reproductive PNECs. Furthermore, the higher tier ecological risk assessment (ERA) based on potential affected fraction and joint probability curves indicated that the ecological risks in the four of above locations needed further concern. The ERA based on both the acute and reproductive toxicity is essential for assessing the ecological risks of NP and TBBPA, otherwise using acute PNECs only may result in an underestimation of ecological risk. The developed tiered ERA method and its framework can provide accurate, detailed, quantitative, locally applicable, and economically technical support for ERA of typical endocrine-disrupting chemicals in China.


Assuntos
Monitoramento Ambiental , Poluentes Químicos da Água , Organismos Aquáticos , China , Monitoramento Ambiental/métodos , Fenóis , Bifenil Polibromatos , Reprodutibilidade dos Testes , Medição de Risco/métodos , Poluentes Químicos da Água/análise
6.
Ecotoxicol Environ Saf ; 243: 114018, 2022 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-36037634

RESUMO

Exposure to antibiotics can result in not only ecotoxicity on aquatic organisms but also the development of antibiotic resistance. In the study, the ecotoxicity data and minimum inhibitory concentrations of the antibiotics were screened to derive predicted no-effect concentrations of ecological (PNECeco) and resistance development risks (PNECres) for 36 antibiotics in fresh surface waters of China. The derived PNECeco and PNECres values were ranged from 0.00175 to 2351 µg/L and 0.037-50 µg/L, respectively. Antibiotic ecological and resistance development risks were geographically widespread, especially in the Yongding River, Daqing River, and Ziya River basins of China. Based on the risk quotients, 11 and 14 of 36 target antibiotics were at high ecological risks and high resistance development risks in at least one basin, respectively. The higher tiered assessments provided more detailed risk descriptions by probability values and ß-lactams (penicillin and amoxicillin) were present at the highest levels for ecological and resistance development risks. Although there was uncertainty based on the limited data and existing methods, this study can indicate the overall situation of the existing risk levels and provide essential insights and data supporting antibiotic management.


Assuntos
Monitoramento Ambiental , Poluentes Químicos da Água , Antibacterianos/análise , Antibacterianos/toxicidade , China , Monitoramento Ambiental/métodos , Medição de Risco/métodos , Rios , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/toxicidade
7.
Zhongguo Zhong Yao Za Zhi ; 47(12): 3215-3223, 2022 Jun.
Artigo em Zh | MEDLINE | ID: mdl-35851114

RESUMO

Advanced glycation end products(AGEs) can lead to many diseases such as diabetes and its complications. In this study, an in vitro non-enzymatic glycosylation reaction model-bovine serum albumin/methylglyoxal(BSA/MGO) reaction system was constructed and incubated with Cortex Moutan extract. High performance liquid chromatography(HPLC) and ultra-high performance liquid chromatography with quadrupole time-of-flight mass spectrometry(UPLC-Q-TOF-MS/MS) were used to detect and identify the active components that inhibited the formation of AGEs in the co-incubation solution of Cortex Moutan extract and MGO, and differential components such as salvianan, paeoniside, benzoylpaeoniflorin, mudanpioside J, galloyloxypaeoniflorin, benzoyloxy-paeoniflorin, 5-hydroxy-3 s-hydroxymethyl-6-methyl-2,3-dihydro benzofuran, and galloylpaeoniflorin were screened out, which were inferred to be the potential active components of Cortex Moutan extract to capture MGO. In addition, BSA-glucose reaction system was performed to investigate the influence of different concentrations of Cortex Moutan extract(decoction concentrations: 40, 80, 120, 160, and 200 mg·mL~(-1)) on inhibiting the production of AGEs in vitro. The inhibitory effects of Cortex Moutan extract and the differential components galloylpaeoniflorin and benzoyl paeoniflorin on the production of AGEs in human umbilical vein endothelial cells(HUVECs) induced by high glucose was further evaluated. Cell apoptosis was observed by acridine orange and ethidium bromide(AO/EB) double fluorescence staining. The results showed that Cortex Moutan Cortex extract and its differential components had certain inhibitory effects on the formation of AGEs, and could reduce cell apoptosis. This study provided reference for the treatment of diabetic vascular complications by Cortex Moutan inhibiting the toxic AGEs.


Assuntos
Medicamentos de Ervas Chinesas , Espectrometria de Massas em Tandem , Medicamentos de Ervas Chinesas/química , Medicamentos de Ervas Chinesas/farmacologia , Glucose , Produtos Finais de Glicação Avançada , Células Endoteliais da Veia Umbilical Humana , Humanos , Óxido de Magnésio
8.
J Am Chem Soc ; 143(2): 628-633, 2021 Jan 20.
Artigo em Inglês | MEDLINE | ID: mdl-33382262

RESUMO

We report the syntheses of highly dispersed CoNi bimetallic catalysts on the surface of α-MoC based on the strong metal support interaction (SMSI) effect. The interaction between the nearly atomically dispersed Co and Ni atoms was observed for the first time by the real-space chemical mapping at the atomic level. Combined with the ability of α-MoC to split water at low temperatures, the as-synthesized CoNi/α-MoC catalysts exhibited robust and synergistic performance for the hydrogen production from hydrolysis of ammonia borane. The metal-normalized activity of the bimetallic 1.5Co1.5Ni/α-MoC catalyst reached 321.1 molH2·mol-1CoNi·min-1 at 298 K, which surpasses all the noble metal-free catalysts ever reported and is four times higher than that of the commercial Pt/C catalyst.

9.
Ecotoxicol Environ Saf ; 207: 111521, 2021 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-33254396

RESUMO

Phthalates (PAEs), bisphenol A (BPA), and oestrogenic compounds have become major concerns due to their endocrine-disrupting effect. However, few studies related to the occurrence of PAEs, BPA, and oestrogen in food and compost from different growth age livestock have been conducted. In this study, faeces, urine and food samples were collected from a typical livestock (cow) and a special livestock (pigeon) from concentrated animal feeding operations (CAFOs). The daily total oestrogen excretion of a single cow ranged from 192 µg/day to 671 µg/day, which was significantly higher than that of a single pigeon (0-0.01 µg/day). Conjugated oestrogens represented 22.0-46.0% of the total oestrogens excreted from cow faeces and 80.7-91.8% of those from cow urine, indicating that the form of the excreted oestrogens depends on the livestock species and type of excrement. BPA was all detected in all livestock manure and food, and the concentration in pigeon was 9.2-40.2 ng/g and 23.1 ng/g respectively, while that in cattle was 50.5-72.0 ng/g and 41.1 ng/g respectively. The results indicated that the food is significant sources of BPA entering the process of cow and pigeon breeding. Diethyl phthalate (DEP) was detected at high frequency in pigeon faeces samples, suggesting that pigeons were highly exposed to these plasticisers. The total oestradiol equivalent quantity (EEQt) of livestock origin in aquatic environments was estimated to be 2.99 ng/L, which was higher than the baseline hazard value (1 ng/L) (Xu et al., 2018). The study provides data on the emissions and sources of PAEs, BPA, and oestrogenic compounds from different livestock in CAFOs and demonstrates that food is a significant source of BPA entering livestock.


Assuntos
Ração Animal/análise , Compostos Benzidrílicos/análise , Poluentes Ambientais/análise , Estrogênios/análise , Contaminação de Alimentos/análise , Fenóis/análise , Ácidos Ftálicos/análise , Animais , Bovinos , China , Fezes/química , Feminino , Contaminação de Alimentos/estatística & dados numéricos , Humanos , Gado , Esterco/análise , Plastificantes
10.
Molecules ; 26(21)2021 Oct 30.
Artigo em Inglês | MEDLINE | ID: mdl-34770982

RESUMO

Per- and polyfluoroalkyl substances (PFASs) are a class of highly fluorinated aliphatic compounds that are persistent and bioaccumulate, posing a potential threat to the aquatic environment. The electroplating industry is considered to be an important source of PFASs. Due to emerging PFASs and many alternatives, the acute toxicity data for PFASs and their alternatives are relatively limited. In this study, a QSAR-ICE-SSD composite model was constructed by combining quantitative structure-activity relationship (QSAR), interspecies correlation estimation (ICE), and species sensitivity distribution (SSD) models in order to obtain the predicted no-effect concentrations (PNECs) of selected PFASs. The PNECs for the selected PFASs ranged from 0.254 to 6.27 mg/L. The ΣPFAS concentrations ranged from 177 to 983 ng/L in a river close to an electroplating industry in Shenzhen. The ecological risks associated with PFASs in the river were below 2.97 × 10-4.

11.
Environ Geochem Health ; 42(6): 1601-1615, 2020 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-31760543

RESUMO

In this study, the effect of biochar (BC) derived from Litchi chinensis Sonn. and its modification, including Ca-biochar (Ca-BC) and Fe-Mn-biochar (Fe-Mn-BC), on the transportation of oestrone (E1) in water and soil was investigated. Fe-Mn-BC showed better adsorption ability than other types of biochar (BC, Ca-BC) under different conditions (humic acid, pH, ionic strength) in an aqueous environment. The maximum mass of sorbent at 298 K increased from 1.12 mg g-1 (BC) to 4.18 mg g-1 (Fe-Mn-BC). Humic acid had a greater impact on aqueous E1 adsorption on these biochars than did the pH and ionic strength. Fe-Mn-BC as a soil amendment had a great control of E1 transport in soil, and no leachate of E1 was observed in the column experiment. E1 mobility showed strong retardation in amended soil with Ca-BC (Rf = 11.2) compared with raw soil (Rf = 7.1). These results suggested that Fe-Mn-BC was more effective in controlling E1 transportation, and Fe-Mn-BC could be used as an alternative and inexpensive adsorbent to reduce E1 contaminants from water and soil.


Assuntos
Carvão Vegetal/química , Estrona/química , Litchi/química , Poluentes do Solo/química , Poluentes Químicos da Água/química , Adsorção , Substâncias Húmicas , Concentração de Íons de Hidrogênio , Ferro/química , Manganês/química , Concentração Osmolar , Solo
12.
Ecotoxicol Environ Saf ; 174: 532-539, 2019 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-30861441

RESUMO

Polybrominated diphenyl ethers (PBDEs) contained in electronic waste (e-waste) can be released to indoor environments and cause occupational health hazards during the recycling process. TVs, washing machines, refrigerators and printed wiring boar (PWB) represent the main domestic e-wastes. In this study, concentrations of Σ7PBDEs in air and dust samples from recycling workshops handling these four major types of e-wastes were measured, and the occupational exposure risk for workers at the corresponding workshops was evaluated. Concentrations of Σ7PBDEs in air and dust were within the ranges of 55.28-369.66 ng/m3 and 158.07-669.81 µg/g, respectively. The highest concentration of Σ7PBDEs in air was detected in the TV recycling workshop, while the refrigerator recycling workshop had the highest level of Σ7PBDEs in dust. The workers at these two e-waste recycling workshops were the most substantially exposed to BDE-209, which accounted for more than 85% of Σ7PBDEs in both air and dust. Compared to other e-waste recycling workshops, the workers at the PWB recycling workshop were also more exposed to BDE-47 and BDE-99. Occupational exposure levels for inhalation and dust ingestion were within the ranges of 3939 pg/kg/d to 26,271 pg/kg/d and 104,945 pg/kg/d to 444,694 pg/kg/d, respectively. The hazard quotient (HQ) values were calculated based on the RfDs provided by the EPA. Total HQ levels of inhalation exposure and dust ingestion were less than 0.222. The results of the HQ indicated that no adverse health effects were expected for workers in these workshops; however, the exposure risk of workers in the PWB recycling workshop (HQ=0.222) was higher than that in other e-waste recycling workshops (HQ=0.022-0.072). At the PWB recycling workshop, BDE-47 and BDE-99 caused the main occupational exposure risk to the workers, while s in the recycling plants handling other types of domestic e-waste BDE-209 was the major contributor to the risk faced by the workers.


Assuntos
Resíduo Eletrônico , Éteres Difenil Halogenados/toxicidade , Exposição Ocupacional , Ar/análise , Animais , China , Poeira/análise , Monitoramento Ambiental , Éteres Difenil Halogenados/análise , Humanos , Reciclagem
13.
Angew Chem Int Ed Engl ; 58(42): 15089-15097, 2019 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-31444841

RESUMO

The development of highly efficient metal-free carbon electrocatalysts for the oxygen reduction reaction (ORR) is one very promising strategy for the exploitation and commercialization of renewable and clean energy, but this still remains a significant challenge. Herein, we demonstrate a facile approach to prepare three-dimensional (3D) N-doped carbon with a sp3 /sp2 carbon interface derived from ionic liquids via a simple pyrolysis process. The tunable hybrid sp3 and sp2 carbon composition and pore structures stem from the transformation of ionic liquids to polymerized organics and introduction of a Co metal salt. Through tuning both composition and pores, the 3D N-doped nanocarbon with a high sp3 /sp2 carbon ratio on the surface exhibits a superior electrocatalytic performance for the ORR compared to that of the commercial Pt/C in Zn-air batteries. Density functional theory calculations suggest that the improved ORR performance can be ascribed to the existence of N dopants at the sp3 /sp2 carbon interface, which can lower the theoretical overpotential of the ORR.

14.
Artigo em Inglês | MEDLINE | ID: mdl-27314419

RESUMO

This study was undertaken to develop an extraction method for seven acidic pharmaceuticals and five steroidal estrogens from wastewater, treated wastewater and sludge samples. The temperature and time of sample derivatization using N,O-bis(trimethylsilyl)trifluoroacetamide was optimized. Our results show that pretreatment combined with solid phase extraction (SPE) for wastewater samples (using an ENVI-C18 cartridge) and liquid-solid extraction combined with SPE (using an HLB cartridge) for sludge samples increased the analytical efficiency for acidic pharmaceuticals and estrogenic hormones using gas chromatography-mass spectrometry (GC-MS). The derivatization conditions were optimized at 40°C for 2 h. In addition, the derivatized samples were stable at ambient temperature. The new method was validated and applied to the analysis of real wastewater and discharged sludge samples from a local wastewater treatment plant. Except for 17α-ethinylestradiol, all acidic pharmaceuticals and estrogens were detected in the influent, effluent and discharged sludge samples. The concentrations of these compounds were particularly high in the discharged sludge samples.


Assuntos
Ácidos/análise , Estrogênios/análise , Preparações Farmacêuticas/análise , Esgotos/química , Águas Residuárias/química , Poluentes Químicos da Água/análise , Acetamidas/química , Cromatografia Gasosa-Espectrometria de Massas , Reprodutibilidade dos Testes , Extração em Fase Sólida , Compostos de Trimetilsilil/química
15.
Chemosphere ; : 142611, 2024 Jun 13.
Artigo em Inglês | MEDLINE | ID: mdl-38878983

RESUMO

Bromophenols has been proven to synthesize hydroxylated polybrominated diphenyl ethers (OH-PBDEs), which may pose additional environmental and health risks in the process of bioremediation. In this study, the removal of 2,4-dibromophenol (2,4-DBP) and 2,4,6-tribromophenol (2,4,6-TBP) and the biosynthetic of OH-PBDEs by Prorocentrum donghaiense were explored. The removal efficiencies of 2,4-DBP and 2,4,6-TBP ranged from 32.71% to 76.89% and 31.15% to 78.12%, respectively. Low concentrations of 2,4-DBP stimulated algal growth, while high concentrations were inhibitory. Furthermore, exposure to 10.00 mg L-1 2,4-DBP resulted in the detection of 2'-hydroxy-2,3',4,5'-tetrabromodiphenyl ether (2'-OH-BDE-68) within P. donghaiense. In contrast, increasing concentrations of 2,4,6-TBP considerably inhibited P. donghaiense growth, with 4'-hydroxy-2,3',4,5',6-pentabromodiphenyl ether (4'-OH-BDE-121) detected within P. donghaiense under 5.00 mg L-1 2,4,6-TBP. Metabolomic analysis further revealed that the synthesized OH-PBDEs exhibited higher toxicity than their precursors and identified the oxidative coupling as a key biosynthetic mechanism. These findings confirm the capacity of P. donghaiense to remove bromophenols and biosynthesize OH-PBDEs from bromophenols, offering valuable insights into formulating algal bioremediation to mitigate bromophenol contamination.

16.
Chemosphere ; 346: 140583, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37918539

RESUMO

Perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), as emerging endocrine-disrupting chemicals (EDCs), pose adverse effects on aquatic organisms. Conventional ecological risk assessment (ERA) not fully considering the mode of toxicity action of PFOS and PFOA, may result in an underestimation of risks and confuse decision-makers. In the study, we developed species sensitivity weighted distribution (SSWD) models based on adverse outcome pathway (AOP) networks for deriving predicted no-effect concentrations (PNECs). Three kinds of weighting criteria (intraspecies variation, trophic level abundance, and data quality) and weighted log-normal distribution methods were adopted. The developed models considered the inter/intraspecies variation and integrated nontraditional endpoints of endocrine-disrupting effects. The PNECs of endocrine disruption effects were derived as 2.52 µg/L (95% confidence intervals 0.667-9.85 µg/L) for PFOS and 18.7 µg/L (5.40-71.0 µg/L) for PFOA, which were more conservative than those derived from the SSD method and were comparable with the values in the literature based on the chronic toxicity data. For PFOS, the effect of growth and development was the most sensitive; however, for PFOA, the effect of reproduction was the most sensitive in the effects of growth and development, reproduction, biochemistry and genetics, and survival. The endocrine-disrupting effects of PFOS and PFOA are significant and need to be fully recognized in the ERA. This study provided an ERA framework that can improve the ecological relevance and reduce the uncertainty of PNECs of EDCs.


Assuntos
Rotas de Resultados Adversos , Ácidos Alcanossulfônicos , Disruptores Endócrinos , Fluorocarbonos , Fluorocarbonos/toxicidade , Fluorocarbonos/análise , Medição de Risco , Ácidos Alcanossulfônicos/toxicidade , Caprilatos/toxicidade , Disruptores Endócrinos/toxicidade
17.
Toxics ; 12(4)2024 Apr 11.
Artigo em Inglês | MEDLINE | ID: mdl-38668504

RESUMO

Dihydroxylated polybrominated diphenyl ethers (DiOH-PBDEs) could be the metabolites of PBDEs of some organisms or the natural products of certain marine bacteria and algae. OH-PBDEs may demonstrate binding affinity to thyroid hormone receptors (TRs) and can disrupt the functioning of the systems modulated by TRs. However, the thyroid hormone disruption mechanism of diOH-PBDEs remains elusive due to the absence of diOH-PBDEs standards. This investigation explores the potential disruptive effects of OH/diOH-PBDEs on thyroid hormones via competitive binding and coactivator recruitment with TRα and TRß. At levels of 5000 nM and 25,000 nM, 6-OH-BDE-47 demonstrated significant recruitment of steroid receptor coactivator (SRC), whereas none of the diOH-PBDEs exhibited SRC recruitment within the range of 0.32-25,000 nM. AutoDock CrankPep (ADCP) simulations suggest that the conformation of SRC and TR-ligand complexes, particularly their interaction with Helix 12, rather than binding affinity, plays a pivotal role in ligand agonistic activity. 6,6'-diOH-BDE-47 displayed antagonistic activity towards both TRα and TRß, while the antagonism of 3,5-diOH-BDE-100 for TRα and TRß was concentration-dependent. 3,5-diOH-BDE-17 and 3,5-diOH-BDE-51 exhibited no discernible agonistic or antagonistic activities. Molecular docking analysis revealed that the binding energy of 3,3',5-triiodo-L-thyronine (T3) surpassed that of OH/diOH-PBDEs. 3,5-diOH-BDE-100 exhibited the highest binding energy, whereas 6,6'-diOH-BDE-47 displayed the lowest. These findings suggest that the structural determinants influencing the agonistic and antagonistic activities of halogen phenols may be more intricate than previously proposed, involving factors beyond high-brominated PBDEs or hydroxyl group and bromine substitutions. It is likely that the agonistic or antagonistic propensities of OH/diOH-PBDEs are instigated by protein conformational changes rather than considerations of binding energy.

18.
Aquat Toxicol ; 272: 106962, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38797068

RESUMO

Diisobutyl phthalate (DiBP), is widely chemical replacement for Dibutyl phthalate (DBP). Although DBP and DiBP have been detected in surface water worldwide, few studies to date have systematically assessed the risks of DBP and its alternatives to aquatic organisms. The present study compared DBP and DiBP for their individual and joint toxicity as well as thyroid hormone levels in zebrafish embryo. Transcripts of key genes related to the hypothalamic-pituitary-thyroid (HPT) axis were investigated in developing zebrafish larvae by application of real time polymerase chain reaction. The median half-lethal concentrations of DBP and DiBP to zebrafish at 96 h were 0.545 mg L-1 and 1.149 mg L-1, respectively. The joint toxic effect of DBP-DiBP (0.25-0.53 mg L-1) with the same ratio showed a synergistic effect. Thyroid hormones levels increased with exposure to 10 µg L-1 of DBP or 50 µg L-1 of DiBP, and exposure to both compounds significantly increased thyroid gland-specific transcription of thyroglobulin gene (tg), hyronine deiodinase (dio2), and transthyretin (ttr), indicating an adverse effect associated with the HPT axis. Molecular docking results indicated that DBP (-7.10 kcal/M and -7.53 kcal/M) and DiBP (-6.63 kcal/M and -7.42 kcal/M) had the same docking energy with thyroid hormone receptors. Our data facilities an understand of potential harmful effects of DBP and its alternative (DiBP).


Assuntos
Dibutilftalato , Embrião não Mamífero , Poluentes Químicos da Água , Peixe-Zebra , Animais , Peixe-Zebra/genética , Dibutilftalato/toxicidade , Dibutilftalato/análogos & derivados , Poluentes Químicos da Água/toxicidade , Embrião não Mamífero/efeitos dos fármacos , Ácidos Ftálicos/toxicidade , Hormônios Tireóideos/metabolismo , Larva/efeitos dos fármacos , Larva/crescimento & desenvolvimento , Larva/genética , Glândula Tireoide/efeitos dos fármacos , Regulação da Expressão Gênica no Desenvolvimento/efeitos dos fármacos
19.
Antiviral Res ; 227: 105917, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38782067

RESUMO

The Fc-fused receptor binding domain (RBD-Fc) vaccine for SARS-CoV-2 has garnered significant attention for its capacity to provide effective and specific immune protection. However, its immunogenicity is limited, highlighting the need for improvement in clinical application. Nanoparticle delivery has been shown to be an effective method for enhancing antigen immunogenicity. In this study, we developed bivalent nanoparticle recombinant protein vaccines by assembling the RBD-Fc of SARS-CoV-2 and Fc-binding homo-oligomers o42.1 and i52.3 into octahedral and icosahedral nanoparticles. The formation of RBD-Fc nanoparticles was confirmed through structural characterization and cell binding experiments. Compared to RBD-Fc dimers, the nanoparticle vaccines induced more potent neutralizing antibodies (nAb) and stronger cellular immune responses. Therefore, using bivalent nanoparticle vaccines based on RBD-Fc presents a promising vaccination strategy against SARS-CoV-2 and offers a universal approach for enhancing the immunogenicity of Fc fusion protein vaccines.


Assuntos
Anticorpos Neutralizantes , Anticorpos Antivirais , Vacinas contra COVID-19 , COVID-19 , Fragmentos Fc das Imunoglobulinas , Nanopartículas , SARS-CoV-2 , Glicoproteína da Espícula de Coronavírus , Nanopartículas/química , SARS-CoV-2/imunologia , Vacinas contra COVID-19/imunologia , Anticorpos Neutralizantes/imunologia , Anticorpos Antivirais/imunologia , Humanos , Fragmentos Fc das Imunoglobulinas/imunologia , Fragmentos Fc das Imunoglobulinas/química , COVID-19/prevenção & controle , COVID-19/imunologia , Glicoproteína da Espícula de Coronavírus/imunologia , Glicoproteína da Espícula de Coronavírus/química , Animais , Camundongos , Vacinas Sintéticas/imunologia , Vacinas Sintéticas/administração & dosagem , Vacinas Sintéticas/química , Proteínas Recombinantes de Fusão/imunologia , Proteínas Recombinantes de Fusão/genética , Proteínas Recombinantes de Fusão/química , Feminino , Multimerização Proteica , Camundongos Endogâmicos BALB C , Desenvolvimento de Vacinas , Ligação Proteica , Imunogenicidade da Vacina , Imunidade Celular , Nanovacinas
20.
Chemosphere ; 312(Pt 1): 137215, 2023 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-36375608

RESUMO

Polybrominated diphenyl ethers (PBDEs) are efficient brominated flame retardants and are released into various environmental media via usage, recycling and disposal. This study investigated the concentrations and ecological risks of two typical PBDEs, 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) and decabromodiphenyl ether (BDE-209), in surface waters across China from 2011 to 2018. The results showed that the concentration of BDE-209 (8.25 ng L-1) was higher than that of BDE-47 (1.02 ng L-1), and the concentrations of BDE-47 and BDE-209 in the lakes (2.56 ng L-1 and 22.19 ng L-1, respectively) were higher than those in the rivers (0.58 ng L-1 and 7.05 ng L-1, respectively). In addition, the concentration of BDE-209 in the wet season (2.61 ng L-1) was lower than that in the dry season (10.83 ng L-1), whereas the concentration of BDE-47 in the wet season (0.24 ng L-1) was a little lower than that in the dry season (0.99 ng L-1). BDE-47 and BDE-209 concentrations showed a gradual decrease in surface waters across China during the eight-year period. Based on the species sensitivity distribution (SSD) models, the 5% hazardous concentration (HC5) and predicted no-effect concentration (PNEC) values were derived using the acute and chronic toxicity data of BDE-47 and BDE-209. Results showed that the PNEC values based on the acute and chronic toxicity data were 2.08 µg L-1 and 0.52 µg L-1 for BDE-47, respectively and 370 µg L-1 and 0.34 µg L-1 for BDE-209, respectively. The risk quotient (RQ) values of BDE-47 in surface waters across China were far smaller than 0.1 (low ecological risk). Similarly, the RQ values of BDE-209 were also smaller than 0.1, except for those at Baiyangdian Lake and Chaohu Lake, where the probability of 0.1 ≤ RQ < 1.0 (medium ecological risk) was approximately 10% based on 10,000 Monte Carlo simulations.


Assuntos
Retardadores de Chama , Éteres Difenil Halogenados , Éteres Difenil Halogenados/análise , Monitoramento Ambiental , Éter , Retardadores de Chama/análise , Medição de Risco , Etil-Éteres , China
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