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1.
Nano Lett ; 24(28): 8580-8586, 2024 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-38967330

RESUMO

By using low-temperature scanning tunneling microscopy and spectroscopy (STM/STS), we observe in-gap states induced by Andreev tunneling through a single impurity state in a low carrier density superconductor (NaAlSi). The energy-symmetric in-gap states appear when the impurity state is located within the superconducting gap. In-gap states can cross the Fermi level, and they show X-shaped spatial variation. We interpret the in-gap states as a consequence of the Andreev tunneling through the impurity state, which involves the formation or breakup of a Cooper pair. Due to the low carrier density in NaAlSi, the in-gap state is tunable by controlling the STM tip-sample distance. Under strong external magnetic fields, the impurity state shows Zeeman splitting when it is located near the Fermi level. Our findings not only demonstrate the Andreev tunneling involving single electronic state but also provide new insights for understanding the spatially dependent in-gap states in low carrier density superconductors.

2.
Phys Rev Lett ; 131(11): 116501, 2023 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-37774284

RESUMO

Here we report a combined study of low-temperature scanning tunneling microscopy and dynamical mean-field theory on PdCrO_{2}, a delafossite metal with an antiferromagnetic order below ∼37.5 K. First, on the CrO_{2}-terminated polar surface we detect a gaplike feature both below and above the Néel temperature. The dynamical mean-field theory calculations indicate that this gap is opened due to the strong correlations of Cr-3d electrons, suggesting the hidden Mott nature of the gap. Then, we observe two kinds of Pd-terminated polar surfaces. One is a well-ordered Pd surface with the Fermi-surface-nesting-induced incommensurate charge modulation, while the other one is a reconstructed Pd surface with the individual nanoscale nonperiodic domain structures. On the well-ordered Pd surface, the interference between the incommensurate charge modulation and the atomic lattice forms the periodic moiré pattern. Our results provide important microscopic information for fully understanding the correlated electronic properties of this class of materials.

3.
Sci Total Environ ; 897: 165319, 2023 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-37414164

RESUMO

Incense burning is a common practice in Asian cultures, releasing hazardous particulate organics. Inhaling incense smoke can result in adverse health effects, yet the molecular compositions of incense-burning organics have not been well investigated due to the lack of measurement of intermediate-volatility and semi-volatile organic compounds (I/SVOCs). To elucidate the detailed emission profile of incense-burning particles, we conducted a non-target measurement of organics emitted from incense combustion. Quartz filters were utilized to trap particles, and organics were analyzed by a comprehensive two-dimensional gas chromatography-mass spectrometer (GC × GC-MS) coupled with a thermal desorption system (TDS). To deal with the complex data obtained by GC × GC-MS, homologs are identified mainly by the combination of selected ion chromatograms (SICs) and retention indexes. SICs of 58, 60, 74, 91, and 97 were utilized to identify 2-ketones, acids, fatty acid methyl esters, fatty acid phenylmethyl esters, and alcohols, respectively. Phenolic compounds contribute the most to emission factors (EFs) among all chemical classes, taking up 24.5 % ± 6.5 % of the total EF (96.1 ± 43.1 µg g-1). These compounds are largely derived from the thermal degradation of lignin. Biomarkers like sugars (mainly levoglucosan), hopanes, and sterols are extensively detected in incense combustion fumes. Incense materials play a more important role in shaping emission profiles than incense forms. Our study provides a detailed emission profile of particulate organics emitted from incense burning across the full-volatility range, which can be used in the health risk assessments. The data processing procedure in this work could also benefit those with less experience in non-target analysis, especially GC × GC-MS data processing.

4.
Nano Lett ; 23(7): 2958-2963, 2023 Apr 12.
Artigo em Inglês | MEDLINE | ID: mdl-37011415

RESUMO

Here we use low-temperature and variable-temperature scanning tunneling microscopy to study the pnictide superconductor, Ba1-xSrxNi2As2. In the low-temperature phase (triclinic phase) of BaNi2As2, we observe the unidirectional charge density wave (CDW) with Q = 1/3 on both the Ba and NiAs surfaces. On the NiAs surface of the triclinic BaNi2As2, there are structural-modulation-induced chain-like superstructures with distinct periodicities. In the high-temperature phase (tetragonal phase) of BaNi2As2, the NiAs surface appears as the periodic 1 × 2 superstructure. Interestingly, in the triclinic phase of Ba0.5Sr0.5Ni2As2, the unidirectional CDW is suppressed on both the Ba/Sr and NiAs surfaces, and the Sr substitution stabilizes the periodic 1 × 2 superstructure on the NiAs surface, which enhance the superconductivity in Ba0.5Sr0.5Ni2As2. Our results provide important microscopic insights for the interplay among the unidirectional CDW, structural modulation, and superconductivity in this class of pnictide superconductors.

5.
Artigo em Inglês | MEDLINE | ID: mdl-36767874

RESUMO

Ship emissions contribute substantial air pollutants when at berth. However, the complexity and diversity of the marine fuels utilized hinder our understanding and mapping of the characteristics of ship emissions. Herein, we applied GC × GC-MS to analyze the components of marine fuel oils. Owing to the high separation capacity of GC × GC-MS, 11 classes of organic compounds, including b-alkanes, alkenes, and cyclo-alkanes, which can hardly be resolved by traditional one-dimensional GC-MS, were detected. Significant differences are observed between light (-10# and 0#) and heavy (120# and 180#) fuels. Notably, -10# and 0# diesel fuels are more abundant in b-alkanes (44~49%), while in 120# and 180#, heavy fuels b-alkanes only account for 8%. Significant enhancement of naphthalene proportions is observed in heavy fuels (20%) compared to diesel fuels (2~3%). Hopanes are detected in all marine fuels and are especially abundant in heavy marine fuels. The volatility bins, one-dimensional volatility-based set (VBS), and two-dimensional VBS (volatility-polarity distributions) of marine fuel oils are investigated. Although IVOCs still take dominance (62-66%), the proportion of SVOCs in heavy marine fuels is largely enhanced, accounting for ~30% compared to 6~12% in diesel fuels. Furthermore, the SVOC/IVOC ratio could be applied to distinguish light and heavy marine fuel oils. The SVOC/IVOC ratios for -10# diesel fuel, 0# diesel fuel, 120# heavy marine fuel, and 180# heavy marine fuel are 0.085 ± 0.046, 0.168 ± 0.159, 0.504, and 0.439 ± 0.021, respectively. Our work provides detailed information on marine fuel compositions and could be further implemented in estimating organic emissions and secondary organic aerosol (SOA) formation from marine fuel storage and evaporation processes.


Assuntos
Poluentes Atmosféricos , Óleos Combustíveis , Compostos Orgânicos Voláteis , Gasolina/análise , Compostos Orgânicos Voláteis/análise , Emissões de Veículos/análise , Cromatografia Gasosa-Espectrometria de Massas , Poluentes Atmosféricos/análise , Aerossóis/análise , Alcanos
6.
J Cancer ; 13(14): 3554-3565, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36484011

RESUMO

Colorectal cancer (CRC) is one of the major killer diseases worldwide, and more effective therapeutic compounds for CRC treatment are urgently needed. Although bioactive natural products derived from endophytic fungi have been extensively employed as antibiotics and anticancer agents, little is known about the effect of Rhytidhysteron sp. BZM-9 (an endophytic fungus)-derived compounds on CRC. Herein, a natural molecule porric acid E was isolated from Rhytidhysteron sp. BZM-9. Alamar Blue cell viability assay, Western blotting, transmission electron microscopy, flow cytometry analysis, and fluorescence image examination were employed to evaluate the antitumor effects of porric acid E on CRC cell lines. To establish the xenograft tumor model, nude mice received subcutaneous implants consisting of CRC cells on their flanks. Then the mice were treated with porric acid E or vehicle to assess the tumor-killing effects. The results revealed that porric acid E exhibited cytotoxicity by inhibiting proliferation and promoting apoptosis in CRC cells in vitro. Additionally, compared with fluorouracil (5-FU), porric acid E exhibited a more potent inhibitory effect on CRC HT29 cells. Importantly, extensive autophagy induced by porric acid E was detected in CRC cells, whereas inhibition of autophagy could significantly ameliorate porric acid E-mediated cytotoxic effect on CRC cells. Moreover, porric acid E treatment could markedly suppress subcutaneous HT29 xenograft tumor growth in vivo. Bioinformatics prediction indicated that Beclin-1 might be the potential target of porric acid E. These findings might afford a useful and important method for the treatment of CRC through fungal endophyte-derived natural compounds.

7.
Environ Sci Technol ; 56(22): 15377-15388, 2022 11 15.
Artigo em Inglês | MEDLINE | ID: mdl-36279129

RESUMO

The primarily emitted compounds by human presence, e.g., skin and volatile organic compounds (VOCs) in breath, can react with typical indoor air oxidants, ozone (O3), and hydroxyl radicals (OH), leading to secondary organic compounds. Nevertheless, our understanding about the formation processes of the compounds through reactions of indoor air oxidants with primary emitted pollutants is still incomplete. In this study we performed real-time measurements of nitrous acid (HONO), nitrogen oxides (NOx = NO + NO2), O3, and VOCs to investigate the contribution of human presence and human activity, e.g., mopping the floor, to secondary organic compounds. During human occupancy a significant increase was observed of 1-butene, isoprene, and d-limonene exhaled by the four adults in the room and an increase of methyl vinyl ketone/methacrolein, methylglyoxal, and 3-methylfuran, formed as secondary compounds through reactions of OH radicals with isoprene. Intriguingly, the level of some compounds (e.g., m/z 126, 6-methyl-5-hepten-2-one, m/z 152, dihydrocarvone, and m/z 194, geranyl acetone) formed through reactions of O3 with the primary compounds was higher in the presence of four adults than during the period of mopping the floor with commercial detergent. These results indicate that human presence can additionally degrade the indoor air quality.


Assuntos
Poluentes Atmosféricos , Poluição do Ar em Ambientes Fechados , Poluentes Ambientais , Ozônio , Compostos Orgânicos Voláteis , Humanos , Poluição do Ar em Ambientes Fechados/análise , Ozônio/análise , Poluentes Atmosféricos/análise , Oxidantes
8.
Nano Lett ; 22(14): 5635-5640, 2022 Jul 27.
Artigo em Inglês | MEDLINE | ID: mdl-35838660

RESUMO

Here, we use low-temperature scanning tunneling microscopy and spectroscopy to study the polar surfaces of PdCoO2. On the CoO2-terminated polar surface, we detect the quasiparticle interference pattern originating from the Rashba-like spin-split surface states. On the well-ordered Pd-terminated polar surface, we observe a regular lattice that has a larger lattice constant than the atomic lattice of PdCoO2. In comparison with the shape of the hexagonal Fermi surface on the Pd-terminated surface, we identify this regular lattice as a fully two-dimensional incommensurate charge modulation that is driven by the Fermi surface nesting. More interestingly, we also find the moiré pattern induced by the interference between the two-dimensional incommensurate charge modulation in the Pd layer and its atomic lattice. Our results not only show a new charge modulation on the Pd surface of PdCoO2 but also pave the way for fully understanding the novel electronic properties of this material.

9.
Nat Commun ; 13(1): 2156, 2022 Apr 20.
Artigo em Inglês | MEDLINE | ID: mdl-35444181

RESUMO

Although the single-impurity Kondo physics has already been well understood, the understanding of the Kondo lattice where a dense array of local moments couples to the conduction electrons is still far from complete. The ability of creating and tuning the Kondo lattice in non-f-electron systems will be great helpful for further understanding the Kondo lattice behavior. Here we show that the Pb intercalation in the charge-density-wave-driven narrow-electronic-band system 1T-TaS2 induces a transition from the insulating gap to a sharp Kondo resonance in the scanning tunneling microscopy measurements. It results from the Kondo screening of the localized moments in the 13-site Star-of-David clusters of 1T-TaS2. As increasing the Pb concentration, the narrow electronic band derived from the localized electrons shifts away from the Fermi level and the Kondo resonance peak is gradually suppressed. Our results pave the way for creating and tuning many-body electronic states in layered narrow-electronic-band materials.

10.
Adv Mater ; 33(42): e2102813, 2021 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-34477250

RESUMO

Superconductivity in topological kagome metals has recently received great research interests. Here, charge density wave (CDW) orders and the evolution of superconductivity under various pressures in CsV3 Sb5 single crystal with V kagome lattice are investigated. By using high-resolution scanning tunneling microscopy/spectroscopy (STM/STS), two CDW orders in CsV3 Sb5 are observed which correspond to 4a × 1a and 2a × 2a superlattices. By applying pressure, the superconducting transition temperature Tc is significantly enhanced and reaches a maximum value of 8.2 K at around 1 GPa. Accordingly, CDW state is gradually declined as increasing the pressure, which indicates the competing interplay between CDW and superconducting state in this material. The broad superconducting transitions around 0.4-0.8 GPa can be related to the strong competition relation among two CDW states and superconductivity. These results demonstrate that CsV3 Sb5 is a new platform for exploring the interplay between superconductivity and CDW in topological kagome metals.

11.
Phys Rev Lett ; 126(25): 256402, 2021 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-34241511

RESUMO

Here we use low-temperature scanning tunneling microscopy and spectroscopy to reveal the roles of the narrow electronic band in two 1T-TaS_{2}-related materials (bulk 1T-TaS_{2} and 4H_{b}-TaS_{2}). 4H_{b}-TaS_{2} is a superconducting compound with alternating 1T-TaS_{2} and 1H-TaS_{2} layers, where the 1H-TaS_{2} layer has a weak charge density wave (CDW) pattern and reduces the CDW coupling between the adjacent 1T-TaS_{2} layers. In the 1T-TaS_{2} layer of 4H_{b}-TaS_{2}, we observe a narrow electronic band located near the Fermi level, and its spatial distribution is consistent with the tight-binding calculations for two-dimensional 1T-TaS_{2} layers. The weak electronic hybridization between the 1T-TaS_{2} and 1H-TaS_{2} layers in 4H_{b}-TaS_{2} shifts the narrow electronic band to be slightly above the Fermi level, which suppresses the electronic correlation-induced band splitting. In contrast, in bulk 1T-TaS_{2}, there is an interlayer CDW coupling-induced insulating gap. In comparison with the spatial distributions of the electronic states in bulk 1T-TaS_{2} and 4H_{b}-TaS_{2}, the insulating gap in bulk 1T-TaS_{2} results from the formation of a bonding band and an antibonding band due to the overlap of the narrow electronic bands in the dimerized 1T-TaS_{2} layers.

12.
Front Oncol ; 11: 656687, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34150623

RESUMO

Triple-negative breast cancer (TNBC) is more aggressive and has poorer prognosis compared to other subtypes of breast cancer. Epithelial-to-mesenchymal transition (EMT) is a process in which epithelial cells transform into mesenchymal-like cells capable of migration, invasion, and metastasis. Recently, we have demonstrated that lovastatin, a 3-hydroxy-3-methylglutaryl-coenzyme A reductase inhibitor and a lipid-lowering drug, could inhibit stemness properties of cancer stem cells (CSCs) derived from TNBC cell in vitro and in vivo. This study is aimed at investigating whether lovastatin inhibits TNBC CSCs by inhibiting EMT and suppressing metastasis and the mechanism involved. In the present study, we found that lovastatin dysregulated lysine succinylation of cytoskeleton-associated proteins in CSCs derived from TNBC MDA-MB-231 cell. Lovastatin inhibited EMT as demonstrated by down-regulation of the protein levels of Vimentin and Twist in MDA-MB-231 CSCs in vitro and vivo and by reversal of TGF-ß1-induced morphological change in MCF10A cells. Lovastatin also inhibited the migration of MDA-MB-231 CSCs. The disruption of cytoskeleton in TNBC CSCs by lovastatin was demonstrated by the reduction of the number of pseudopodia and the relocation of F-actin cytoskeleton. Combination of lovastatin with doxorubicin synergistically inhibited liver metastasis of MDA-MB-231 CSCs. Bioinformatics analysis revealed that higher expression levels of cytoskeleton-associated genes were characteristic of TNBC and predicted survival outcomes in breast cancer patients. These data suggested that lovastatin could inhibit the EMT and metastasis of TNBC CSCs in vitro and in vivo through dysregulation of cytoskeleton-associated proteins.

13.
Biomater Sci ; 9(6): 2020-2031, 2021 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-33439161

RESUMO

Colorectal cancer (CRC) is the third most common cancer around the world. Recent findings suggest that cancer stem cells (CSCs) play a pivotal role in the resistance to current therapeutic modalities, including surgery and chemotherapy. Photodynamic therapy (PDT) is a promising non-invasive therapeutic strategy for advanced metastatic CRC. Traditional photosensitizers such as pyropheophorbide-a (Pyro) lack tumor selectivity, causing unwanted treatment-related toxicity to the surrounding normal tissue. In order to enhance the targeting properties of Pyro, we synthesize a novel photosensitizer, CD133-Pyro, via the conjugation of Pyro to a peptide domain targeting CD133, which is highly expressed on CRC CSCs and correlated with poor prognosis of CRC patients. We demonstrate that CD133-Pyro possesses the targeted delivery capacity both in CRC CSCs derived from HT29 and SW620 cell lines and in a xenograft mouse model of tumor growth. CD133-Pyro PDT can promote the production of reactive oxygen species (ROS), suppress the stemness properties, and induce autophagic cell death in CRC CSCs. Furthermore, CD133-Pyro PDT has a potent inhibitory effect on CRC CSC-derived xenograft tumors in nude mice. These findings may offer a useful and important strategy for the treatment of CRC through targeting CSCs.


Assuntos
Neoplasias Colorretais , Fotoquimioterapia , Animais , Linhagem Celular Tumoral , Neoplasias Colorretais/tratamento farmacológico , Humanos , Camundongos , Camundongos Nus , Células-Tronco Neoplásicas , Peptídeos/uso terapêutico , Fármacos Fotossensibilizantes/uso terapêutico
14.
Nano Lett ; 20(12): 8854-8860, 2020 Dec 09.
Artigo em Inglês | MEDLINE | ID: mdl-33170704

RESUMO

Water-solid interactions are crucial for many fundamental phenomena and technological processes. Here, we report a scanning tunneling microscopy study about the charge density wave (CDW) transition in 1T-TaS2 driven by a single water dipole layer. At low temperature, pristine 1T-TaS2 is a prototypical CDW compound with 13 × 13 charge order. After growing a highly ordered water adlayer, a new charge order with 3 × 3 periodicity emerges on water-covered 1T-TaS2. After water desorption, the entire 1T-TaS2 surface appears as localized 13 × 13 CDW domains that are separated by residual-water-cluster-pinned CDW domain walls. First-principles calculations show that the electric dipole moments in the water adlayer attract electrons to the top layer of 1T-TaS2, which shifts the phonon softening mode and induces the 13 × 13 to 3 × 3 charge order transition. Our results pave the way for creating new collective quantum states of matter with a molecular dipole layer.

15.
Nat Commun ; 11(1): 4002, 2020 Aug 10.
Artigo em Inglês | MEDLINE | ID: mdl-32778641

RESUMO

Layered kagome-lattice 3d transition metals are emerging as an exciting platform to explore the frustrated lattice geometry and quantum topology. However, the typical kagome electronic bands, characterized by sets of the Dirac-like band capped by a phase-destructive flat band, have not been clearly observed, and their orbital physics are even less well investigated. Here, we present close-to-textbook kagome bands with orbital differentiation physics in CoSn, which can be well described by a minimal tight-binding model with single-orbital hopping in Co kagome lattice. The capping flat bands with bandwidth less than 0.2 eV run through the whole Brillouin zone, especially the bandwidth of the flat band of out-of-plane orbitals is less than 0.02 eV along Γ-M. The energy gap induced by spin-orbit interaction at the Dirac cone of out-of-plane orbitals is much smaller than that of in-plane orbitals, suggesting orbital-selective character of the Dirac fermions.

16.
Environ Sci Technol ; 54(15): 9519-9528, 2020 08 04.
Artigo em Inglês | MEDLINE | ID: mdl-32609501

RESUMO

Although the bioaccumulation of organophosphate flame retardants (OPFRs) in aquatic organisms has been investigated, little information is available about their bioaccumulation in mammals following chronic inhalation exposure. To address this knowledge gap, C57BL/6 mice were exposed to 7 PM2.5-associated OPFRs via the trachea to study their bioaccumulation, tissue distribution, and urinary metabolites. Low (corresponding to the real PM2.5 concentrations occurring during winter in Guangzhou), medium, and high dosages were examined. After 72 days' exposure, ∑OPFR concentrations in tissues from mice in the medium dosage group decreased in the order of intestine > heart > stomach > testis > kidney > spleen > brain > liver > lung > muscle. Of the OPFRs detected in all three exposure groups, chlorinated alkyl OPFRs were most heavily accumulated in mice. We found a significant positive correlation between the bioaccumulation ratio and octanol-air partition coefficient (KOA) in mice tissues for low log KOW OPFR congeners (log KOW ≤ 4, p < 0.05). Three urinary metabolites (di-p-cresyl phosphate: DCrP, diphenyl phosphate: DPhP, dibutyl phosphate: DnBP) were detected from the high dosage group. These results provide important insights into the bioaccumulation potential of OPFRs in mammals and emphasize the health risk of chlorinated alkyl OPFRs.


Assuntos
Retardadores de Chama , Animais , Biomarcadores , Exposição Ambiental , Retardadores de Chama/análise , Retardadores de Chama/toxicidade , Masculino , Camundongos , Camundongos Endogâmicos C57BL , Organofosfatos/análise , Organofosfatos/toxicidade , Material Particulado
17.
Nanoscale ; 12(21): 11619-11626, 2020 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-32435779

RESUMO

Minimizing the invasiveness of scanning tunneling measurements is paramount for observation of the magnetic properties of unperturbed atomic-scale objects. We show that the invasiveness of STM inspection on few-atom spin systems can be drastically reduced by means of a remote detection scheme, which makes use of a sensor spin weakly coupled to the sensed object. By comparing direct and remote measurements we identify the relevant perturbations caused by the local probe. For direct inspection we find that tunneling electrons strongly perturb the investigated object even for currents as low as 3 pA. Electrons injected into the sensor spin induce perturbations with much reduced probability. The sensing scheme uses standard differential conductance measurements, and is decoupled both by its non-local nature, and by dynamic decoupling due to the significantly different time scales at which the sensor and sensed object evolve. The latter makes it possible to effectively remove static interactions between the sensed object and the spin sensor while still allowing the spin sensing. In this way we achieve measurements with a reduction in perturbative effects of up to 100 times relative to direct scanning tunneling measurements, which enables minimally invasive measurements of a few-atom magnet's fragile spin states with STM.

18.
Talanta ; 207: 120260, 2020 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-31594598

RESUMO

Metabolomics tactics have been applied in the research associated with embryonic zebrafish. However, the report regarding the evaluation of impacts of sample pretreatment on metabolomics results from zebrafish embryos is limited. In the present study, different data normalization approaches, extraction solvents, and extraction strategies for off-line derivatization gas chromatography coupled with mass spectrometry-based metabolomics analysis of zebrafish eleutheroembryos were evaluated and optimized. The results showed that, when 4-chlorophenylalanine normalization, sample homogenization and pure methanol combined with ultrasonic extraction were conducted, better repeatabilities, higher signals and broader coverages of detected metabolites can be achieved. The recovery and standard deviation of most standards were in the range of 82%-121% and 6.6%-12%, respectively, while the relative standard deviation of major detected metabolites ranged from 5.4% to 19%, indicating good extraction efficiencies and method precision. Under the developed method, 87 important endogenous metabolites such as citric acid and hypoxanthine were identified by universal databases or standards among 270 extracted metabolites, which consisted of sugars, amines, amino acids, nucleotides, fatty acids, and sterols. Therefore, the results could provide a proper pretreatment protocol for the analysis of wide-coverage metabolome in embryonic zebrafish. In addition, this study highlights the impact of normalization and extraction methods on the data quality of metabolomics analysis.


Assuntos
Métodos Analíticos de Preparação de Amostras/métodos , Cromatografia Gasosa-Espectrometria de Massas , Metabolômica/métodos , Peixe-Zebra/embriologia , Animais , Solventes/química
19.
Talanta ; 194: 320-328, 2019 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-30609538

RESUMO

Toxic chemicals such as flame retardants are associated with atmospheric fine particles (PM2.5), which are an important pollutant in the world. In this study, a sensitive method using gas chromatography-tandem triple quadrupole mass spectrometry combined with ultrasonic-assisted extraction and multi-phase column purification was developed for simultaneously determination of 29 flame retardants including halogenated flame retardants (HFRs) and organophosphate flame retardants (OPFRs) in PM2.5 samples. Extraction time, as well as the type and volume of elution solvent were optimized. The recoveries of all target flame retardants from PM2.5 samples were in the range of 70%‒130%, with good repeatability and reproducibility (0.39%‒17.4%). The instrumental detection limits (IDLs) and method quantitation limits (MQLs) of HFRs were in the range of 0.004‒5.44 pg and 0.002‒2.52 pg m-3, while those of OPFRs were 0.003‒0.23 pg and 0.07‒5.41 pg m-3, respectively. The developed method has been successfully applied for analysis of target flame retardants in atmospheric PM2.5 collected from the cities of Guangzhou and Taiyuan, China. HFRs were found at concentrations of 45.7‒1230 pg m-3 and 51.2‒82.3 pg m-3 in Guangzhou and Taiyuan. The concentrations of HFRs were lower than those of OPFRs, which were detected at concentrations of 6004‒49,800 pg m-3 and 16,741‒34,346 pg m-3 in Guangzhou and Taiyuan. Accordingly, the analytical method is robust and useful for further elucidating the contamination profiles of flame retardants in PM2.5.

20.
Environ Toxicol Chem ; 38(4): 794-805, 2019 04.
Artigo em Inglês | MEDLINE | ID: mdl-30614048

RESUMO

Climbazole is an antifungal active ingredient used in personal care products. After application this chemical reaches the aquatic environment and may pose a risk to fish. In the present study, we measured the transcriptional effects of essential genes related to a wide range of signaling pathways on zebrafish eleutheroembryos exposed to climbazole at environmentally relevant and predicted worst-case environmental concentrations, and explored the potential biomarkers via partial least squares discriminant analysis. Transcription analysis covering up to 73 genes revealed significant down-regulation of circadian rhythm- and steroidogenesis-related genes in zebrafish embryos and larvae after exposure to environmentally relevant concentrations of climbazole. This topical antifungal agent also modulated the transcripts of genes involved in inflammation, oxidative stress, oocyte maturation, and sexual differentiation at predicted worst-case environmental concentrations. In addition, mprα, igf3, nr1d1, nr1d2b, cyp19a1a, vtg1, il-1ß, and il-8 were chosen as potential biomarkers in embryonic zebrafish following exposure to climbazole. These findings can help us understand the remarkable transcriptional response to climbazole in the early life stage of zebrafish. Future research should elucidate whether the transcriptional modulation translates into metabolic phenotypes associated with the corresponding signaling pathways. Environ Toxicol Chem 2019;38:794-805. © 2019 SETAC.


Assuntos
Embrião não Mamífero/efeitos dos fármacos , Imidazóis/toxicidade , Transcrição Gênica/efeitos dos fármacos , Poluentes Químicos da Água/toxicidade , Peixe-Zebra/genética , Animais , Biomarcadores/metabolismo , Embrião não Mamífero/metabolismo , Larva/efeitos dos fármacos , Larva/metabolismo , Diferenciação Sexual/efeitos dos fármacos , Diferenciação Sexual/genética , Transdução de Sinais , Peixe-Zebra/embriologia , Peixe-Zebra/metabolismo
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