h i g h l i g h t sThe absorption, bioaccumulation, metabolism and internal exposure of OPFRs are reviewed. Inhalation, ingestion and dermal contact are the main OPFRs absorptionpathways for humans. General in vivo and in vitro metabolic pathways of three different types of OPFRs are proposed. DAPs and MAPs are considered as putative biomarkers for the assessment of internal exposure of OPFRs in humans. a r t i c l e i n f o t r a c tDue to their widespread use, organophosphate flame retardants (OPFRs) are commonly detected in various environmental matrices and have been identified as emerging contaminants. Considering the adverse effects of OPFRs, many researchers have paid their attention on the absorption, bioaccumulation, metabolism and internal exposure processes of OPFRs in animals and humans. In this article, we first review the diverse absorption routes of OPFRs by animals and humans (e.g., inhalation, ingestion, dermal absorption and gill absorption). Bioaccumulation and biomagnification potentials of OPFRs in different types of organisms and food webs are also summarized, based on quite limited available data and results. For metabolism, we review the Phase-I and Phase-II metabolic processes for each type of OPFRs (chlorinated OPFRs, alkyl-OPFRs and aryl-OPFRs) in the animals and humans, as well as toxicokinetic information and putative exposure biomarkers on OPFRs. Finally, we highlight gaps in our knowledge and critical directions for future internal exposure studies of OPFRs in animals and humans.

Tris(2-butoxyethyl) phosphate (TBOEP) and tris( n-butyl) phosphate (TNBP) are the most commonly used alkyl organophosphate esters (alkyl-OPEs), and they increasingly accumulate in organisms and create potential health hazards. This study examined the metabolism of TNBP and TBOEP in Carassius carassius liver and intestinal microsomes and the production of their corresponding monohydroxylated and dealkylated metabolites. After 140 min of incubation with fish liver microsomes, the rapid depletion of TNBP and TBOEP were both best fitted to the Michaelis-Menten model (at administrated concentrations ranging from 0.5 to 200 μM), with a CL (intrinsic clearance) of 3.1 and 3.9 μL·min·mg protein, respectively. But no significant ( P > 0.05) biotransformation was observed for these compounds in intestinal microsomes at any administrated concentrations. In fish liver microsomes assay, bis(2-butoxyethyl) hydroxyethyl phosphate (BBOEHEP) and bis(2-butoxyethyl) 3-hydroxyl-2-butoxyethyl phosphate (3-OH-TBOEP) were the most abundant metabolites of TBOEP, and dibutyl-3-hydroxybutyl phosphate (3-OH-TNBP) was the predominant metabolite of TNBP. Similarly, the apparent V values (maximum metabolic rate) of BBOEHEP and 3-OH-TNBP were also respectively highest among those of other metabolites. Further inhibition studies were conducted to identify the specific cytochrome P450 (CYP450) isozymes involved in the metabolism of TNBP and TBOEP in liver microsomes. It was confirmed that CYP3A4 and CYP1A were the significant CYP450 isoforms catalyzing the metabolism of TNBP and TBOEP in fish liver microsomes. Overall, this study emphasized the importance of hydroxylated metabolites as biomarkers for alkyl-OPEs exposure, and further research is needed to validate the in vivo formation and toxicological implications of these metabolites.

Organophosphate flame retardants (PFRs) can be rapidly metabolized in the body, and recent studies have shown that the di-alkyl phosphates (DAPs) are important metabolites. The accumulation and distribution of 8 PFRs and their 4 DAPs metabolites were first investigated in whole-body samples and various tissues of three freshwater fish species (topmouth gudgeon, crucian carp and loach) with different feeding habits from locations around Beijing, China. Concentrations of ΣPFRs in whole-body samples across all sampling locations ranged from 264.7 to 1973 ng g lipid weight (lw), while all the paired DAP metabolites were detected in the total range from 35.3 to 510 ng g lw. The calculated log bioconcentration factors (BCFs) of PFRs in whole fish were correlated with their log K (P < 0.05). The metabolite/parent ratios (MPRs) of ΣDAPs were calculated and ranged from 0.10 to 1.12 in whole-fish of all species. The MPRs of BBOEP/TBOEP were the highest. With respect to their distribution in different tissues, both the parent PFRs and metabolites were found at relatively higher levels in the liver than in other tissues (muscle, intestine, kidney and ovary), which was markedly different from those observed in avian species in previous studies. The accumulation of PFRs and DAPs in various tissues was not significantly correlated with the lipid content. The highest PFRs level in the liver may be related to the active hepatic accumulation processes. Meanwhile, the MPRs for all 4 pairs were the highest in the kidney relative to the other tissues. To the best of our knowledge, this is first study of DAPs in wild animals, and our study may improve the understanding of the accumulation and metabolism of PFRs in the body.

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We report the growth of high-quality AlN films on nano-patterned sapphire substrates (NPSSs) by graphene-assisted quasi-van der Waals epitaxy, which enables rapid coalescence to shorten the growth time. Due to the presence of graphene (Gr), AlN tends to be two-dimensional laterally expanded on the NPSS, leading to the reduction of dislocation density and strain release in the AlN epitaxial layer. Using first-principles calculations, we confirm that Gr can reduce the surface migration barrier and promote the lateral migration of metal Al atoms. Furthermore, the electroluminescence results of deep ultraviolet light emitting diodes (DUV-LEDs) have exhibited greatly enhanced emission located at 280 nm by inserting the Gr interlayer. The present work may provide the potential to solve the bottleneck of high efficiency DUV-LED.

Microbially derived extracellular polymeric substances (EPSs) occupy a large portion of dissolved organic matter (DOM) in surface waters, but the understanding of the photochemical behaviors of EPS is still very limited. In this study, the photochemical characteristics of EPS from different microbial sources (Shewanella oneidensis, Escherichia coli, and sewage sludge flocs) were investigated in terms of the production of reactive species (RS), such as triplet intermediates (3EPS*), hydroxyl radicals (•OH), and singlet oxygen (1O2). The steady-state concentrations of •OH, 3EPS*, and 1O2 varied in the ranges of 2.55–8.73 × 10–17, 3.01–4.56 × 10–15, and 2.08–2.66 × 10–13 M, respectively, which were within the range reported for DOM from other sources. The steady-state concentrations of RS varied among different EPS isolates due to the diversity of their composition. A strong photochemical degradation of the protein-like components in EPS isolates was identified by excitation emission matrix fluorescence with parallel factor analysis, but relatively, humic-like components remained stable. Fourier-transform ion cyclotron resonance mass spectrometry further revealed that the aliphatic portion of EPS was resistant to irradiation, while other portions with lower H/C ratios and higher O/C ratios were more susceptible to photolysis, leading to the phototransformation of EPS to higher saturation and lower aromaticity. With the phototransformation of EPS, the RS derived from EPS could effectively promote the degradation of antibiotic tetracycline. The findings of this study provide new insights into the photoinduced self-evolution of EPS and the interrelated photochemical fate of contaminants in the aquatic environment.

No abstract

Metal halide perovskite has attracted enhanced interest for its diverse electronic and optoelectronic applications. However, the fabrication of micro‐ or nanoscale crystalline perovskite functional devices remains a great challenge due to the fragility, solvent, and heat sensitivity of perovskite crystals. Here, a strategy is proposed to fabricate electronic and optoelectronic devices by directly growing perovskite crystals on microscale metallic structures in liquid phase. The well‐contacted perovskite/metal interfaces ensure these heterostructures serve as high‐performance field effect transistors (FETs) and excellent photodetector devices. When serving as an FET, the on/off ratio is as large as 106 and the mobility reaches up to ≈2.3 cm2 V−1 s−1. A photodetector is displayed with high photoconductive switching ratio of ≈106 and short response time of ≈4 ms. Furthermore, the photoconductive response is proved to be band‐bending‐assisted separation of photoexcited carriers at the Schottky barrier of the silver and p‐type perovskites.