Nationwide distribution of perfluoroalkyl ether carboxylic acids in Chinese diets: An emerging concern.

With the phase-out of perfluorooctanoic acid (PFOA) and its replacement by perfluoroalkyl ether carboxylic acids (PFECAs), there is a potential for increased exposure to various new PFECAs among the general population in China. While there are existing studies on dietary exposure to legacy perfluoroalkyl and polyfluoroalkyl substances (PFASs), research on dietary exposure to PFECAs, especially among the general Chinese populace, remains scarce. In the present study, we investigated the distribution of PFECAs in dietary sources from 33 cities across five major regions in China, along with the associated dietary intake. Analysis indicated that aquatic animal samples contained higher concentrations of legacy PFASs compared to those from terrestrial animals and plants. In contrast, PFECAs were found in higher concentrations in plant and terrestrial animal samples. Notably, hexafluoropropylene oxide dimer (HFPO-DA) was identified as the dominant compound in vegetables, cereals, pork, and mutton across the five regions, suggesting widespread dietary exposure. PFECAs constituted the majority of PFAS intake (57 %), with the estimated daily intake (EDI) of HFPO-DA ranging from 2.33 to 3.96 ng/kg bw/day, which corresponds to 0.78-1.32 times the reference dose (RfD) (3.0 ng/kg bw/day) set by the United States Environmental Protection Agency. Given the ubiquity of HFPO-DA and many other PFECAs in the nationwide diet of China, there is an urgent need for further research into these chemicals to establish relevant safety benchmarks or consumption advisory values for the diet.

Kynurenic Acid Plays a Protective Role in Hepatotoxicity Induced by HFPO-DA in Male Mice.

Following its introduction as an alternative to perfluorooctanoic acid, hexafluoropropylene oxide dimer acid (HFPO-DA) has been extensively detected in various environmental matrices. Despite this prevalence, limited information is available regarding its hepatotoxicity biomarkers. In this study, toxicokinetic simulations indicated that under repeated treatment, HFPO-DA in mice serum reached a steady state by the 4th day. To assess its subacute hepatic effects and identify potential biomarkers, mice were administered HFPO-DA orally at doses of 0, 0.1, 0.5, 2.5, 12.5, or 62.5 mg/kg/d for 7 d. Results revealed that the lowest observed adverse effect levels were 0.5 mg/kg/d for hepatomegaly and 2.5 mg/kg/d for hepatic injury. Serum metabolomics analysis identified 34, 58, and 118 differential metabolites in the 0.1, 0.5, and 2.5 mg/kg/d groups, respectively, compared to the control group. Based on weighted gene coexpression network analysis, eight potential hepatotoxicity-related metabolites were identified; among them, kynurenic acid (KA) in mouse serum exhibited the highest correlation with liver injury. Furthermore, liver-targeted metabolomics analysis demonstrated that HFPO-DA exposure induced metabolic migration of the kynurenine pathway from KA to nicotinamide adenine dinucleotide, resulting in the activation of endoplasmic reticulum stress and the nuclear factor kappa-B signaling pathway. Notably, pretreatment with KA significantly attenuated liver injury induced by HFPO-DA exposure in mice, highlighting the pivotal roles of KA in the hepatotoxicity of HFPO-DA.

Comprehensive Assessment of Exposure Pathways for Perfluoroalkyl Ether Carboxylic Acids (PFECAs) in Residents Near a Fluorochemical Industrial Park: The Unanticipated Role of Cereal Consumption.

With the replacement of perfluorooctanoic acid (PFOA) with perfluorinated ether carboxylic acids (PFECAs), residents living near fluorochemical industrial parks (FIPs) are exposed to various novel PFECAs. Despite expectations of low accumulation, short-chain PFECAs, such as perfluoro-2-methoxyacetic acid (PFMOAA), previously displayed a considerably high body burden, although the main exposure routes and health risks remain uncertain. Here, we explored the distribution of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in diverse environmental media surrounding a FIP in Shandong Province, China. PFECAs were found at elevated concentrations in all tested matrices, including vegetables, cereals, air, and dust. Among residents, 99.3% of the ∑36PFAS exposure, with a 43.9% contribution from PFECAs, was due to gastrointestinal uptake. Dermal and respiratory exposures were negligible at 0.1 and 0.6%, respectively. The estimated daily intake (EDI) of PFMOAA reached 114.0 ng/kg body weight (bw)/day, ranking first among all detected PFECAs. Cereals emerged as the dominant contributor to PFMOAA body burden, representing over 80% of the overall EDI. The median EDI of hexafluoropropylene oxide dimer acid (HFPO-DA) was 17.9 ng/kg bw/day, markedly higher than the USEPA reference doses (3.0 ng/kg bw/day). The absence of established threshold values for other PFECAs constrains a comprehensive risk assessment.

Accumulation and glucocorticoid signaling suppression by four emerging perfluoroethercarboxylic acids based on animal exposure and cell testing.

Various perfluoroethercarboxylic acids (PFECA) have emerged as next-generation replacements of legacy per- and polyfluoroalkyl substances (PFAS). However, there is a paucity of information regarding their bioaccumulation ability and hazard characterization. Here, we explored the accumulation and hepatotoxicity of four PFECA compounds (HFPO-DA, HFPO-TA, PFO4DA, and PFO5DoDA) in comparison to perfluorooctanoic acid (PFOA) after chronic low-dose exposure in mice. Except for HFPO-DA, the levels of all tested PFAS in the liver exceeded that in serum. High molecular weight PFECA compounds (PFO5DoDA and HFPO-TA) showed stronger accumulation capacity and longer half-lives (t1/2) than low molecular weight PFECA compounds (HFPO-DA and PFO4DA) and even legacy PFOA. Although hepatomegaly is a common apical end point of PFAS exposure, the differentially expressed gene (DEG) profiles in the liver suggested significant differences between PFOA and the four PFECA compounds. Gene enrichment analysis supported a considerable inhibitory effect of PFECA, but not PFOA, on the glucocorticoid receptor (GR) signaling pathway. Both HFPO-TA and PFO5DoDA demonstrated a more pronounced ability to perturb RNA expression profiles in vivo and to suppress GR signaling in vitro compared to HFPO-DA and PFO4DA. Calculated reference doses (RfDs) emphasized the potential hazard of PFECA to human health. Overall, our findings indicate that PFECA alternatives do not ease the concerns raised from legacy PFAS pollution.

miR-452-5p regulates the responsiveness of intestinal epithelial cells in inflammatory bowel disease through Mcl-1.

Inflammatory bowel diseases (IBDs) are chronic immune disorders that occur in the intestinal tract. Previous studies have revealed that intestinal epithelial cells (IECs) play critical roles in the development of IBDs, and therapies targeting IECs hold great potential for the treatment of IBDs. However, the roles of microRNAs (miRs) in the regulation of IEC properties and whether they can be used as targets for IEC regulation and IBD treatment are largely unknown. The aim of the present study was to investigate the role of the miR-452-5p/Mcl-1 axis in the regulation of the properties of IECs during the pathology of IBD. A dextran sulfate sodium-induced mouse model of ulcerative colitis (UC) and an in vitro lipopolysaccharide-stimulated IEC-6 cell model were investigated. The results revealed that miR-452-5p expression in the IECs of the mice increased significantly upon UC induction, and the knockdown of miR-452-5p alleviated the IBD symptoms. Furthermore, the suppression of miR-452-5p downregulated the expression of the inflammatory cytokines IL-6, IL-8 and TNFα, and upregulated the expression of intestinal barrier-associated molecules, namely occludin, zona occludens 1 and mucin-2 in IECs in vitro and in vivo. Notably, the results indicated that miR-452-5p modulated the responses of IECs by negatively regulating the expression of Mcl-1, as the knockdown of Mcl-1 abrogated the effects of miR-452-5p suppression on IECs. The present study suggested that miR-452-5p regulated the responsiveness of IECs to influence the development of UC in an Mcl-1-dependent manner. These observations provide important information to improve the understanding of IBD pathogenesis and indicate that targeting the miR-452-5p-Mcl-1 signaling axis in IECs holds potential for IBD treatment.

Evaluation of self-cleaning performance of the modified g-C3N4 and GO based PVDF membrane toward oil-in-water separation under visible-light.

Photocatalytic membranes (PMs), coupling of membrane filtration and photocatalysis, have exhibited the potential for application in the wastewater treatment. In this study, we firstly adopted the supramolecular aggregates of melamine (M), cyanuric acid (C), and urea (U) in specific dimethyl sulfoxide (DMSO) as precursors to prepare carbon nitride MCU-C3N4 with high photocatalytic performance, and a kind of novel-designed photocatalytic membrane was prepared via filtrating the mixture of graphene oxide (GO) nanosheets and MCU-C3N4 on PVDF membrane supports, and then crosslinked using glutaraldehyde (GA) to construct a steady coating on the GO/MCU-C3N4/PVDF membrane. GO/MCU-C3N4/PVDF composite membrane exhibited higher permeation flux than that of GO/PVDF membrane and exhibited excellent separation performance for oil-in-water emulsion. A visible light-driven self-cleaning four-stage filtration by a self-built dead-end filtration system was carried out to evaluate membrane antifouling property, and GO/MCU-C3N4/PVDF membrane (M2) possessed higher flux recovery ratio (FRR) (∼92.36%) and lower irreversible fouling resistance (Rir) ratio (∼8%) under 30min visible-light irradiation, maintaining relatively higher FRR (>72%) during 4 cycling of four-stage filtrating experiments. GO/MCU-C3N4/PVDF PMs are equipped with high permeation flux, separation performance, anti-fouling property and stability, indicating potential application in water treatment.

Evaluation of self-cleaning and photocatalytic properties of modified g-C3N4 based PVDF membranes driven by visible light.

Recently, the application of membranes faces a big challenge due to membrane fouling, to alleviate this situation, the hybridization of photocatalysis and membrane filtration has aroused significant attention. In this study, we firstly introduced melamine, cyanuric acid and urea in dimethyl sulfoxide (DMSO) as precursors to fabricated the MCU(DMSO)-C3N4 material with excellent photocatalytic performance, and immobilized it on PVDF membranes by vacuum filtration, subsequently adding polyethylene glycol and glutaraldehyde as crosslinkers from MCU-C3N4/PVDF membrane. The results demonstrate that with the MCU-C3N4 ratio increasing, the membrane flux was gradually decreased. Besides, the photocatalytic efficiencies of MCU-C3N4/PVDF for rhodamine B (RhB) and tetracycline hydrochloride (TC) degradation are 84.24% and 71.26% respectively, which are about 8 times higher than that of the original membrane. To evaluate antifouling performance of photocatalytic membranes, we conducted a four-stage filtration system, and the flux recovery ratio (FRR) of MCU-C3N4/PVDF membranes reached over 80% (optimum 91%) under visible light irradiating (λ > 420 nm) for 30 min. Meanwhile, under visible light irradiation reversible fouling (Rr) gradually became the dominant fouling factor instead of the irreversible fouling (Rir), indicating the excellent antifouling performance of MCU-C3N4/PVDF membranes. This novel method to modify membranes with MCU-C3N4 gives insight to photocatalytic and self-cleaning properties of photocatalytic composite membranes, providing theoretical basis for their broad application.

Membrane layers intensifying quorum quenching alginate cores and its potential for membrane biofouling control.

Quorum quenching (QQ) has been proved to be an efficient method to mitigate biofouling in membrane bioreactors (MBRs). In this paper, in order to enhance practicability of QQ microcapsules, we prepared three types microcapsules with same alginate cores (SAs). The microcapsules with polyacrylonitrile (PAN) layer showed excellent performance in preventing cell leakage from the microcapsules, increasing service life and improving mechanical strength. And confocal laser scanning microscopy images demonstrated that there were very little dead bacteria in the microcapsules with both chitosan and PAN layer than microcapsules with only PAN layer because chitosan layer can protect bacteria entrapped in cores from the hurt caused by poisonous PAN solution. At the same time, the microcapsules with PAN layer presented more efficient anti-biofouling ability in the physical washing test. At last, the bacterial microcapsules coated with both chitosan and PAN layer showed an obvious biofouling mitigation during the MBRs operation.

Enantioselective Construction of Cyclobutanes: A New and Concise Approach to the Total Synthesis of (+)-Piperarborenine B.

A highly diastereoselective and enantioselective Cu(II)/SaBOX-catalyzed [2 + 2] cycloaddition of methylidenemalonate and multisubstituted alkenes was developed to furnish optically active cyclobutanes in high yields with >99/1 dr and up to >99% ee. By application of the newly developed method, the total synthesis of (+)-piperarborenine B was completed in eight steps from methylidenemalonate and olefin in 17% overall yield with >99/1 dr and 99% ee.

Water temperature significantly impacts the formation of iodinated haloacetamides during persulfate oxidation.

The use of persulfate oxidation processes is receiving increasing interest for the removal of aquatic contaminants. However, it is unknown whether its application in the presence of iodide has the potential to directly form iodinated DBPs. This study investigated formation of six chlorinated, brominated and iodinated di-haloacetamides (DHAcAms) during persulfate oxidation in the presence of bromide and iodide. Formation of the same DHAcAms during chlorination was monitored for comparison. Persulfate oxidation of natural water formed diiodoacetamide (DIAcAm), and heat-activated persulfate, at 45 °C and 55 °C, generated bromoiodoacetamide (BIAcAm) and dibromoacetamide (DBAcAm), besides DIAcAm. At an ambient iodide concentration of 0.3 µM, total DHAcAms increased slightly from 0.43 to 0.57 nM as the water temperature increased from 4 °C to 35 °C, respectively (only DIAcAm detected), then significantly increased to 1.6 nM at 55 °C (DIAcAm, BIAcAm and DBAcAm detected). Equivalent total DHAcAm concentrations in the presence of 3.0 µM iodide were 0.5, 0.91 and 2.1 nM, respectively. Total DHAcAms formed during chlorination, predominantly dichloroacetamide (DCAcAm) and bromochloroacetamide (BCAcAm), were always significantly higher than that during persulfate oxidation. However, an integrated risk assessment showed the toxicity resulting from the DHAcAms was higher during persulfate oxidation than chlorination. An increase in water temperature from 25 °C to 55 °C significantly increased the integrated toxic risk values for both persulfate oxidation and chlorination. Use of persulfate oxidation should be weighed against the formation of high-toxicity iodinated HAcAms in waters with high ambient iodide concentrations.

Asymmetric Annulation of Donor-Acceptor Cyclopropanes with Dienes.

An efficient [4 + 3] cycloaddition reaction of D-A cyclopropanes with dienes has been successfully developed. The reaction proceeds well with various dienolsilyl ethers in the presence of Lewis acid, delivering a variety of cycloheptenes and [n,5,0]carbobicycles with excellent stereoselectivity. The asymmetric version of this reaction is also realized using a newly designed chiral Cy-TOX ligand, providing a new approach to access optically active cycloheptenes and [n,5,0]carbobicycles. Mechanisic study reveals that the reaction involves a stepwise pathway, which undergoes an unusual ring opening of five-membered [3 + 2] intermediate and sequential intramolecular cyclization to afford the thermodynamically stable [4 + 3] annulation product.

Highly diastereoselective and enantioselective formal [4 + 3] cycloaddition of donor-acceptor cyclobutanes with nitrones.

The first highly diastereoselective and enantioselective catalytic formal [4 + 3] cycloaddition of 1,1-cyclobutane diester with nitrone has been developed. Sterically hindered chiral SaBOX/Cu(II) complex promotes the reaction efficiently with a broad substrate scope, producing a range of multifunctionalized optically active 1,2-oxazepanes with excellent stereocontrol (up to >99/1 dr and 97% ee).

Highly dispersed pd catalyst locked in knitting aryl network polymers for Suzuki-Miyaura coupling reactions of aryl chlorides in aqueous media.

Highly dispersed palladium chloride catalysts locked in triphenylphosphine-functionalized knitting aryl network polymers (KAPs) are developed and exhibit excellent activity under mild conditions in the Suzuki-Miyaura cross-coupling reactions of aryl chlorides in aqueous media. This work highlights that the microporous polymers not only play the role of support materials, but also protect the Pd species from aggregation and precipitation, hence, positively effect the catalysis activity.

Adsorption of roxarsone from aqueous solution by multi-walled carbon nanotubes.

Roxarsone, an organoarsenic compound serving as a common feeding additive in poultry industry, brings about potential risk of the toxic inorganic arsenate contamination in ambient environment. Current understanding in the dynamics of roxarsone removal and the determining environmental processes remains unclear, thus restricts the progress in roxarsone-contaminated wastewater treatment. In this study, the adsorption of roxarsone on multi-walled carbon nanotubes (MWCNTs) was investigated. The adsorption of roxarsone on MWCNTs decreased dramatically with increasing pH from 2.0 to 11.7 and decreased significantly with increasing ionic strength from 0 to 1.0 mol/L KCl. It was found that the sorption isotherms of roxarsone on MWCNTs were nonlinear, which can be well described according to the Freundlich and Polanyi-Manes models. Thermodynamic analysis indicates that the adsorption of roxarsone on MWCNTs is an exothermic and spontaneous process. Sorption site energy analysis reveals a distribution of sorption energy and the heterogeneous adsorption sites of roxarsone on MWCNTs. The dynamic adsorption with column shows the potential of the practical application for the roxarsone-contaminated wastewater treatment by MWCNTs. The FTIR analysis indicates that EDA interaction and electrostatic repulsion might be the dominant mechanisms for the adsorption of roxarsone on MWCNTs.

An efficient palladium catalyst system for the oxidative carbonylation of glycerol to glycerol carbonate.

Glycerol carbonate can be readily synthesized from the oxidative carbonylation of glycerol catalyzed by PdCl(2)(phen) (phen=1,10-phenanthroline) with the aid of CuI. High conversion (95 %) and selectivity (98 %) are achieved and the turnover frequency (TOF) reaches 455 h(-1). Furthermore, a new zeolite-Y-confined Pd catalyst, PdCl(2)(phen)@Y, has been successfully prepared by a ''flexible ligand'' method. The structure and composition of the heterogeneous catalyst have been characterized by atomic absorption spectroscopy, elemental analysis, N(2) sorption, XRD, FTIR, solid-state NMR, and X-ray photoelectron spectroscopy. This catalyst exhibits a comparable activity to its homogeneous counterpart and could be reused five times without significant decrease in activity. This is the most efficient heterogeneous system for synthesizing glycerol carbonate by the oxidative carbonylation of glycerol to date.

Facile synthesis of hierarchical nanocrystalline ZSM-5 zeolite under mild conditions and its catalytic performance.

Hierarchical nanocrystalline ZSM-5 zeolite (NZ5) was synthesized at 100 °C under atmospheric pressure using methylamine as a mineralizing agent. The crystallization process of NZ5 was characterized by dynamic light scattering (DLS), X-ray diffraction (XRD), and infrared spectroscopy (FTIR). The results of contrastive experiments showed that evaporation of the solvent promoted the aggregation of primary particles, and the addition of methylamine accelerated the crystallization process. The NZ5 aggregate consisted of 20 nm individual particles, as shown in scanning electron microscope (SEM). The lattice fringes in the transmission electron microscope (TEM) images and the XRD results indicated that individual particles of NZ5 were highly crystalline. N(2) adsorption-desorption isotherms showed that NZ5 had high BET surface areas with mesopores having a mean diameter of about 9 nm. NZ5 exhibited a long lifetime, a stable and high yield of liquid hydrocarbons, and a high anti-coking performance in methanol-to-hydrocarbons reaction. Catalytic testing and TGA results showed that the lifetime of NZ5 was about ten times longer than that of micro-sized ZSM-5 zeolite (MZ5), and the average coking rate with NZ5 was one fifth over that of MZ5.