Revealing the construction of CuOCe interfacial sites via increased support utilization for enhanced CO2 electroreduction and Li-CO2 batteries.

Leveraging designed electronic oxide-metal interactions (EOMI), cerium-supported copper demonstrates remarkable competitiveness in the carbon dioxide reduction reaction (CO2RR). Nevertheless, the limited utilization efficiency of conventional cerium oxide (CeO2) support hampers the EOMI effect. Furthermore, a comprehensive understanding of the influence of distinct crystalline surfaces of CeO2 on the loaded active copper (Cu) species remains elusive. Herein, oxide carriers with diverse crystal facets are acquire for loading to load Cu species through the incorporation of cerium-based metal organic frameworks (MOFs) precursors. Simultaneously, owing to the elevated specific surface area conferred by MOF precursors, Cu/CeO2 hosts ample catalytically active sites for carbon dioxide (CO2) electrocatalytic reactions and as catalytic cathodes for lithium-CO2 (Li-CO2) batteries. Furthermore, the carbon converted from organic ligands in MOFs precursors not only proficiently immobilizes and disperses the active sites, but also enhances the inherent conductive stability of the oxide while augmenting energy utilization efficiency. Leveraging these advantages, the electrocatalyst derived from MOFs achieves a peak CO2-to-methane Faradaic efficiency of 57.9 %, whereas the assembled Li-CO2 batteries exhibit notable activity and durability, boasting a substantial full-discharge capacity of 8907 mAh/g, a discharge voltage of 2.65 V, and an extended cycle life exceeding 1000 h. Mechanistic investigations were conducted using density functional theory (DFT) calculations to thoroughly explore the impact of CeO2 carrier crystal facets, specifically (111), (100), and (110), on the loaded copper species. Notably, (110) was identified as the optimal facet due to its favorable contributions to electronic structure optimization and stability enhancement.

Insight into the binding model of per- and polyfluoroalkyl substances to proteins and membranes.

Legacy per- and polyfluoroalkyl substances (PFASs) have elicited much concern because of their ubiquitous distribution in the environment and the potential hazards they pose to wildlife and human health. Although an increasing number of effective PFAS alternatives are available in the market, these alternatives bring new challenges. This paper comprehensively reviews how PFASs bind to transport proteins (e.g., serum albumin, liver fatty acid transport proteins and organic acid transporters), nuclear receptors (e.g., peroxisome proliferator activated receptors, thyroid hormone receptors and reproductive hormone receptors) and membranes (e.g., cell membrane and mitochondrial membrane). Briefly, the hydrophobic fluorinated carbon chains of PFASs occupy the binding cavities of the target proteins, and the acid groups of PFASs form hydrogen bonds with amino acid residues. Various structural features of PFAS alternatives such as chlorine atom substitution, oxygen atom insertion and a branched structure, introduce variations in their chain length and hydrophobicity, which potentially change the affinity of PFAS alternatives for endogenous proteins. The toxic effects and mechanisms of action of legacy PFASs can be demonstrated and compared with their alternatives using binding models. In future studies, in vitro experiments and in silico quantitative structure-activity relationship modeling should be better integrated to allow more reliable toxicity predictions for both legacy and alternative PFASs.

Parental exposure to propiconazole at environmentally relevant concentrations induces thyroid and metabolism disruption in zebrafish (Danio rerio) offspring: An in vivo, in silico and in vitro study.

Propiconazole is used against fungal growth in agriculture and is released into the environment, but is a potential health threat to aquatic organisms. Propiconazole induces a generational effect on zebrafish, although the toxic mechanisms involved have not been described. The aim of this study was to investigate the potential mechanisms of abnormal offspring development after propiconazole exposure in zebrafish parents. Zebrafish were exposed to propiconazole at environmentally realistic concentrations (0.1, 5, and 250 µg/L) for 100 days and their offspring were grown in control solution for further study. Heart rate, hatching rate, and body length of hatched offspring were reduced. An increase in triiodothyronine (T3) content and the T3/T4 (tetraiodothyronine) ratio was observed, indicating disruption of thyroid hormones. Increased protein level of transthyretin (TTR) in vivo was consistent with the in silico molecular docking results and T4 competitive binding in vitro assay, suggests higher binding affinity between propiconazole and TTR, more than with T4. Increased expression of genes related to the hypothalamus-pituitary-thyroid (HPT) axis and altered metabolite levels may have affected offspring development. These findings emphasizes that propiconazole, even on indirect exposure, represents health and environmental risk that should not be ignored.

Polystyrene Nanoplastics Toxicity to Zebrafish: Dysregulation of the Brain-Intestine-Microbiota Axis.

In animal species, the brain-gut axis is a complex bidirectional network between the gastrointestinal (GI) tract and the central nervous system (CNS) consisting of numerous microbial, immune, neuronal, and hormonal pathways that profoundly impact organism development and health. Although nanoplastics (NPs) have been shown to cause intestinal and neural toxicity in fish, the role of the neurotransmitter and intestinal microbiota interactions in the underlying mechanism of toxicity, particularly at environmentally relevant contaminant concentrations, remains unknown. Here, the effect of 44 nm polystyrene nanoplastics (PS-NPs) on the brain-intestine-microbe axis and embryo-larval development in zebrafish (Danio rerio) was investigated. Exposure to 1, 10, and 100 µg/L PS-NPs for 30 days inhibited growth and adversely affected inflammatory responses and intestinal permeability. Targeted metabolomics analysis revealed an alteration of 42 metabolites involved in neurotransmission. The content of 3,4-dihydroxyphenylacetic acid (DOPAC; dopamine metabolite formed by monoamine oxidase activity) was significantly decreased in a dose-dependent manner after PS-NP exposure. Changes in the 14 metabolites correlated with changes to 3 microbial groups, including Proteobacteria, Firmicutes, and Bacteroidetes, as compared to the control group. A significant relationship between Firmicutes and homovanillic acid (0.466, Pearson correlation coefficient) was evident. Eight altered metabolites (l-glutamine (Gln), 5-hydroxyindoleacetic acid (5-HIAA), serotonin, 5-hydroxytryptophan (5-HTP), l-cysteine (Cys), l-glutamic acid (Glu), norepinephrine (NE), and l-tryptophan (l-Trp)) had a negative relationship with Proteobacteria although histamine (His) and acetylcholine chloride (ACh chloride) levels were positively correlated with Proteobacteria. An Associated Network analysis showed that Firmicutes and Bacteroidetes were highly correlated (0.969). Furthermore, PS-NPs accumulated in the gastrointestinal tract of offspring and impaired development of F1 (2 h post-fertilization) embryos, including reduced spontaneous movements, hatching rate, and length. This demonstration of transgenerational deficits is of particular concern. These findings suggest that PS-NPs cause intestinal inflammation, growth inhibition, and restricted development of zebrafish, which are strongly linked to the disrupted regulation within the brain-intestine-microbiota axis. Our study provides insights into how xenobiotics can disrupt the regulation of brain-intestine-microbiota and suggests that these end points should be taken into account when assessing environmental health risks of PS-NPs to aquatic organisms.

Exposure to difenoconazole induces reproductive toxicity in zebrafish by interfering with gamete maturation and reproductive behavior.

Difenoconazole (DCZ) is a triazole fungicide that negatively affects aquatic organisms and humans. However, data regarding the reproductive toxicity of DCZ are insufficient. In this study, we used zebrafish (from 2 h post-fertilization [hpf] to adulthood) as a model to evaluate whether DCZ at environmentally relevant concentrations (0.1, 1.0, and 10.0 µg/L) induces reproductive toxicity. After exposure to DCZ, egg production and fertilization rates were reduced by 1.0 and 10.0 µg/L. A significant decrease in gamete frequency (late vitellogenic oocytes and spermatozoa) was observed at 10.0 µg/L. The concentrations of 17ß-estradiol (E2), testosterone (T), and vitellogenin (VTG) were disrupted in females and males by 1.0 and 10.0 µg/L. Exposure to 10.0 µg/L DCZ significantly inhibited the contact time between female and male fish, which was mainly achieved by affecting male fish. The transcription of genes involved in the hypothalamus-pituitary-gonad (HPG) axis was significantly changed after treatment with DCZ. Overall, these data show that the endocrine-disrupting effect of DCZ on the zebrafish HPG axis inhibited gamete maturation and disrupted reproductive behavior, reducing fertility.

Charge-specific adverse effects of polystyrene nanoplastics on zebrafish (Danio rerio) development and behavior.

Nanoplastics are being detected with increasing frequency in aquatic environments. Although evidence suggests that nanoplastics can cause overt toxicity to biota across different trophic levels, but there is little understanding of how materials such as differently charged polystyrene nanoplastics (PS-NP) impact fish development and behavior. Following exposure to amino-modified (positive charge) PS-NP, fluorescence accumulation was observed in the zebrafish brain and gastrointestinal tract. Positively charged PS-NP induced stronger developmental toxicity (decreased spontaneous movement, heartbeat, hatching rate, and length) and cell apoptosis in the brain and induced greater neurobehavioral impairment as compared to carboxyl-modified (negative charge) PS-NP. These findings correlated well with fluorescence differences indicating PS-NP presence. Targeted neuro-metabolite analysis by UHPLC-MS/MS reveals that positively charged PS-NP decreased levels of glycine, cysteine, glutathione, and glutamic acid, while the increased levels of spermine, spermidine, and tyramine were induced by negatively charged PS-NP. Positively charged PS-NP interacted with the neurotransmitter receptor N-methyl-D-aspartate receptor 2B (NMDA2B), whereas negatively charged PS-NP impacted the G-protein-coupled receptor 1 (GPR1), each with different binding energies that led to behavioral differences. These findings reveal the charge-specific toxicity of nanoplastics to fish and provide new perspective for understanding PS-NP neurotoxicity that is needed to accurately assess potential environmental and health risks of these emerging contaminants.

Insights into the mechanisms of organic pollutant toxicity to earthworms: Advances and perspectives.

Earthworms play positive ecological roles in soil formation, structure, and fertility, environmental protection, and terrestrial food chains. For this review, we searched the Web of Science database for articles published from 2011 to 2021 using the keywords "toxic" and "earthworm" and retrieved 632 publications. From the perspective of bibliometric analysis, we conducted a co-occurrence network analysis using the keywords "toxic" and "earthworm" to identify the most and least reported topics. "Eisenia fetida," "bioaccumulation," "heavy metals," "oxidative stress," and "pesticides" were the most common terms, and "microbial community," "bacteria," "PFOS," "bioaugmentation," "potentially toxic elements," "celomic fluid," "neurotoxicity," "joint toxicity," "apoptosis," and "nanoparticles" were uncommon terms. Additionally, in this review we highlight the main routes of organic pollutant entry into soil, and discuss the adverse effects on the soil ecosystem. We then systematically review the mechanisms underlying organic pollutant toxicity to earthworms, including oxidative stress, energy and lipid metabolism disturbances, neurological toxicity, intestinal inflammation and injury, gut microbiota dysbiosis, and reproductive toxicity. We conclude by discussing future research perspectives, focusing on environmentally relevant concentrations and conditions, novel data processing approaches, technologies, and detoxification and mitigation methods. This review has implications for soil management in the context of environmental pollution.

Tralopyril affects locomotor activity of zebrafish (Danio rerio) by impairing tail muscle tissue, the nervous system, and energy metabolism.

Tralopyril (TP), an antifouling biocide, is widely used to prevent heavy biofouling, and can have potential risks to aquatic organisms. In this study, the effect of TP on locomotor activity and related mechanisms were evaluated in zebrafish (Danio rerio) larvae. TP significantly reduced locomotor activity after 168 -h exposure. Adverse modifications in tail muscle tissue, the nervous system, and energy metabolism were also observed in larvae. TP caused thinning of the muscle bundle in the tail of larvae. In conjunction with the metabolomics results, changes in dopamine (DA) and acetylcholine (ACh), acetylcholinesterase (AChE) activity, and the expression of genes involved in neurodevelopment, indicate that TP may disrupt the nervous system in zebrafish larvae. The change in metabolites (e.g., glucose 6-phosphate, cis-Aconitic acid, acetoacetyl-CoA, coenzyme-A and 3-Oxohexanoyl-CoA) involved in carbohydrate and lipid metabolism indicates that TP may disrupt energy metabolism. TP exposure may inhibit the locomotor activity of zebrafish larvae by impairing tail muscle tissue, the nervous system, and energy metabolism.

Bioaccumulation, Metabolism and the Toxic Effects of Chlorfenapyr in Zebrafish (Danio rerio).

Chlorfenapyr is widely used as an insecticide/miticide. Tralopyril, the active metabolite of chlorfenapyr, is used as an antifouling biocide in antifouling systems, and negatively affects aquatic environments. However, it is unclear whether tralopyril is a metabolite of chlorfenapyr in aquatic vertebrates, and there is little data on the bioaccumulation and toxicity of chlorfenapyr to aquatic vertebrates. In this study, the bioaccumulation and elimination of chlorfenapyr in zebrafish were assessed, and tralopyril, the active metabolite of chlorfenapyr, was determined. The effects of chronic exposure to chlorfenapyr on zebrafish liver and brain oxidative damage, apoptosis, immune response, and metabolome were investigated. These results showed that chlorfenapyr has a high bioaccumulation in zebrafish, with bioaccumulation factors of 864.6 and 1321.9 after exposure to 1.0 and 10 µg/L chlorfenapyr for 21 days, respectively. Chlorfenapyr at these concentrations also rapidly accumulated in zebrafish, reaching 615.5 and 10336 µg/kg on the second and third days of exposure, respectively. Chlorfenapyr was degraded to tralopyril in zebrafish; therefore, both chlorfenapyr and tralopyril should be considered when evaluating the risk of chlorfenapyr to aquatic organisms. In addition, chronic exposure caused oxidative damage, apoptosis, and immune disorders in zebrafish liver. Chronic exposure also altered the levels of endogenous metabolites in liver and brain. After 9 days of depuration, some indicators of oxidative damage, apoptosis, and immunity returned to normal levels, but the concentration of endogenous metabolites in zebrafish liver was still altered. Overall, these results provide useful information for evaluating the toxicity and environmental fate of chlorfenapyr in aquatic vertebrates.

Toxic effects of broflanilide exposure on development of zebrafish (Danio rerio) embryos and its potential cardiotoxicity mechanism.

Diamide insecticides are a threat to aquatic organisms but the toxicity of broflanilide remains largely undefined. In this study, to clarify the risk of broflanilide to aquatic organisms and explore its possible mechanism, lethal and sub-lethal exposure of zebrafish embryos were performed. The acute toxicity LC50 (50% lethal concentration) (96 h) of broflanilide to zebrafish embryos and larvae were 3.72 mg/L and 1.28 mg/L, respectively. It also caused toxic symptoms including reduced heart rate, pericardial edema, yolk sac edema and shortened larval body length at ≥ 0.2 mg/L. Understanding the cellular and molecular changes underlying developmental toxicity in early stages of zebrafish may be very important to further improvement of this study. Here, we found cell apoptosis in embryonic heart, significant up-regulation in expression of genes associated with apoptosis and increased activity of caspase-9. In particular, we detected the levels of genes and TBX5 (T-box protein 5) related to cardiac development, which were significantly increased in this study and may be contribution to the cardiotoxicity of embryos. In general, our results identified the aquatic toxicity of broflanilide to the early stage of zebrafish and provide insights into the underlying mechanism in developmental toxicity especially cardiotoxicity of embryos.

Immobilization properties and adsorption mechanism of nickel(II) in soil by biochar combined with humic acid-wood vinegar.

Biochar (BC) combined with humic acid (HA) and wood vinegar (WV) was designed and prepared as an inexpensive, effective, and environmentally friendly immobilization material (BHW) for metal-polluted soil. The influences of the wood vinegar and humic acid on the immobilization properties and adsorption mechanism of this new material were also investigated. The remediation performance was evaluated using a laboratory-made, nickel-contaminated soil with a Ni2+ concentration of 200 mg per kg surface soil (top 20 cm from agricultural land). The results indicated that the immobilization ratio sequence of nickel (II) in the soil was BC< BH< BHW. The maximum adsorption capacity increased in the same order: BC< BH< BHW. All three adsorption isotherms were better fitted by the Freundlich model, which were consistent with the surface heterogeneity of the remediation materials. The cause of this surface heterogeneous migration may be due to the increase in oxygen-containing groups in the BC introduced by the HA and WV. The WV can increase the number of the oxygen-containing groups in the BC combined with HA, which enhanced the adsorption and immobilization of Ni2+ ions. The results suggested that BHW is recommended for the remediation of metal-contaminated soils, because of its high efficacy, economic feasibility, environmental and food safety.

Recent advances in the development of nanomedicines for the treatment of ischemic stroke.

Ischemic stroke is still a serious threat to human life and health, but there are few therapeutic options available to treat stroke because of limited blood-brain penetration. The development of nanotechnology may overcome some of the problems related to traditional drug development. In this review, we focus on the potential applications of nanotechnology in stroke. First, we will discuss the main molecular pathological mechanisms of ischemic stroke to develop a targeted strategy. Second, considering the important role of the blood-brain barrier in stroke treatment, we also delve mechanisms by which the blood-brain barrier protects the brain, and the reasons why the therapeutics must pass through the blood-brain barrier to achieve efficacy. Lastly, we provide a comprehensive review related to the application of nanomaterials to treat stroke, including liposomes, polymers, metal nanoparticles, carbon nanotubes, graphene, black phosphorus, hydrogels and dendrimers. To conclude, we will summarize the challenges and future prospects of nanomedicine-based stroke treatments.

Cross-Domain Image Captioning via Cross-Modal Retrieval and Model Adaptation.

In recent years, large scale datasets of paired images and sentences have enabled the remarkable success in automatically generating descriptions for images, namely image captioning. However, it is labour-intensive and time-consuming to collect a sufficient number of paired images and sentences in each domain. It may be beneficial to transfer the image captioning model trained in an existing domain with pairs of images and sentences (i.e., source domain) to a new domain with only unpaired data (i.e., target domain). In this paper, we propose a cross-modal retrieval aided approach to cross-domain image captioning that leverages a cross-modal retrieval model to generate pseudo pairs of images and sentences in the target domain to facilitate the adaptation of the captioning model. To learn the correlation between images and sentences in the target domain, we propose an iterative cross-modal retrieval process where a cross-modal retrieval model is first pre-trained using the source domain data and then applied to the target domain data to acquire an initial set of pseudo image-sentence pairs. The pseudo image-sentence pairs are further refined by iteratively fine-tuning the retrieval model with the pseudo image-sentence pairs and updating the pseudo image-sentence pairs using the retrieval model. To make the linguistic patterns of the sentences learned in the source domain adapt well to the target domain, we propose an adaptive image captioning model with a self-attention mechanism fine-tuned using the refined pseudo image-sentence pairs. Experimental results on several settings where MSCOCO is used as the source domain and five different datasets (Flickr30k, TGIF, CUB-200, Oxford-102 and Conceptual) are used as the target domains demonstrate that our method achieves mostly better or comparable performance against the state-of-the-art methods. We also extend our method to cross-domain video captioning where MSR-VTT is used as the source domain and two other datasets (MSVD and Charades Captions) are used as the target domains to further demonstrate the effectiveness of our method.

Wood vinegar enhances humic acid-based remediation material to solidify Pb(II) for metal-contaminated soil.

Heavy metal lead is a typical widespread potentially toxic element (PET) contamination due to their extensive and wide applications in industrial processes. The development of cost-effective methods for preventing potentially toxic element lead residues from soil into food is thus highly desirable. A new type of humic acid-based remediation material (HA/WV) incorporating humic acid salt (HA), biochar powder (BC), and wood vinegar (WV), which is a cheap and environmentally friendly industrial by-product from charcoal processing, was prepared and evaluated. The results showed that 0.10 g remediation material HA/WV with a mass ratio of 1:1 was added to 1 kg surface soil of 0-20 cm from agricultural land contaminated by 300 mg Pb2+, the reduction ratio of available Pb in soil can reach 61.4%. Especially, wood vinegar can enhance the reduction ratio of available Pb by at least 14.7% over without wood vinegar. Furthermore, according to the analysis of adsorption interaction and the electrostatic attraction between Pb(II) and oxygen-containing functional groups on HA/WV are the dominant mechanisms responsible for Pb(II) sorption. The wood vinegar liquid can improve the oxygen-containing group in HA/WV, which can enhance the complexation of remediation materials and Pb(II) ion.

Bandwidth Cost Minimization via User Association for Enterprise WLANs.

Enterprise Wireless LANs (E-WLANs) such as airport WiFi, have become a convenient way for Internet access for mobile users. In an E-WLAN, access points (APs) are usually deployed with high-density around the infrastructure to provide sufficient coverage and for a better service, where a mobile user chooses one AP to associate with among multiple available APs in the vicinity. Many studies have been done on developing user association techniques to increase system performance, with various objectives including network throughput maximization, load balancing etc. Our work is unique in that we focused on bandwidth cost minimization via user association from the perspective of the E-WLAN operators. Specifically, by considering the bandwidth demands from mobile users, we modeled the joint user association and cost minimization problem in the heterogeneous E-WLAN with additional constraints from individual bandwidth demands as an optimization problem. To solve the optimization problem efficiently, we propose an approximation algorithm using relaxation and rounding techniques. We prove that the proposed algorithm has performance bound with a constant ratio to the optimization problem. Furthermore, our simulation results exhibit the superiority of our proposed algorithm over prior schemes.