In-situ activation of biomimetic single-site bioorthogonal nanozyme for tumor-specific combination therapy.

Copper-catalyzed click chemistry offers creative strategies for activation of therapeutics without disrupting biological processes. Despite tremendous efforts, current copper catalysts face fundamental challenges in achieving high efficiency, atom economy, and tissue-specific selectivity. Herein, we develop a facile "mix-and-match synthetic strategy" to fabricate a biomimetic single-site copper-bipyridine-based cerium metal-organic framework (Cu/Ce-MOF@M) for efficient and tumor cell-specific bioorthogonal catalysis. This elegant methodology achieves isolated single-Cu-site within the MOF architecture, resulting in exceptionally high catalytic performance. Cu/Ce-MOF@M favors a 32.1-fold higher catalytic activity than the widely used MOF-supported copper nanoparticles at single-particle level, as first evidenced by single-molecule fluorescence microscopy. Furthermore, with cancer cell-membrane camouflage, Cu/Ce-MOF@M demonstrates preferential tropism for its parent cells. Simultaneously, the single-site CuII species within Cu/Ce-MOF@M are reduced by upregulated glutathione in cancerous cells to CuI for catalyzing the click reaction, enabling homotypic cancer cell-activated in situ drug synthesis. Additionally, Cu/Ce-MOF@M exhibits oxidase and peroxidase mimicking activities, further enhancing catalytic cancer therapy. This study guides the reasonable design of highly active heterogeneous transition-metal catalysts for targeted bioorthogonal reactions.

Hierarchical core-shelled CoMo layered double hydroxide@CuCo2S4 nanowire arrays/nickel foam for advanced hybrid supercapacitors.

The development of core-shelled heterostructures with the unique morphology can improve the electrochemical properties of hybrid supercapacitors (HSC). Here, CuCo2S4 nanowire arrays (NWAs) are vertically grown on nickel foam (NF) utilizing hydrothermal synthesis. Then, CoMo-LDH nanosheets are uniformly deposited on the CuCo2S4 NWAs by electrodeposition to obtain the CoMo-LDH@CuCo2S4 NWAs/NF electrode. Due to the superior conductivity of CuCo2S4 (core) and good redox activity of CoMo-LDH (shell), the electrode shows excellent electrochemical properties. The electrode's specific capacity is 1271.4 C g-1 at 1 A g-1, and after 10, 000 cycles, its capacity retention ratio is 92.2 % at 10 A g-1. At a power density of 983.9 W kg-1, the CoMo-LDH@CuCo2S4 NWAs/NF//AC/NF device has an energy density of 52.2 Wh kg-1. This indicates that CoMo-LDH@CuCo2S4/NF has a great potential for supercapacitors.

Preparation of cathode catalysts for efficient direct lignin fuel cells by nitrogen doping reduction of oxidized graphene with phthalocyanine iron and Kraft lignin.

Direct lignin fuel cells (DLFC) are one of the important forms of high value-added utilization of lignin. In this study, lignin was studied not only as a fuel but also as a catalyst. Specifically, Kraft lignin was modified with ZnCl2, KOH and THF (Tetrahydrofuran) respectively, and added to the catalyst after activation. The results of scanning electron microscope (SEM), transmission electron microscope (TEM), energy dispersive spectrometer (EDS), Brunauer - Emmett - Teller (BET), X-ray photoelectron spectroscopy (XPS), X-ray diffractometer (XRD), Fourier transform infrared spectroscopy (FT-IR) and Raman spectra shown that AL/FePc-NrGO (activated lignin/iron phthalocyanine/nitrogen-doped reduction of graphene oxide) three-dimensional composite catalyst has been synthesized. The results showed that KOH-activated Kraft lignin had the best performance as an oxygen reduction reaction (ORR) catalyst, with a half-wave potential (E1/2) of 0.73 V and a limiting diffusion current density of 4.3 mA cm-1. The THF-modified catalyst showed similar stability and methanol resistance to 20 % Pt/C at ORR. The ORR catalyst applied to the DLFC has the best electrical performance with an open circuit voltage (OCV) was 0.53 V and the maximum power density it could reach 95.29 mW m-2 when the catalyst was modified with THF. It is encouraging that the AL/FePc-NrGO catalyst has better-generated electricity performance than 20 % Pt/C. This work has provided a new idea for developing non-noble metal catalysts and studying direct biomass liquid fuel cells.

Surface engineering of metal-organic framework nanoparticles-based miRNA carrier: Boosting RNA stability, intracellular delivery and synergistic therapy.

MicroRNAs (miRNAs) are small noncoding RNAs that are critical for the regulation of multiple physiological and pathological processes, thus holding great clinical potential. However, the therapeutic applications of miRNAs are severely limited by their biological instability and poor intracellular delivery. Herein, we describe a dual-layers surface engineering strategy to design an efficient miRNA delivery nanosystem based on metal-organic frameworks (MOFs) incorporating lipid coating. The resulting nanoparticle system was demonstrated to protect miRNA from ribonuclease degradation, enhance cellular uptake and facilitate lysosomal escape. These ensured effective miRNA mediated gene therapy, which synergized with MOF-specific photodynamic therapy and pre-encapsulated doxorubicin (Dox) chemotherapy to provide a multifunctional with therapeutic effectiveness against cencer cells The mechanisms of miRNA binding and Dox loading were revealed, demonstrating the potential of the present MOFs surface-engineered strategy to overcome their inherent pore-size restriction for macromolecular miRNA carrying, enableefficient co-delivery. In vitro studies revealed the potential of our multifunctional system for miRNA delivery and the demonstrated the therapeutic effectiveness against cancer cells, thereby providing a versatile all-in-one MOFs strategy for delivery of nucleic acids and diverse therapeutic molecules in synergistic therapy.

Iron-copper bimetallic photo-Fenton system promoted photothermal-hydrogen peroxide production for efficient low-temperature wastewater treatment.

Enhancing the velocity of the oxidation-reduction cycle is crucial for improving the catalytic efficiency of Fenton processes. Therefore, the development of an effective strategy for wastewater degradation at low temperatures is essential. In this context, we present the preparation of an NH2-MIL-88B (Fe)/CuInS2 S-scheme heterojunction. Specifically, CuInS2 nanoparticles are introduced onto the Ferro-organic skeleton, resulting in the exposure of a significant number of active surface sites. Furthermore, NH2-MIL-88B (Fe)/CuInS2 demonstrates an extended photoresponse into the long-wavelength region, which contributes to its excellent photothermal properties. Notably, the degradation rate of tetracycline in low-temperature aqueous environments reaches as high as 99.7 %, several times higher than that of the original sample. Additionally, the hydrogen production of NH2-MIL-88B (Fe)/CuInS2 is 2.23 times that of single NH2-MIL-88B (Fe) and 3.46 times that of single CuInS2. Moreover, the system exhibits good H2O2 evolution performance, forming an efficient photo-Fenton system. The charge transfer process in S-scheme heterojunction is confirmed using in-situ X-ray photoelectron spectroscopy and electron paramagnetic resonance. Both transient photoluminescence and photo electrochemical tests further validate the enhanced photoelectrochemical properties of the NH2-MIL-88B (Fe)/CuInS2 S-scheme heterojunction. The exceptional performance of this system can be attributed to the synergistic effects of the S-scheme heterojunction and the bimetallic codoped photo-Fenton system. This research presents a novel approach for the breakdown of low-temperature wastewater using an improved photocatalytic Fenton system.

Ultrasmall iridium-encapsulated porphyrin metal-organic frameworks for enhanced photodynamic/catalytic therapy by producing reactive oxygen species storm.

Transition metal-coordinated porphyrin metal-organic frameworks (MOFs) were perspective in photodynamic therapy (PDT) and catalytic therapy. However, the tumor hypoxia and the insufficient endogenous hydrogen peroxide (H2O2) seriously limited their efficacies. Herein, by encapsulating ultrasmall iridium (Ir) and modifying glucose oxidase (GOx), an iron-coordinated porphyrin MOF (Fe-MOF) nanoplatform (Fe-MOF@Ir/GOx) was designed to strengthen PDT/catalytic therapy by producing reactive oxygen species (ROS) storm. In this nanoplatform, Fe-MOF showed glutathione (GSH)-responsive degradation, by which porphyrin, GOx and ultrasmall Ir were released. Moreover, ultrasmall Ir possessed dual-activities of catalase (CAT)-like and peroxidase (POD)-like, which provided sufficient oxygen (O2) to enhance PDT efficacy, and hydroxyl radical (·OH) production was also improved by combining Fenton reaction of Fe2+. Further, GOx catalyzed endogenous glucose produced H2O2, also reduced pH value, which accelerated Fenton reaction and resulted in generation of ROS storm. Therefore, the developed Fe-MOF@Ir/GOx nanoplatform demonstrated enhanced PDT/catalytic therapy by producing ROS storm, and also provided a promising strategy to promote degradation/metabolism of inorganic nanoplatforms.

Outcomes of multi-hole self-expandable metal stents versus fully covered self-expandable metal stents for malignant distal biliary obstruction in unresectable pancreatic cancer.

Objectives: The multi-hole self-expandable metal stent (MHSEMS) is a novel SEMS with multiple small side holes on the covering membrane to prevent stent migration while minimizing tumor ingrowth. This study aimed to evaluate the clinical outcomes of MHSEMS in comparison with conventional covered SEMS (c-CMS). Methods: Consecutive patients with unresectable pancreatic cancer who underwent initial SEMS placement (MHSEMS or c-CMS) for malignant distal biliary obstruction were analyzed. Technical success, clinical success, causes of recurrent biliary obstruction (RBO), non-RBO adverse events, time to RBO (TRBO), and endoscopic reintervention were compared between groups. Results: A total of 65 patients were included (MHSEMS: 27, c-CMS: 38). The technical success, clinical success, and non-RBO adverse event rates were similar between groups. Although stent migration was less frequently observed in the MHSEMS group (0% vs. 17.6%, p = 0.032), overall RBO rates were similar between groups (53.8% vs. 55.9%, p > 0.99). The most common cause of RBO within 14 days in the MHSEMS group was non-occlusion cholangitis. Median TRBO was significantly shorter in the MHSEMS group (101 vs. 227 days, p = 0.030) and MHSEMS was an independent predictor for shorter TRBO in multivariate analysis (hazard ratio, 2.27; 95% confidence interval, 1.06-4.86; p = 0.034). Outcomes after endoscopic interventio were not significantly different between groups. Stent removal was successful in all attempted cases in both groups. Conclusions: MHSEMS was associated with a significantly shorter TRBO compared to c-CMS. Further modifications of the present MHSEMS may be needed.

Efficacy and safety of a novel polytetrafluoroethylene-coated self-expandable metal stent for distal malignant biliary obstruction.

Background: Stent migration and sludge formation remain significant problems associated with covered self-expandable metal stents (CSEMSs). The EGIS biliary stent fully covered flare type (EGIS biliary stent), a new type of polytetrafluoroethylene-coated self-expandable metal stent with low axial force and an anti-migration system, was developed to overcome these disadvantages. We conducted this study to evaluate the efficacy and safety of this stent in comparison with conventional CSEMS (c-CSEMS). Methods: We retrospectively analyzed consecutive patients with unresectable pancreatic cancer who received initial CSEMS for distal malignant biliary obstruction. The primary outcome was time to recurrent biliary obstruction (RBO). Secondary outcomes included technical success rate, functional success rate, stent-related adverse events, causes of RBO, and re-intervention. Results: A total of 40 patients were included (EGIS group: 20; c-CSEMS group: 20). The technical and functional success rates were similar between the two groups. Stent-related adverse event rates (20% vs. 15%, p > 0.99) and overall RBO rates (56% vs. 50%, p > 0.99) were not significantly different between the two groups. Stent migration was the most common cause of RBO in the EGIS group, while stent occlusion was in the c-CSEMS group. The median time to RBO (102 vs. 434 days, p = 0.10) was not significantly different between the two groups. Endoscopic transpapillary re-intervention was successful in most patients in both groups. Conclusions: The EGIS biliary stent was not associated with a longer time to RBO compared to c-CSEMS. Further improvements, especially against stent migration, are needed to improve its efficacy.

An effective procedure used metal-organic framework for determination of cadmium ions in real tap water and human blood plasma samples.

A newly developed 2H5MA-MOF sensor by covalently linking NH2-MIL-53(Al) with 2'-Hydroxy-5'-methylacetophenon, designed for highly sensitive and selective detection of Cd2+ ions using fluorometric methods. Detailed structural and morphological analyses confirmed the sensor's unique properties. It demonstrated an impressive linear detection range from 0 to 2 ppm, with an exceptionally low detection limit of 5.77 × 10-2 ppm and a quantification limit of 1.75 × 10-1 ppm, indicating its high sensitivity (R2 = 0.9996). The sensor also responded quickly, detecting Cd2+ within just 30 s at pH 4. We successfully tested it on real samples of tap water and human blood plasma, achieving recovery rates between 96 % and 104 %. The accuracy of these findings was further validated by comparison with ICP-OES. Overall, the 2H5MA-MOF sensor shows great potential for fast, ultra-sensitive, and reliable detection of Cd2+ ions, making it a promising tool for environmental and biomedical applications.

Assessment of internal exposure risk from metals pollution of occupational and non-occupational populations around a non-ferrous metal smelting plant.

Non-ferrous metal smelting poses significant risks to public health. Specifically, the copper smelting process releases arsenic, a semi-volatile metalloid, which poses an emerging exposure risk to both workers and nearby residents. To comprehensively understand the internal exposure risks of metal(loid)s from copper smelting, we explored eighteen metal(loid)s and arsenic metabolites in the urine of both occupational and non-occupational populations using inductively coupled plasma mass spectrometry with high-performance liquid chromatography and compared their health risks. Results showed that zinc and copper (485.38 and 14.00 µg/L), and arsenic, lead, cadmium, vanadium, tin and antimony (46.80, 6.82, 2.17, 0.40, 0.44 and 0.23 µg/L, respectively) in workers (n=179) were significantly higher compared to controls (n=168), while Zinc, tin and antimony (412.10, 0.51 and 0.15 µg/L, respectively) of residents were significantly higher than controls. Additionally, workers had a higher monomethyl arsenic percentage (MMA%), showing lower arsenic methylation capacity. Source appointment analysis identified arsenic, lead, cadmium, antimony, tin and thallium as co-exposure metal(loid)s from copper smelting, positively relating to the age of workers. The hazard index (HI) of workers exceeded 1.0, while residents and control were approximately at 1.0. Besides, all three populations had accumulated cancer risks exceeding 1.0 × 10-4, and arsenite (AsIII) was the main contributor to the variation of workers and residents. Furthermore, residents living closer to the smelting plant had higher health risks. This study reveals arsenic exposure metabolites and multiple metals as emerging contaminants for copper smelting exposure populations, providing valuable insights for pollution control in non-ferrous metal smelting.

Adsorption removal of mercury from flue gas by metal selenide: A review.

Mercury (Hg) pollution has been a global concern in recent decades, posing a significant threat to entire ecosystems and human health due to its cumulative toxicity, persistence, and transport in the atmosphere. The intense interaction between mercury and selenium has opened up a new field for studying mercury removal from industrial flue gas pollutants. Besides the advantages of good Hg° capture performance and low secondary pollution of the mineral selenium compounds, the most noteworthy is the relatively low regeneration temperature, allowing adsorbent regeneration with low energy consumption, thus reducing the utilization cost and enabling recovery of mercury resources. This paper reviews the recent progress of mineral selenium compounds in flue gas mercury removal, introduces in detail the different types of mineral selenium compounds studied in the field of mercury removal, reviews the adsorption performance of various mineral selenium compounds adsorbents on mercury and the influence of flue gas components, such as reaction temperature, air velocity, and other factors, and summarizes the adsorption mechanism of different fugitive forms of selenium species. Based on the current research progress, future studies should focus on the economic performance and the performance of different carriers and sizes of adsorbents for the removal of Hg0 and the correlation between the gas-particle flow characteristics and gas phase mass transfer with the performance of Hg0 removal in practical industrial applications. In addition, it remains a challenge to distinguish the oxidation and adsorption of Hg0 quantitatively.

2D copper-iron bimetallic metal-organic frameworks for reduction of nitrate with boosted efficiency and ammonia selectivity.

Electrocatalytic reduction of nitrate to ammonia has been considered a promising and sustainable pathway for pollutant treatment and ammonia has significant potential as a clean energy. Therefore, the method has received much attention. In this work, Cu/Fe 2D bimetallic metal-organic frameworks were synthesized by a facile method applied as cathode materials without high-temperature carbonization. Bimetallic centers (Cu, Fe) with enhanced intrinsic activity demonstrated higher removal efficiency. Meanwhile, the 2D nanosheet reduced the mass transfer barrier between the catalyst and nitrate and increased the reaction kinetics. Therefore, the catalysts with a 2D structure showed much better removal efficiency than other structures (3D MOFs and Bulk MOFs). Under optimal conditions, Cu/Fe-2D MOF exhibited high nitrate removal efficiency (87.8%) and ammonium selectivity (89.3%) simultaneously. The ammonium yielded up to significantly 907.2 µg/(hr·mgcat) (7793.8 µg/(hr·mgmetal)) with Faradaic efficiency of 62.8% at an initial 100 mg N/L. The catalyst was proved to have good stability and was recycled 15 times with excellent effect. DFT simulations confirm the reduced Gibbs free energy of Cu/Fe-2D MOF. This study demonstrates the promising application of Cu/Fe-2D MOF in nitrate reduction to ammonia and provides new insights for the design of efficient electrode materials.

Impact of coking plant to heavy metal characteristics in groundwater of surrounding areas: Spatial distribution, source apportionment and risk assessments.

Coking industry is a potential source of heavy metals (HMs) pollution. However, its impacts to the groundwater of surrounding residential areas have not been well understood. This study investigated the pollution characteristics and health risks of HMs in groundwater nearby a typical coking plant. Nine HMs including Fe, Zn, Mo, As, Cu, Ni, Cr, Pb and Cd were analyzed. The average concentration of total HMs was higher in the nearby area (244.27 µg/L) than that of remote area away the coking plant (89.15 µg/L). The spatial distribution of pollution indices including heavy metal pollution index (HPI), Nemerow index (NI) and contamination degree (CD), all demonstrated higher values at the nearby residential areas, suggesting coking activity could significantly impact the HMs distribution characteristics. Four sources of HMs were identified by Positive Matrix Factorization (PMF) model, which indicated coal washing and coking emission were the dominant sources, accounted for 40.4%, and 31.0%, respectively. Oral ingestion was found to be the dominant exposure pathway with higher exposure dose to children than adults. Hazard quotient (HQ) values were below 1.0, suggesting negligible non-carcinogenic health risks, while potential carcinogenic risks were from Pb and Ni with cancer risk (CR) values > 10-6. Monte Carlo simulation matched well with the calculated results with HMs concentrations to be the most sensitive parameters. This study provides insights into understanding how the industrial coking activities can impact the HMs pollution characteristics in groundwater, thus facilitating the implement of HMs regulation in coking industries.

Occupational respiratory disease in Eastern Slovakia between 1990-2021: a shift from agriculture to industrial manufacturing.

OBJECTIVES: Occupational allergic respiratory diseases frequently occur in individuals working in the agricultural and food production sectors, textile manufacturing, and industries involving exposure to isocyanates. The study aimed to describe trends surrounding the prevalence of occupational asthma (OA), occupational rhinitis (OR), and occupational hypersensitivity pneumonitis (OHP) in Eastern Slovakia between 1990-2021. METHODS: All cases of OA, OR, and OHP registered in a database at the Louis Pasteur University Hospital in Kosice, Slovakia, between 1990 and 2021, were divided into categories based on economic sector (agricultural, food production sectors, textile manufacturing, healthcare, industrial manufacturing, and tertiary sector) and causal agent. Changes in disease prevalence, causal agents, and economic sector association over time were analysed. RESULTS: There were 287 occupational respiratory cases (179 OA, 65 OR, and 43 OHP cases). The annual prevalence of OA declined significantly over the study period (p < 0.05). Overall, there was a significant decrease in cases from the agricultural (p < 0.001) and an increase in the industrial manufacturing (p < 0.01). The number of cases due to farming agents fell markedly over the study period, while metalworking fluids (MWFs) were found to be the most common causes of allergic respiratory diseases since 2018. CONCLUSIONS: This study found a decrease in the number of OA cases, as well as changes in economic sectors and causal agents associated with OA and OHP, specifically, in the agricultural sector, with MWFs from the industrial manufacturing sector now being the most common aetiological agent.

Detection and Prediction of Toxic Aluminum Concentrations in High-Priority Salmon Rivers in Nova Scotia.

Elevated concentrations of toxic cationic aluminum (Ali) are symptomatic of terrestrial and freshwater acidification and are particularly toxic to salmonid fish species such as Atlantic salmon (Salmo salar). Speciated metal samples are rarely included in standard water monitoring protocols, and therefore the processes affecting Ali dynamics in freshwater remain poorly understood. Previous analysis of Ali concentrations in Nova Scotia (Canada) rivers found that the majority of study rivers had concentrations exceeding the threshold for aquatic health, but a wide-scale survey of Ali in Nova Scotia has not taken place since 2006 (Dennis, I. F., & Clair, T. A., 2012, Canadian Journal of Fisheries and Aquatic Sciences, 69(7), 1174-1183). The observed levels of dissolved aluminum in Atlantic salmon (Salmo salar) rivers of Atlantic Canada have potential serious and harmful effects for aquatic populations. We present the findings of the first large-scale assessment of the Ali status of Nova Scotia rivers in 17 years; we measured Ali concentrations and other water chemistry parameters at 150 sites throughout the Southern Uplands region of Nova Scotia from 2015 to 2022. We found that Ali concentrations exceeded toxic thresholds at least once during the study period at 80% of the study sites and that Ali concentrations increased during the study period at all four large-sample study sites. Modeling of relationships between Ali concentrations and other water chemistry parameters showed that the most important predictors of Ali are concentrations of the dissolved fractions of Al, iron, titanium, and calcium, as well as dissolved organic carbon and fluoride. We developed a fully Bayesian linear mixed model to predict Ali concentrations from a test data set within 15 µg/L. This model may be a valuable tool to predict Ali concentrations in rivers and to prioritize areas where Ali should be monitored. Environ Toxicol Chem 2024;00:1-12. © 2024 The Author(s). Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Three-dimensional gas-foamed scaffolds decorated with metal phenolic networks for cartilage regeneration.

Inflammation is a major impediment to the healing of cartilage injuries, yet bioactive scaffolds suitable for cartilage repair in inflammatory environments are extremely rare. Herein, we utilized electrospinning to fabricate a two-dimensional nanofiber scaffold (2DS), which was then subjected to gas foaming to obtain a three-dimensional scaffold (3DS). 3DS was modified with metal phenolic networks (MPNs) composed of epigallocatechin gallate (EGCG) and strontium ions (Sr2+) to afford a MPNs-modified 3D scaffold (3DS-E). Gas-foamed scaffold exhibited multilayered structure conducive to cellular infiltration and proliferation. Compared to other groups, 3DS-E better preserved chondrocytes under interleukin (IL)-1ß induced inflammatory environment, showing less apoptosis of chondrocytes and higher expression of cartilage matrix. Additionally, 3DS-E facilitated the regeneration of more mature cartilage in vivo, reduced cell apoptosis, and decreased the expression of pro-inflammatory cytokines. Taken together, 3DS-E may offer an ideal candidate for cartilage regeneration.

Endoscopic ultrasound-guided biliary drainage after failed endoscopic retrograde cholangiopancreatography: The road is open for almighty biliopancreatic endoscopists!

Commentary on the article written and published by Peng et al, investigating the role of endoscopic ultrasound (EUS)-guided biliary drainage for palliation of malignant biliary obstruction after failed endoscopic retrograde cholangiopancreatography (ERCP). For 40 years endoscopic biliary drainage was synonymous with ERCP, and EUS was used mainly for diagnostic purposes. The advent of therapeutic EUS has revolutionized the field, especially with the development of a novel device such as electrocautery-enhanced lumen-apposing metal stents. Complete biliopancreatic endoscopists with both skills in ERCP and in interventional EUS, would be ideally suited to ensure patients the best drainage technique according to each individual situation.

Bioaccumulation, organotropism and fate of cadmium in Gammarus fossarum exposed through dietary pathway.

Despite a good knowledge of cadmium accumulation in Gammarus fossarum, studies to date have focused on Cd accumulated via the dissolved pathway, leaving aside the trophic pathway. The aim of this study was to assess cadmium organotropism and bioaccumulation processes following a trophic exposure of the species Gammarus fossarum. Adult male gammarids were fed with 109Cd contaminated alder leaves discs for 6 days and then with clean alder leaves for 12 days. During both phases, some gammarids were collected and dissected, and intestines, hepatopancreas, cephalons, gills and remaining tissues were separated to measure their Cd concentrations. Their relative proportions of Cd and their respective BMFs were estimated. The ingestion rate (IR) measured during the exposure phase was divided by 3 between days 2 and 6, indicating that gammarids reduced their feeding activity and therefore the exposure pressure. A multi-compartments TK model was developed, and an iterative inference process was run to select the most parsimonious model that best fits all organ datasets simultaneously. The results showed that: i) intestine and hepatopancreas bioconcentrate Cd the most; ii) no cadmium was quantified in gills, meaning that they do not appear to play a role in Cd storage or elimination with a trophic exposure; iii) Cd elimination occurs only through the intestine; and iv) the general pattern of Cd fate in gammarids, obtained here after dietary highlights once again the importance of the intestine and hepatopancreas, as for the dissolved pathway.

A(CoFe)(S2)2/CoFe heterostructure constructed in S, N co-doped carbon nanotubes as an efficient oxygen electrocatalyst for zinc-air battery.

Transition metal alloys can exhibit synergistic intermetallic effects to obtain high activities for oxygen reduction/evolution reactions (ORR/OER). However, due to the insufficient stability of active sites in alkaline electrolytes, conventional alloy catalysts still do not meet practical needs. Herein, by using polypyrrole tubes and cobalt-iron (CoFe) Prussian blue analogs as precursors, CoFe sulfides is in-situ formed on CoFe alloys to construct (CoFe)(S2)2/CoFe heterostructure in sulfur (S) and nitrogen (N) co-doped carbon nanotubes (CoFe@NCNTs-nS) via a low-temperature sulfidation strategy. The as-marked CoFe@NCNTs-12.5S exhibits a comparable ORR activity (half-wave potential of 0.901 V) to Pt/C (0.903 V) and a superior OER activity (overpotential of 272 mV at 10 mA cm-2) to RuO2 (299 mV). CoFe@NCNTs-12.5S also exhibits ultralow charge transfer resistances (ORR-6.36 Ω and OER-0.21 Ω) and an excellent potential difference of 0.617 V. The sulfidation-induced (CoFe)(S2)2/CoFe heterojunctions can accelerate interfacial charge transfer process. Tubular structure not only disperses the (CoFe)(S2)2/CoFe heterostructure, but also reduces the corrosion of active-sites to enhance catalysis stability. Zinc-air battery with CoFe@NCNTs-12.5S achieves a high specific capacity (718.1 mAh g-1), maintaining a voltage gap of 0.957 V after 400 h. This work reveals the potential of interface engineering for boosting ORR/OER activities of alloys via in-situ heterogenization.

Investigating the relationship of co-exposure to multiple metals with chronic kidney disease: An integrated perspective from epidemiology and adverse outcome pathways.

Systematic studies on the associations between co-exposure to multiple metals and chronic kidney disease (CKD), as well as the underlying mechanisms, remain insufficient. This study aimed to provide a comprehensive perspective on the risk of CKD induced by multiple metal co-exposures through the integration of occupational epidemiology and adverse outcome pathway (AOP). The study participants included 401 male mine workers whose blood metal, ß2-microglobulin (ß2-MG), and cystatin C (Cys-C) levels were measured. Generalized linear models (GLMs), quantile g-computation models (qgcomp), least absolute shrinkage and selection operator (LASSO), and bayesian kernel machine regression (BKMR) were utilized to identify critical nephrotoxic metals. The mean concentrations of lead, cadmium, mercury, arsenic, and manganese were 191.93, 3.92, 4.66, 3.11, 11.35, and 16.33 µg/L, respectively. GLM, LASSO, qgcomp, and BKMR models consistently identified lead, cadmium, mercury, and arsenic as the primary contributors to kidney toxicity. Based on our epidemiological analysis, we used a computational toxicology method to construct a chemical-genetic-phenotype-disease network (CGPDN) from the Comparative Toxicogenomics Database (CTD), DisGeNET, and GeneCard databases, and further linked key events (KEs) related to kidney toxicity from the AOP-Wiki and PubMed databases. Finally, an AOP framework of multiple metals was constructed by integrating the common molecular initiating events (reactive oxygen species) and KEs (MAPK signaling pathway, oxidative stress, mitochondrial dysfunction, DNA damage, inflammation, hypertension, cell death, and kidney toxicity). This is the first AOP network to elucidate the internal association between multiple metal co-exposures and CKD, providing a crucial basis for the risk assessment of multiple metal co-exposures.