Regulation of electron density redistribution for efficient alkaline hydrogen evolution reaction and overall water splitting.

The rational design of morphology and heterogeneous interfaces for non-precious metal electrocatalysts is crucial in electrochemical water decomposition. In this paper, a bifunctional electrocatalyst (Ni/NiFe LDH), which coupling nickel with nickel-iron layer double hydroxide (NiFe LDH), is synthesized on carbon cloth. At current density of 10 mA cm-2, the Ni/NiFe LDH exhibits a low hydrogen evolution reaction (HER) overpotential of only 36 mV due to the accelerated electrolyte penetration, which is caused by superhydrophilic interface. Moreover, an alkaline electrolyzer is formed and provide a current density of 10 mA cm-2 with a voltage of only 1.49 V. It is confirmed by the density functional theory (DFT) that electron from the Ni layer is transferred to NiFe LDH layer, redistributing the local electron density around the heterogeneous phase interface. Thus, the Gibbs free energy for hydrogen adsorption is optimized. This work provides a promising strategy for the rational regulation of electrons at heterogeneous interfaces and the synthesis of flexible electrocatalysts.

Cell type-dependent response to benzo(a)pyrene exposure of human placental cell lines under normoxic, hypoxic, and pro-inflammatory conditions.

Benzo(a)pyrene (BaP) can be detected in the human placenta. However, little is known about the effects of BaP exposure on different placental cells under various conditions. In this study, we aimed to investigate the effects of BaP on mitochondrial function, pyrin domain-containing protein 3 (NLRP3) inflammasome, and apoptosis in three human trophoblast cell lines under normoxia, hypoxia, and inflammatory conditions. JEG-3, BeWo, and HTR-8/SVneo cell lines were exposed to BaP under normoxia, hypoxia, or inflammatory conditions for 24 h. After treatment, we evaluated cell viability, apoptosis, aryl hydrocarbon receptor (AhR) protein and cytochrome P450 (CYP) gene expression, mitochondrial function, including mitochondrial DNA copy number (mtDNAcn), mitochondrial membrane potential (ΔΨm), intracellular adenosine triphosphate (iATP), and extracellular ATP (eATP), nitric oxide (NO), NLPR3 inflammasome proteins, and interleukin (IL)-1ß. We found that BaP upregulated the expression of AhR or CYP genes to varying degrees in all three cell lines. Exposure to BaP alone increased ΔΨm in all cell lines but decreased NO in BeWo and HTR-8/SVneo, iATP in HTR-8/SVneo, and cell viability in JEG-3, without affecting apoptosis. Under hypoxic conditions, BaP did not increase the expression of AhR and CYP genes in JEG-3 cells but increased CYP gene expression in two others. Pro-inflammatory conditions did not affect the response of the 3 cell lines to BaP with respect to the expression of CYP genes and changes in the mitochondrial function and NLRP3 inflammasome proteins. In addition, in HTR-8/SVneo cells, BaP increased IL-1ß secretion in the presence of hypoxia and poly(I:C). In conclusion, our results showed that BaP affected mitochondrial function in trophoblast cell lines by increasing ΔΨm. This increased ΔΨm may have rescued the trophoblast cells from activation of the NLRP3 inflammasome and apoptosis after BaP treatment. We also observed that different human trophoblast cell lines had cell type-dependent responses to BaP exposure under normoxia, hypoxia, or pro-inflammatory conditions.

Activating and Stabilizing a Reversible four Electron Redox Reaction of I-/I+ for Aqueous Zn-Iodine Battery.

Low capacity and poor cycle stability greatly inhibit the development of zinc-iodine batteries. Herein, a high-performance Zn-iodine battery has been reached by designing and optimizing both electrode and electrolyte. The Br- is introduced as the activator to trigger I+, and coupled with I+ forming interhalogen to stabilize I+ to achieve a four-electron reaction, which greatly promotes the capacity. And the Ni-Fe-I LDH nanoflowers serve as the confinement host to enable the reactions of I-/I+ occurring in the layer due to the spacious and stable interlayer spacing of Ni-Fe-I LDH, which effectively suppresses the iodine-species shuttle ensuring high cycling stability. As a result, the electrochemical performance is greatly enhanced, especially in specific capacity (as high as 350 mAh g-1 at 1 A g-1 far higher than two-electron transfer Zn-iodine batteries) and cycling performance (94.6 % capacity retention after 10000 cycles). This strategy provides a new way to realize high capacity and long-term stability of Zn-iodine batteries.

Spatiotemporal variation of 6PPD and 6PPDQ in dust and soil from e-waste recycling areas.

N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) and its derivative 6PPDQ have been detected in various environmental media, with harmful consequences for both ecosystems and biological health. However, the distribution of 6PPD and 6PPDQ in areas around e-waste recycling areas is currently unknown. We collected soil and dust samples from areas around a traditional e-waste recycling zone, an emerging recycling park, and a reference area. Higher levels of 6PPD were found in dust from residential areas around the traditional e-waste recycling zone compared to the reference area (median: 108.99 versus 33.57 ng/g, P < 0.01). Lower levels of 6PPDQ were detected in dust samples from around the emerging e-waste recycling parks compared to traditional e-waste recycling zones (median: 15.40 versus 46.37 ng/g, P < 0.05). The median concentrations of 6PPD and 6PPDQ were higher in the dust samples than in the soil samples (P < 0.001). The concentrations of 6PPD and 6PPDQ in the dust and soil varied seasonally, with the highest total concentrations occurring in the winter. Results from a multiple linear regression analysis indicate that 6PPDQ is negatively correlated with temperature and positively correlated with 6PPD, O3, and radiation. This study confirms that e-waste is a potential contributor to 6PPD and 6PPDQ. In residential areas, 6PPD and 6PPDQ are more likely to accumulate in dust than in soil. The emerging e-waste recycling parks have greatly improved the local 6PPDQ pollution situation. Further studies are necessary to understand the distribution of newly found substances in various settings.

GIMAP5 deficiency reveals a mammalian ceramide-driven longevity assurance pathway.

Preserving cells in a functional, non-senescent state is a major goal for extending human healthspans. Model organisms reveal that longevity and senescence are genetically controlled, but how genes control longevity in different mammalian tissues is unknown. Here, we report a new human genetic disease that causes cell senescence, liver and immune dysfunction, and early mortality that results from deficiency of GIMAP5, an evolutionarily conserved GTPase selectively expressed in lymphocytes and endothelial cells. We show that GIMAP5 restricts the pathological accumulation of long-chain ceramides (CERs), thereby regulating longevity. GIMAP5 controls CER abundance by interacting with protein kinase CK2 (CK2), attenuating its ability to activate CER synthases. Inhibition of CK2 and CER synthase rescues GIMAP5-deficient T cells by preventing CER overaccumulation and cell deterioration. Thus, GIMAP5 controls longevity assurance pathways crucial for immune function and healthspan in mammals.

Association between 6PPD-quinone exposure and BMI, influenza, and diarrhea in children.

N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine-quinone (6PPD-quinone) has received extensive attention due to its ubiquitous distribution and potential toxicity. However, the distribution characteristics of 6PPD-quinone in dust from e-waste recycling areas and the consequential health risks to children are unclear. A total of 183 dust samples were collected from roads (n = 40), homes (n = 91), and kindergartens (n = 52) in Guiyu (the e-waste-exposed group) and Haojiang (the reference group) from 2019 to 2021. The results show that the concentrations of 6PPD-quinone in kindergarten and house dust from the exposed group were significantly higher than those from the reference group (P < 0.001). These findings show that e-waste may be another potential source of 6PPD-quinone, in addition to rubber tires. The exposure risk of 6PPD-quinone in children was assessed using their daily intake. The daily intake of 925 kindergarten children was calculated using the concentration of 6PPD-quinone in kindergarten dust. The daily intake of 6PPD-quinone via ingestion was approximately five orders of magnitude higher than via inhalation. Children in the exposed group had a higher exposure risk to 6PPD-quinone than the reference group. A higher daily intake of 6PPD-quinone from kindergarten dust was associated with a lower BMI and a higher frequency of influenza and diarrhea in children. This study reports the distribution of 6PPD-quinone in an e-waste recycling town and explores the associated health risks to children.

Effects of endocrine disrupting chemicals and their interactions with genetic risk scores on cardiometabolic traits.

Ubiquitous non-persistent endocrine disrupting chemicals (EDCs) have inconsistent associations with cardiometabolic traits. Additionally, large-scale genome-wide association studies (GWASs) have yielded many genetic risk variants for cardiometabolic traits and diseases. This study aimed to investigate the associations between a wide range of EDC exposures (parabens, bisphenols, and phthalates) and 14 cardiometabolic traits and whether these are moderated by their respective genetic risk scores (GRSs). Data were from 1074 participants aged 18 years or older of the Lifelines Cohort Study, a large population-based biobank. GRSs for 14 cardiometabolic traits were calculated based on genome-wide significant common variants from recent GWASs. The concentrations of 15 EDCs in 24-hour urine were measured by isotope dilution liquid chromatography tandem mass spectrometry technology. The main effects of trait-specific GRSs and each of the EDC exposures and their interaction effects on the 14 cardiometabolic traits were examined in multiple linear regression. The present study confirmed significant main effects for all GRSs on their corresponding cardiometabolic trait. Regarding the main effects of EDC exposures, 26 out of 280 EDC-trait tests were significant with explained variances ranging from 0.43 % (MMP- estimated glomerular filtration rate (eGFR)) to 2.37 % (PrP-waist-hip ratio adjusted body mass index (WHRadjBMI)). We confirmed the association of MiBP and MBzP with WHRadjBMI and body mass index (BMI), and showed that parabens, bisphenol F, and many other phthalate metabolites significantly contributed to the variance of WHRadjBMI, BMI, high-density lipoprotein (HDL), eGFR, fasting glucose (FG), and diastolic blood pressure (DBP). Only one association between BMI and bisphenol F was nominally significantly moderated by the GRS explaining 0.36 % of the variance. However, it did not survive multiple testing correction. We showed that non-persistent EDC exposures exerted effects on BMI, WHRadjBMI, HDL, eGFR, FG, and DBP. However no evidence for a modulating role of GRSs was found.

A genome-wide association study of 24-hour urinary excretion of endocrine disrupting chemicals.

Ubiquitous exposure to environmental endocrine disrupting chemicals (EDCs) instigates a major public health problem, but much remains unknown on the inter-individual differences in metabolism and excretion of EDCs. To examine this we performed a two-stage genome-wide association study (GWAS) for 24-hour urinary excretions of four parabens, two bisphenols, and nine phthalate metabolites. Results showed five genome-wide significant (p-value < 5x10-8) and replicated single nucleotide polymorphisms (SNPs) representing four independent signals that associated with mono-(2-ethyl-5-carboxypentyl) phthalate (MECPP) and mono-(2-ethyl-5-hydroxyhexyl) phthalate (MEHHP). Three of the four signals were located on chromosome 10 in a locus harboring the cytochrome P450 (CYP) genes CYP2C9, CYP2C58P, and CYP2C19 (rs117529685, pMECPP = 5.38x10-25; rs117033379, pMECPP = 1.96x10-19; rs4918798, pMECPP = 4.01x10-71; rs7895726, pMEHHP = 1.37x10-15, r2 with rs4918798 = 0.93). The other signal was on chromosome 6 close to the solute carrier (SLC) genes SLC17A1, SLC17A3, SLC17A4, and SCGN (rs1359232, pMECPP = 7.6x10-16). These four SNPs explained a substantial part (8.3 % - 9.2 %) of the variance in MECPP in the replication cohort. Bioinformatics analyses supported a likely causal role of CYP2C9 and SLC17A1 in metabolism and excretion of MECPP and MEHHP. Our results provide biological insights into mechanisms of phthalate metabolism and excretion with a likely causal role for CYP2C9 and SLC17A1.

Engineering Fluorine-rich Double Protective Layer on Zn Anode for Highly Reversible Aqueous Zinc-ion Batteries.

The high thermodynamic instability and side reactions of Zn-metal anode (ZMA), especially at high current densities, greatly impede the commercialization of aqueous zinc-ion batteries (AZIBs). Herein, a fluorine-rich double protective layer strategy is proposed to obtain the high reversibility of AZIBs through the introduction of a versatile tetradecafluorononane-1,9-diol (TDFND) additive in aqueous electrolyte. TDFND molecule with large adsorption energy (-1.51 eV) preferentially absorbs on the Zn anode surface to form a Zn(OR)2 - (R=-CH2 -(CF2 )7 -CH2 -) cross-linking complex network, which balances space electric field and controls the Zn2+ ion flux, thus enabling the uniform and compact deposition of Zn (002) crystal planes. Meanwhile, TDFND with low Lowest unoccupied molecular orbital (LUMO, 0.10 eV) energy level is priorly decomposed to regulate the interfacial chemistry of ZMA by building a ZnF2 -rich solid electrode/electrolyte interface (SEI) layer. It is found that a 14 nm-thick SEI layer delivers excellent structural integrity to suppress parasitic reactions by blocking the direct contact of active water and ZMA. Consequently, the Zn electrode exhibits a superior cycling life over 430 h at 10 mA cm-2 and a high average Coulombic efficiency of 99.8 % at 5 mA cm-2 . Furthermore, a 68 mAh pouch cell delivers 80.3 % capacity retention for 1000 cycles.

Effects of polycyclic aromatic hydrocarbons (PAHs) on pregnancy, placenta, and placental trophoblasts.

Polycyclic aromatic hydrocarbons (PAHs) are a group of persistent organic pollutants that are carcinogenic, mutagenic, endocrine-toxic, and immunotoxic. PAHs can be found in maternal and fetal blood and in the placenta during pregnancy. They may thus affect placental and fetal development. Therefore, the exposure levels and toxic effects of PAHs in the placenta deserve further study and discussion. This review aims to summarize current knowledge on the effects of PAHs and their metabolites on pregnancy and birth outcomes and on placental trophoblast cells. A growing number of epidemiological studies detected PAH-DNA adducts as well as the 16 high-priority PAHs in the human placenta and showed that placental PAH exposure is associated with adverse fetal outcomes. Trophoblasts are important cells in the placenta and are involved in placental development and function. In vitro studies have shown that exposure to either PAH mixtures, benzo(a)pyrene (BaP) or BaP metabolite benzo(a)pyrene-7,8-dihydrodiol-9,10-epoxide (BPDE) affected trophoblast cell viability, differentiation, migration, and invasion through various signaling pathways. Furthermore, similar effects of BPDE on trophoblast cells could also be observed in BaP-treated mouse models and were related to miscarriage. Although the current data show that PAHs may affect placental trophoblast cells and pregnancy outcomes, further studies (population studies, in vitro studies, and animal studies) are necessary to show the specific effects of different PAHs on placental trophoblasts and pregnancy outcomes.

General Synthesis of Single-Crystal Spinel Cathodes with the Tailored Orientation of Exposed Crystal Planes for Advanced Lithium-Ion Batteries.

The spinel Mn-based cathodes with 3D Li+ diffusion channels, high voltage, and low-cost show promise for developing high-power lithium-ion batteries (LIBs). But the disproportionation and Jahn-Teller distortion lead to structural degeneration and capacity decay, especially at high working temperatures. Herein, considering the merits of single crystals and orientation of exposed crystal planes, single-crystal truncated octahedral LiMn2 O4 (TO-LMO) with exposed {111}, {100} and {110} facets is rationally designed, in which the mainly exposed {111} facets are truncated by a small portion of {100} and {110} facets. The Li-deficient intermediate phase is innovatively proposed to prepare the single-crystal TO-LMO. The synergistic effects of single crystals and the orientation of exposed crystal planes significantly reduce the disproportionation of Mn3+ ions and thereby improve their structural stability. Consequently, the cycling stability of the single-crystal TO-LMO is remarkably enhanced, obtaining outstanding capacity retention of 84.3% after 2000 cycles, much better than that of 61.2% for octahedral LiMn2 O4 . The feasibility of preparing single-crystal truncated octahedral LiNi0.5 Mn1.5 O4 with exposed {111}, {100}, and {110} facets via the Li-deficient intermediate phase is further demonstrated. These findings offer new insight into regulating the orientation of exposed crystal planes and improving the reversibility of Mn-based redox couples in LIBs.

An Ultrathin Inorganic Molecular Crystal Interfacial Layer for Stable Zn Anode.

Zn metal anode suffers from dendrite growth and side reactions during cycling, significantly deteriorating the lifespan of aqueous Zn metal batteries. Herein, we introduced an ultrathin and ultra-flat Sb2 O3 molecular crystal layer to stabilize Zn anode. The in situ optical and atomic force microscopes observations show that such a 10 nm Sb2 O3 thin layer could ensure uniform under-layer Zn deposition with suppressed tip growth effect, while the traditional WO3 layer undergoes an uncontrolled up-layer Zn deposition. The superior regulation capability is attributed to the good electronic-blocking ability and low Zn affinity of the molecular crystal layer, free of dangling bonds. Electrochemical tests exhibit Sb2 O3 layer can significantly improve the cycle life of Zn anode from 72 h to 2800 h, in contrast to the 900 h of much thicker WO3 even in 100 nm. This research opens up the application of inorganic molecular crystals as the interfacial layer of Zn anode.

A thermodynamically stable O2-type cathode with reversible O2-P2 phase transition for advanced sodium-ion batteries.

Low-cost sodium-ion batteries (SIBs) have shown very promise in the applications of renewable energy and low-speed electric vehicles. The development of a new O2-type cathode in SIBs is very challenging in that this compound is only stable as an intermediate product of P2-type oxides during redox reactions. Here, we report a thermodynamically stable O2-type cathode obtained by Na/Li ion exchange from P2-type oxide in a binary molten salt system. It is demonstrated that the as-prepared O2-type cathode exhibits a highly reversible O2-P2 phase transition during Na+ de-intercalation. The unusual O2-P2 transition has a low volume change of ∼11%, much lower than that of 23.2% for P2-O2 transformation in the P2-type cathode. The lowered lattice volume change of this O2-type cathode gives rise to superior structural stability upon cycling. Therefore, the O2-type cathode possesses a reversible capacity of about 100 mAh/g with a good capacity retention of 87.3% even after 300 cycles at 1C, indicating outstanding long-term cycling stability. These achievements will promote the development new class of cathode materials with high capacity and structural stability for advanced SIBs.

Accelerating the solar-thermal energy storage via inner-light supplying with optical waveguide.

Solar-thermal storage with phase-change material (PCM) plays an important role in solar energy utilization. However, most PCMs own low thermal conductivity which restricts the thermal charging rate in bulk samples and leads to low solar-thermal conversion efficiency. Here, we propose to regulate the solar-thermal conversion interface in spatial dimension by transmitting the sunlight into the paraffin-graphene composite with side-glowing optical waveguide fiber. This inner-light-supply mode avoids the overheating surface of the PCM, accelerates the charging rate by 123% than that of the traditional surface irradiation mode and increases the solar thermal efficiency to ~94.85%. Additionally, the large-scale device with inner-light-supply mode works efficiently outdoors, indicating the potential of this heat localization strategy in practical application.

Blood lead levels of children exposed to e-waste: a systematic review and meta-analysis.

Blood lead levels (BLLs) have been decreasing worldwide for decades. However, systematic reviews and quantitative syntheses of BLLs in electronic waste (e-waste)-exposed children are lacking. To summarize temporal trend of BLLs among children in e-waste-recycling areas. Fifty-one studies met the inclusion criteria and included participants from six countries. Meta-analysis was performed using the random-effects model. Results showed that among e-waste-exposed children, the total geometric mean (GM) BLL was 7.54 µg/dL (95% CI: 6.77, 8.31). Children's BLLs displayed a decreasing temporal trend, from 11.77 µg/dL in phase I (2004-2006) to 4.63 µg/dL in phase V (2016-2018). Almost 95% of eligible studies found that children exposed to e-waste had significantly higher BLLs than reference groups. The difference of children's BLLs between the exposure group and the reference group was from 6.60 µg/dL (95% CI: 6.14, 7.05) in 2004 to 1.99 µg/dL (95% CI: 1.61, 2.36) in 2018. For subgroup analyses, except for Dhaka and Montevideo, the BLLs of children from Guiyu in the same survey year were higher than those of children from other regions. Our findings indicate that the gap between BLLs of children exposed to e-waste and those of reference group children is closing, and we appeal that the critical value for blood lead poisoning in children should be lowered in key e-waste-dismantling areas of developing countries, such as Guiyu.

Interface strong-coupled 3D Mo-NiS@Ni-Fe LDH flower-cluster as exceptionally efficient electrocatalyst for water splitting in wide pH range.

It is crucial to create a bifunctional catalyst with high efficiency and low cost for electrochemical water splitting under alkaline and neutral pH conditions. This study investigated the in-situ creation of ultrafine Mo-NiS and NiFe LDH nanosheets as an effective and stable electrocatalyst with a three-dimensional (3D) flower-cluster hierarchical structure (Mo-NiS@NiFe LDH). The strong interfacial connection between Mo-NiS and NiFe LDH enhances the formation of metal higher chemical states in the material, optimizes the electronic structure, increases OH- adsorption capacity improves electron transfer/mass diffusion, and promotes O2/H2 gas release. As a result, at 10 mA cm-2, Mo-NiS@NiFe LDH/NF demonstrates the outstanding bifunctional electrocatalytic activity of just 107 mV (HER, hydrogen evolution reaction) and 184 mV (hydrogen evolution reaction) (OER, oxygen evolution reaction). The catalytic performance is remarkably stable after 72 h of continuous operation in 1 M KOH at high current densities (300 mA cm-2). More interestingly, in the overall water splitting system, the cell voltages for anode and cathode in both alkaline and neutral electrolytes for Mo-NiS@NiFe LDH/NF are only 1.54 V (alkaline) and 2.06 V (neutral) at 10 mA cm-2. These results demonstrated that the bifunctional electrocatalyst design concept is a viable solution for water splitting in both alkaline and neutral systems.

In-situ growth of 3D hierarchical γ-FeOOH/Ni3S2 heterostructure as high performance electrocatalyst for overall water splitting.

Obtaining efficient, stable, and low-cost electrocatalysts is the key to realizing large-scale water splitting. In this work, three-dimensional (3D) hierarchical γ-iron oxyhydroxide (γ-FeOOH)/Ni3S2 electrocatalyst on Ni foam is constructed for electrochemical overall water splitting. The 3D γ-FeOOH/Ni3S2 heterostructure can effectively enhance active sites and charge transfer capability, also the heterostructure can benefit electronic effect at the interfaces and synergistic effect of multiple components. Therefore, the γ-FeOOH/Ni3S2 exhibits excellent electrocatalytic activity with low overpotentials of 279 mV at 50 mA⋅cm-2 for oxygen evolution reaction and 92 mV at 10 mA⋅cm-2 for hydrogen evolution reaction, respectively. In addition, only a potential of 1.66 V is needed to attain 10 mA⋅cm-2 for the overall water splitting. In particular, the γ-FeOOH/Ni3S2 exhibits long-term stability for 120 h at 10 mA⋅cm-2 without significant degradation. This work provides a valuable idea for obtaining low-cost and high performance bifunctional electrocatalysts for water splitting.