Simulation study on functional group-modified Ni-MOF-74 for CH4/N2 adsorption separation.

This study employs grand canonical Monte Carlo (GCMC) simulations to investigate the impact of functional group modifications (CH3, OH, NH2, and OLi) on the adsorption performance of CH4/N2 on Ni-MOF-74. The results revealed that functional group modifications significantly increased the adsorption capacity of Ni-MOF-74 for both CH4 and N2. The packed methyl groups in CH3-Ni-MOF-74 create an environment conducive to CH4, leading to the highest CH4 adsorption capacity. The electrostatic potential distribution indicates that the strong electron-donating effect introduced by the alkali metal Li results in the highest electrostatic potential gradient in Li-O-Ni-MOF-74, leading to the strongest adsorption of N2, this is unfavorable for CH4/N2 separation. At 1500 kPa the selectivity order of adsorbents for mixed gases was as follows: CH3-Ni-MOF-74 > NH2-Ni-MOF-74 > OH-Ni-MOF-74 > Ni-MOF-74 > Li-O-Ni-MOF-74. This study highlights that CH3-Ni-MOF-74 possesses optimal CH4 selectivity and adsorption performance. Given the current lack of research on functionalized MOF-74 for the separation of CH4 and N2, the findings of this study will serve as a theoretical guide and provide references for the applications of CH4 adsorption and CH4/N2 separation.

YTHDF2 in dentate gyrus is the m6A reader mediating m6A modification in hippocampus-dependent learning and memory.

N6-methyladenosine (m6A) has been demonstrated to regulate learning and memory in mice. To investigate the mechanism by which m6A modification exerts its function through its reader proteins in the hippocampus, as well as to unveil the specific subregions of the hippocampus that are crucial for memory formation, we generated dentate gyrus (DG)-, CA3-, and CA1-specific Ythdf1 and Ythdf2 conditional knockout (cKO) mice, respectively. Surprisingly, we found that only the DG-specific Ythdf2 cKO mice displayed impaired memory formation, which is inconsistent with the previous report showing that YTHDF1 was involved in this process. YTHDF2 controls the stability of its target transcripts which encode proteins that regulate the elongation of mossy fibers (MF), the axons of DG granule cells. DG-specific Ythdf2 ablation caused MF overgrowth and impairment of the MF-CA3 excitatory synapse development and transmission in the stratum lucidum. Thus, this study identifies the m6A reader YTHDF2 in dentate gyrus as the only regulator that mediates m6A modification in hippocampus-dependent learning and memory.

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.

Halogen-Bonding-Promoted C-H Malonylation of Indoles under Visible-Light Irradiation.

Herein, we report a halogen-bonding-based electron donor-acceptor (EDA) complex-promoted photoreaction for the synthesis of C2-malonylated indoles. The protocol provides access to a broad range of functionalized indoles in good yields through the coupling reaction of indoles with diethyl bromomalonate under visible-light irradiation without the need for any transition-metal catalyst or photocatalyst.

A Metallofullertube of Ce2 @C100 with a Carbon Nanotube Segment: Synthesis, Single-Molecule Conductance and Supramolecular Assembly.

Tubular fullerenes can be considered as end-capped carbon nanotubes with accurate structure, which are promising nanocarbon materials for advanced single-molecule electronic devices. Herein, we report the synthesis and characterization of a metallofullertube Ce2 @D5 (450)-C100 , which has a tubular C100 cage with a carbon nanotube segment and two fullerene end-caps. As there are structure correlations between tubular Ce2 @D5 (450)-C100 and spherical Ce2 @Ih -C80 , their structure-property relationship has been compared by means of experimental and theoretical methods. Notably, single-molecule conductance measurement determined that the conductivity of Ce2 @D5 (450)-C100 was up to eight times larger than that of Ce2 @Ih -C80 . Furthermore, supramolecular assembly of Ce2 @D5 (450)-C100 and a [12]CPP nanohoop was investigated, and theoretical calculations revealed that metallofullertube Ce2 @D5 (450)-C100 adopted a "standing" configuration in the cavity of [12]CPP. These results demonstrate the special nature of this kind of metallofullertube.

Unveiling the Mechanism, Origin of Stereoselectivity, and Ligand-Dependent Reactivity in the Pd(II)-Catalyzed Unbiased Methylene C(sp3)-H Alkenylation-Aza-Wacker Cyclization Reaction.

The mechanism, origin of stereoselectivity, and ligand-dependent reactivity of Pd(II)-catalyzed methylene C(sp3)-H alkenylation-aza-Wacker cyclization to form (E)-ß-stereogenic γ-lactam have been comprehensively studied by density functional theory (DFT) calculations. The calculated results reveal that the methylene C-H activation assisted by K2CO3 via the concerted metalation-deprotonation mechanism is found to be the most preferred pathway, where the enantioselectivity is distinguished by the orientation of the methyl group of a substrate relative to a chiral ligand. However, the stereochemistry of the olefin moiety in the generated product is mainly determined by the oxidative addition step, where the coulombic interaction and dispersion effect differentiate the energy difference of diastereomeric transition states. In terms of the agostic interaction nature of "three-center two-electron" transition states, the discrepancy of reactivities caused by different Pd catalysts is attributed to the electron induction effect of substituents on the chiral ligands. In other words, the use of an electron-withdrawing group (e.g., -CN) in place of an electron-donating group (e.g., -OMe) enhances the oxidation state of the Pd atom and lowers vacant d orbitals of the palladium atom of the catalyst and in turn facilitates a larger amount of σ-electronic-charge injection into an empty 3d shell of the palladium center. Thus, the higher catalytic activity of the Pd catalyst with ligands substituted by an electron-withdrawing group is anticipated.

Vanadate-induced antiproliferative and apoptotic response in esophageal squamous carcinoma cell line EC109.

Vanadate is a transition element that present in nature and was shown to be a nonspecific inhibitor of protein tyrosine phosphatases. It was reported that vanadium (Vd) compounds exhibit antitumor actions in several cancer cell lines. This study aimed to examine the antiproliferative and apoptotic actions of different concentrations of sodium vanadate (NaVd) (+5) in esophageal squamous carcinoma cell line EC109 by determining the protein expression levels of cyclin D1 and caspase-3 following incubation for various times from 15 min up to 4 h. In addition, cell proliferation of EC109 treated with different concentrations (NaVd) was also measured using the MTT assay at 4, 12, 24, and 48 h. The cell cycle of EC109 cells exposed to different concentrations of NaVd was detected using flow cytometry determination at 24 h. Data showed that NaVd greater than 100 µM significantly increased cyclin D1. In contrast, reduced caspase-3 protein expression levels occurred at 50 µM. Cellular proliferation was significantly decreased at 50uM. The cell cycle was arrested at S phase with 100 µM NaVd. Taken together, data indicate that NaVd produced concentration- and time-dependent antitumor actions in EC109 cell line.

Metallofullerenes encaging mixed-metal clusters: synthesis and structural studies of Gdx Ho3-x N@C80 and Gdx Lu3-x N@C80.

Metallofullerenes of Gdx Ho3-x N@C80 and Gdx Lu3-x N@C80 encapsulating mixed-metal nitride clusters were synthesized. Spectroscopic characterization of Gdx Ho3-x N@C80 and Gdx Lu3-x N@C80 was employed to reveal their structural and vibrational properties. The structural properties of these species were analyzed by using theoretical calculations. The studies of Gdx Ho3-x N@C80 and Gdx Lu3-x N@C80 laid the foundations for these species to be used as multifunctional molecules.

Theoretical study on experimentally detected Sc2S@C84.

Sc(2)S@C(84) has recently been detected but not structurally characterized.1 Density functional theory calculations on C(84) and Sc(2)S@C(84) show that the favored isomer of Sc(2)S@C84 shares the same parent cage as Sc(2)C2@C(84), whereas Sc(2)S@C(84):51383, which violates the isolated-pentagon rule, is the second lowest energy isomer with the widest HOMO-LUMO gap and shows high kinetic stability. The analysis shows that Sc(2)S@C(84):51575 is favored when the temperature exceeds 2,800 K and it can transform into the most favorable isomer Sc(2)S@C(84):51591. Molecular orbital analysis indicates that both Sc(2)S and Sc(2)C(2) formally transfer four electrons to the cage, and quantum theory of atoms in molecules analysis demonstrates that there is a covalent interaction between Sc(2)S and C(84):51591. The IR spectra of Sc(2)S@C(84) are provided to aid future structural identification.

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.

Alterations of gut microbiota and its metabolomics in children with 6PPDQ, PBDE, PCB, and metal(loid) exposure.

The composition and metabolites of the gut microbiota can be altered by environmental pollutants. However, the effect of co-exposure to multiple pollutants on the human gut microbiota has not been sufficiently studied. In this study, gut microorganisms and their metabolites were compared between 33 children from Guiyu, an e-waste dismantling and recycling area, and 34 children from Haojiang, a healthy environment. The exposure level was assessed by estimating the daily intake (EDI) of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), 6PPD-quinone (6PPDQ), and metal(loid)s in kindergarten dust. Significant correlations were found between the EDIs of 6PPDQ, BDE28, PCB52, Ni, Cu, and the composition of gut microbiota and specific metabolites. The Bayesian kernel machine regression model showed negative correlations between the EDIs of five pollutants (6PPDQ, BDE28, PCB52, Ni, and Cu) and the composition of gut microbiota. The EDIs of these five pollutants were positively correlated with the levels of the metabolite 2,4-diaminobutyric acid, while negatively correlated with the levels of d-erythro-sphingosine and d-threitol. Our study suggests that exposure to 6PPDQ, BDE28, PCB52, Ni, and Cu in kindergarten dust is associated with alterations in the composition and metabolites of the gut microbiota. These alterations may be associated with children's health.

Theoretical Study on a Supramolecular Dimeric Structure Constructed by Metallofullerene Y3N@C80 and Figure-of-Eight Nanoring.

A new supramolecular complex with a dimeric structure (2Y3N@C80⊂OPP) constructed by metallofullerene Y3N@Ih-C80 and figure-of-eight molecular nanoring of oligoparaphenylene (OPP) was investigated using dispersion-corrected density functional theory (DFT-D3). The interactions between the Y3N@Ih-C80 guest and the OPP host were studied theoretically at the B3LYP-D3/6-31G(d)∼SDD level. By analyzing geometric characteristics and host-guest binding energies, it is revealed that the OPP is an ideal host molecule for the Y3N@Ih-C80 guest. Typically, the OPP can well induce the orientation of the endohedral Y3N cluster on the plane of nanoring. Meanwhile, the configuration of the dimeric structure demonstrates that OPP presents excellent elastic adaptability and shape flexibility during the encapsulation of Y3N@Ih-C80. Highly accurate binding energy suggests that 2Y3N@C80⊂OPP (∼-443.82 kJ mol-1 at the ωB97M-V/def2-QZVPP level of theory) is an extremely stable host-guest complex. Thermodynamic information indicates that the formation of the 2Y3N@C80⊂OPP dimer is thermodynamically spontaneous. Furthermore, electronic property analysis reveals that this dimeric structure has a strong electron-attracting ability. Energy decomposition and real-space function analyses of host-guest interactions reveal the characteristics and nature of the noncovalent interactions in the supramolecules. These results provide theoretical support for the design of new host-guest systems based on metallofullerene and nanoring.

Theoretical exploration of noncovalent interactions in Sc2C2@C2n (n = 40, 41, and 42)⊂[12]CPP, PF[12]CPP.

The encapsulation of fullerenes by carbon nanorings has gained increasing attention because of the unique molecular structure and special properties of the formed complexes. The host-guest interactions between the fullerenes and the carbon nanorings can influence the metal ion orientation and the molecular electronic structure. In this study, we hooped a series of carbide cluster metallofullerenes, namely Sc2C2@C2v(5)-C80, Sc2C2@C3v(8)-C82, and Sc2C2@D2d(23)-C84, with molecular carbon nanorings of [12]cycloparaphenylene ([12]CPP) and perfluoro[12]cycloparaphenylene (PF[12]CPP). The formed complexes were computationally studied via dispersion-corrected density functional theory calculations. The results showed that the deformation rate of PF[12]CPP after the formation of the fullerene-containing complexes was significantly smaller than that of [12]CPP. The binding energy and thermodynamic information showed that PF[12]CPP was more suitable for fullerene encapsulation. Moreover, charge population analysis showed that PF[12]CPP transferred more electrons to Sc2C2@C2n (n = 40, 41, and 42) compared with [12]CPP. Energy decomposition and real-space function analyses of host-guest interactions revealed the characteristics and nature of the noncovalent interactions in the supramolecules. These results provide theoretical support for the study of host-guest systems based on metallofullerenes.

Kindergarten dust heavy metal(loid) exposure associates with growth retardation in children.

Heavy metal contamination from electronic waste recycling sites is present in dust found in indoor kindergartens located in e-waste recycling areas, and its potential impact on child health is a significant concern. The association between heavy metal(loid)s and the child developmental indicators is still unclear. In 2019 and 2020, we enrolled 325 and 319 children in an e-waste recycling town, respectively. Corresponding 61 and 121 dust samples were collected from roads, houses, and kindergartens in the two years. The median concentrations of metals, including Cr, Ni, Cu, Zn, and Pb exceeded the allowable limits. The highest amount of cumulative enrichment (cEF) was observed in indoor kindergarten dust (cEF = 112.3400), followed by house dust (cEF = 76.6950) and road dust (cEF = 39.7700). Children residing in the e-waste town had below-average height and weight compared to their Chinese peers. Based on linear regression analysis, the daily intake of Cd, V, Mn, and Pb in indoor kindergarten dust was found to be negatively associated with head circumference (HeC) (P < 0.05). Similarly, the daily intake of As, Cd, and Ba in indoor kindergarten dust was found to be negatively associated with chest circumference (ChC) (P < 0.05). In addition, the daily intake of As, Cd, and Ba in indoor kindergarten dust was negatively correlated with body mass index (BMI), as per the results of the study (P < 0.05). Cross-product term analysis revealed a negative correlation between daily intake of heavy metal(loid)s and HeC, ChC, and BMI, with age and sex serving as influencing factors. In conclusion, exposure to heavy metal(loid)s in indoor kindergarten dust increases the risk of growth retardation and developmental delay in children.

Structure and single-molecule conductance of two endohedral metallofullerenes with large C88 cage.

Endohedral metallofullerenes are capable of holding peculiar metal clusters inside the carbon cage. Additionally, these display many chemical and physical properties originating from the complexation between the metal clusters and carbon cages, which could be acquired for wide applications. In this study, two metallofullerenes (Ce2O@C88 and Ce3N@C88) with an identical large C88-D2(35) cage, and their molecular structures and single-molecule conductance properties were investigated comparatively. Characterizations of UV-vis-NIR absorption spectroscopy, Raman spectroscopy, and DFT calculations were employed to determine the geometries and electronic structures of Ce2O@C88 and Ce3N@C88. These molecules revealed varied energy gaps, structural parameters, vibrational modes, and molecular frontier orbitals. Although the two metallofullerenes have an identical cage isomer of C88-D2(35), their different endohedral clusters can influence their structures and physicochemical properties. Furthermore, the single-molecule conductance properties were measured using the scanning tunneling microscopy break junction technique (STM-BJ). The experimental results revealed that Ce2O@C88 has a higher conductance than Ce3N@C88 and C60. This revealed the cluster-dependent electron transportation as well as the significant research value of metallofullerenes with large carbon cages. These results provide guidance for fabricating single-molecule electronic devices.

Improvement of light extraction efficiency of GaN-based light-emitting diodes using Ag nanostructure and indium tin oxide grating.

Based on the analysis of the evanescent wave from total internal reflection, a light-emitting diode (LED) structure with a plasmonic Ag nanostructure and indium tin oxide (ITO) grating was proposed to enhance the extraction efficiency. The two-dimensional finite-difference time-domain method was used to study the spectral properties of the hybrid structure and the effects of structure parameters on extraction enhancement. The results demonstrate that the plasmonic Ag nanostructure can couple the evanescent wave to a propagation wave around the GaN/ITO interface, and then the photons are scattered out of the LED chips by the ITO grating with high extraction efficiency. Under the optimal parameters, the light extraction efficiency can reach approximately three times the original value at a relatively longer wavelength.

Photoelectrochemical Response Enhancement for Metallofullerene-[12]Cycloparaphenylene Supramolecular Complexes.

The photoelectrochemical properties of three metallofullerene-[12]cycloparaphenylene ([12]CPP) supramolecular complexes of Sc3N@C78⊂[12]CPP, Sc3N@C80⊂[12]CPP, and Sc2C2@C82⊂[12]CPP were studied. It was revealed that the photocurrent responses of these supramolecular complexes show enhancement compared with those of pristine metallofullerenes, indicating the efficient photocurrent generation and promoted charge carrier transport caused by the supramolecular interaction. The results show that Sc2C2@C82 and Sc2C2@C82⊂[12]CPP have the strongest photocurrents. Then, by comparing the photocurrent intensities of the metallofullerene-biphenyl derivates mixture and the metallofullerene⊂[12]CPP complexes, it was demonstrated that the host-guest interaction is the key factor promoting photocurrent enhancement. At the same time, by observing the microscopic morphologies of pristine fullerenes and supramolecular complexes, it was found that the construction of supramolecules helps to improve the morphology of metallofullerenes on FTO glass. Additionally, their electrical conductivity in optoelectronic devices was tested, respectively, indicating that the construction of supramolecules facilitates the transport of charge carriers. This work discloses the potential application of metallofullerene supramolecular complexes as photodetector and photoelectronic materials.

Visible and near-infrared photoluminescence of a supramolecular complex constructed from a cycloparaphenylene nanoring and an erbium metallofullerene.

Erbium metallofullerenes exhibit near-infrared photoluminescence from the Er3+ ions, which has potential applications in telecommunications, optical devices and bioscience. In this manuscript, we report the construction of a supramolecular complex of metallofullerene Er3N@C80 and cycloparaphenylene [12]CPP to adjust the near-infrared photoluminescence of Er3N@C80 through host-guest interactions. Moreover, this supramolecular complex shows a multiwavelength luminescence property. Mass spectrometry, electrochemical measurements and proton NMR spectroscopy were used to characterize the structure of Er3N@C80⊂[12]CPP. The electrochemical results of Er3N@C80⊂[12]CPP show the negatively shifted redox potentials compared to pristine Er3N@C80 and the 1H NMR signals of Er3N@C80⊂[12]CPP shift upfield compared to pristine [12]CPP. More importantly, the photoluminescence spectra show that the [12]CPP nanoring can affect the near-infrared emission of encapsulated Er3+ ions in Er3N@C80, with the characteristic emission peak of Er3+ at 1.5 µm being broadened and enhanced in the Er3N@C80⊂[12]CPP complex, while the fluorescence lifetime of Er3+ also becomes longer after assembly formation. Furthermore, the Er3N@C80 guest also can influence the photoluminescence property of [12]CPP, whose emission peaks exhibit a slight blue-shift in the Er3N@C80⊂[12]CPP complex. This study illustrates that the outer nanoring can be employed to adjust the photoluminescence of the encapsulated Er3+ ion in Er3N@C80.

Maternal exposure to atmospheric PM2.5 and fetal brain development: Associations with BAI1 methylation and thyroid hormones.

Maternal exposure to atmospheric fine particulate matter (PM2.5) during pregnancy is associated with adverse fetal development, including abnormal brain development. However, the underlying mechanisms and influencing factors remain uncertain. This study investigated the roles of DNA methylation in genes involving neurodevelopment and thyroid hormones (THs) in fetal brain development after maternal exposure to PM2.5 from e-waste. Among 939 healthy pregnant women recruited from June 2011 to September 2012, 101 e-waste-exposed and 103 reference mother-infant pairs (204 pairs totally) were included. Annual ground-level PM2.5 concentrations over e-waste-exposed area (116.38°E, 23.29°N) and reference area (116.67°E, 23.34°N) in 2011, 2012 were obtained by estimates and maternal exposure was evaluated by calculating individual chronic daily intakes (CDIs) of PM2.5. Methylation and THs including thyroid-stimulating hormone (TSH), free triiodothyronine (FT3) and free thyroxine (FT4) level were measured in umbilical cord blood collected shortly after delivery. We found higher ground-level PM2.5 concentrations led to greater individual CDI of PM2.5 in e-waste-exposed pregnant women. After adjustment for gender and birth BMI, significant mediation effects on the adverse associations of maternal PM2.5 exposure with birth head circumference were observed for methylations at positions +13 and + 32 (respectively mediated proportion of 9.8% and 5.3%, P < 0.05 and P < 0.01) in the brain-specific angiogenesis inhibitor 1 (BAI1) gene, but not for methylations in the catenin cadherin-associated protein, alpha 2 (CTNNA2) gene. BAI1 (position +13) methylation was also significantly correlated with FT3 levels (rs = -0.156, P = 0.032), although maternal CDI of PM2.5 was positively associated with higher odds of abnormal TSH levels (OR = 5.03, 95% CI: 1.00, 25.20, P = 0.05) rather than FT3 levels. Our findings suggest that methylation (likely linked to THs) in neonates may play mediation roles associated with abnormal brain development risk due to maternal exposure to atmospheric PM2.5 from e-waste.

Visible-Light Carbon Nitride-Catalyzed Aerobic Cyclization of Thiobenzanilides under Ambient Air Conditions.

A metal-free heterogeneous photocatalysis has been developed for the synthesis of benzothiazoles via intramolecular C-H functionalization/C-S bond formation of thiobenzanilides by inexpensive graphitic carbon nitride (g-C3N4) under visible-light irradiation. This reaction provides access to a broad range of 2-substituted benzothiazoles in high yields under an air atmosphere at room temperature without addition of a strong base or organic oxidizing reagents. In addition, the catalyst was found to be stable and reusable after five reaction cycles.