Bis(μ-2,2′-biimidazole-κ2 N 3:N 3′)bis­[aqua­copper(I)] sulfate

In the structure of the title compound, [Cu2(C6H6N4)2(H2O)2]SO4, the asymmetric unit contains half each of two 2,2′-diimidazole ligands, one Cu+ cation, one water mol­ecule and half of a sulfate anion (2 symmetry). The dinuclear complex is completed through a twofold rotation axis, leading to a twisted ten-membered ring mol­ecule. The dihedral angle between the two symmetry-related 2,2′-diimidazole ligands is 23.6 (1)°. The copper centre is coordinated by two N atoms of two symmetry-related 2,2′-diimidazole ligands in an almost linear fashion. The water mol­ecule exhibits a weak coordination to Cu+ with a more remote distance of 2.591 (2) Å. The distance between the two copper centres is 2.5956 (6) Å. O—H⋯O and N—H⋯O hydrogen bonds between the complex cation, the water mol­ecule and the sulfate anion lead to the formation of a three-dimensional network

Diaqua-1κO,2κO-(2,2′-bi-1H-imidazole-1κ2 N 3,N 3′)(oxalato-2κ2 O 1,O 2)di-μ-oxido-κ4 O:O-dioxido-1κO,2κO-dimolyb­denum(V) trihydrate

In the title compound, [Mo2(C2O4)O4(C6H6N4)(H2O)2]·3H2O, the coordination polyhedra for both Mo(V) atoms consist of two bridging O atoms, two atoms of the chelating ligand (oxalate or diimidazole), a terminal O atom and one H2O mol­ecule. The two distorted octa­hedrally coordinated Mo(V) atoms are linked together via O—O edge-sharing and Mo—Mo inter­actions with a Mo—Mo bond length of 2.564 (5) Å. Uncoordinated water mol­ecules are situated in the voids of the crystal structure. N—H⋯O and O—H⋯O hydrogen bonding between the neutral mol­ecules and the water mol­ecules lead to a consolidation of the structure

(μ-Oxalato-κ4 O 1,O 2:O 1′,O 2′)bis­[bis­(2,2′-bipyridine-κ2 N,N′)cobalt(II)] μ6-oxido-dodeca-μ2-oxido-hexa­oxido-hexa­tungstate(VI)

The asymmetric unit of the title compound, [Co2(C2O4)(C10H8N2)4][W6O19], consists of one half of the complex [Co2(C2O4)(C10H8N2)4]2+ cation and one half of the Lindqvist-type [W6O19]2− isopolyanion. Both constituents are completed by crystallographic inversion symmetry. In the dimeric cation, the CoII atom is surrounded in a distorted octa­hedral coordination by four N atoms from two chelating 2,2′-bipyridine ligands and by two O atoms from the chelating oxalate anion. The Lindqvist-type anion exhibits the characteristic W—O bond-length distribution, with the shortest bonds being the W—Oterminal bonds and the longest being those to the central O atom

Tris{aqua­bis[3-(2-pyrid­yl)-1H-pyrazole]copper(II)} di-μ9-arsenato-hexa­triaconta-μ2-oxido-octa­deca­oxidoocta­deca­molybdate(VI)

The title compound, [Cu(C8H7N3)2(H2O)]3[As2Mo18O62], consists of two subunits, viz. an α-Dawson-type [As2Mo18O62]6− anion and a complex [Cu(C8H7N3)2(H2O)]2+ cation. The copper(II) ion (site symmetry .2) is penta­coordinated in a distorted square-pyramidal manner by four N atoms from two chelating 3-(2-pyrid­yl)pyrazole ligands in equatorial positions and one water mol­ecule in the apical position. In the heteropolyanion, two O atoms of the AsO4 group (3. symmetry) are equally disordered about the threefold rotation axis. N—H⋯O and O—H⋯O hydrogen bonding between the neutral mol­ecules and the water mol­ecules leads to a consolidation of the structure

Ubiquitin ligase RNF125 targets PD-L1 for ubiquitination and degradation

As a critical immune checkpoint molecule, PD-L1 is expressed at significantly higher levels in multiple neoplastic tissues compared to normal ones. PD-L1/PD-1 axis is a critical target for tumor immunotherapy, blocking the PD-L1/PD-1 axis is recognized and has achieved unprecedented success in clinical applications. However, the clinical efficacy of therapies targeting the PD-1/PD-L1 pathway remains limited, emphasizing the need for the mechanistic elucidation of PD-1/PD-L1 expression. In this study, we found that RNF125 interacted with PD-L1 and regulated PD-L1 protein expression. Mechanistically, RNF125 promoted K48-linked polyubiquitination of PD-L1 and mediated its degradation. Notably, MC-38 and H22 cell lines with RNF125 knockout, transplanted in C57BL/6 mice, exhibited a higher PD-L1 level and faster tumor growth than their parental cell lines. In contrast, overexpression of RNF125 in MC-38 and H22 cells had the opposite effect, resulting in lower PD-L1 levels and delayed tumor growth compared with parental cell lines. In addition, immunohistochemical analysis of MC-38 tumors with RNF125 overexpression showed significantly increased infiltration of CD4+, CD8+ T cells and macrophages. Consistent with these findings, analyses using The Cancer Genome Atlas (TCGA) public database revealed a positive correlation of RNF125 expression with CD4+, CD8+ T cell and macrophage tumor infiltration. Moreover, RNF125 expression was significantly downregulated in several human cancer tissues, and was negatively correlated with the clinical stage of these tumors, and patients with higher RNF125 expression had better clinical outcomes. Our findings identify a novel mechanism for regulating PD-L1 expression and may provide a new strategy to increase the efficacy of immunotherapy

Study on Construction Influence of Shield Tunnel of Urban Rail Transit on Large-Section Mining Tunnel

Due to the increasingly expanding of urban rail transit, shield tunnelling adjacent to existing tunnels has become more and more common in cities. Construction of new tunnels will pose great risks to the safety of existing tunnels. This paper focused on the influence of shield tunnelling on the large-section mining tunnel in the argillaceous siltstone stratum and proposed the influence zone based on the surface subsidence criterion. By carrying out numerical simulations and model test, the surface subsidence, the internal force of the mining tunnel, and the surrounding rock pressure were monitored and the accuracy of the influence zone was verified. The research shows that the shield machine tunnels forward from one time the excavation diameter before the monitoring section until the monitoring section completes the segment assembly. This process is the main stage that causes the increase in the corresponding surface settlement and the additional displacement of the existing mining tunnel. The excavating tunnel influences on the mining tunnel structure were mainly shown at the vertical additional deformation, which is manifested as the overall floating of the mining tunnel. The influence of internal force was performed as the asymmetric change of internal force of the mining tunnel. The mining tunnel is closer to the shield tunnel, showing more significant changes of the internal force of the structures. The structure near the shield tunnel is strengthened by pressure, and the structure far away from the shield tunnel is more prone to tensile failure

Experimental and theoretical study on the extraction of keratin from human hair using protic ionic liquids

Keratin, the naturally derived biomaterials have been developed and widely applied in many different fields. Among the resources containing keratin, human hair is one of the most abundant natural fibers rich in keratin and one of the most abundant waste materials produced by humans. It is critical for both value-added human hair utilization and environmental protection if suitable solvents for the dissolution and regeneration of the keratin were developed. Ionic liquids (ILs) have been evidenced to be the green solvents to extract keratin from waste human hair. In this work, five novel Protic ILs were designed and synthesized in one step with inexpensive raw materials under mild conditions. The effect of different anions and cations, temperature, and water content on the dissolution ability of Protic ILs for human hair was investigated in depth. The best IL [MEA]HCOO with high solubilization capacity (9 h, 130 degrees C) for human hair was finally obtained by considering the time required for complete hair dissolution and the properties of regenerated keratin. The results of FTIR, XRD, and TGA showed that the a-helix structure of regenerated keratin was not destroyed. The recycling result indicates that the dissolution ability of [MEA]HCOO for human hair kept stable after 5 times recovery. Furthermore, the density functional theory (DFT) calculations and independent gradient model (IGM) analysis uncover the dissolution of human hair by ILs through synergistic interaction between the cations and anions of ILs. (c) 2022 Elsevier B.V. All rights reserved

Experimental and theoretical study on the extraction of keratin from human hair using protic ionic liquids

Keratin, the naturally derived biomaterials have been developed and widely applied in many different fields. Among the resources containing keratin, human hair is one of the most abundant natural fibers rich in keratin and one of the most abundant waste materials produced by humans. It is critical for both value-added human hair utilization and environmental protection if suitable solvents for the dissolution and regeneration of the keratin were developed. Ionic liquids (ILs) have been evidenced to be the green solvents to extract keratin from waste human hair. In this work, five novel Protic ILs were designed and synthesized in one step with inexpensive raw materials under mild conditions. The effect of different anions and cations, temperature, and water content on the dissolution ability of Protic ILs for human hair was investigated in depth. The best IL [MEA]HCOO with high solubilization capacity (9 h, 130 degrees C) for human hair was finally obtained by considering the time required for complete hair dissolution and the properties of regenerated keratin. The results of FTIR, XRD, and TGA showed that the a-helix structure of regenerated keratin was not destroyed. The recycling result indicates that the dissolution ability of [MEA]HCOO for human hair kept stable after 5 times recovery. Furthermore, the density functional theory (DFT) calculations and independent gradient model (IGM) analysis uncover the dissolution of human hair by ILs through synergistic interaction between the cations and anions of ILs. (c) 2022 Elsevier B.V. All rights reserved

On the Divergent Evolution of ENSO After the Coastal El Niños in 2017 and 2023

Abstract Coastal El Niño is an extreme situation of El Niño‐Southern Oscillation (ENSO) with sea surface temperature warming confined in the far‐eastern equatorial Pacific. Some coastal El Niños evolve into a basin scale El Niño, and some don't, implying a diversity in ENSO evolutions after a coastal El Niño event. In this study, the coastal El Niños in 2017 and 2023 are selected to examine their subsequent evolution. Both coastal El Niños developed after a La Niña, with the former followed by a La Niña and the latter by a basin‐scale El Niño. The cold (warm) subsurface temperatures in 2017 (2023) were key factors leading to the divergent ENSO evolution. Convection over the western tropical Pacific and the atmospheric circulation anomalies across the equatorial Pacific also contributed to the differences. Model predictions suggest that differences in ENSO evolution after a coastal El Niño are associated with differences in ENSO predictability

Loss of CDKN2A at chromosome 9 has a poor clinical prognosis and promotes lung cancer progression

Abstract Objective This study aimed to identify critical genes involved in the tumor biology of lung cancer via datamining of The Cancer Genome Atlas (TCGA) with special focus on gene copy number variation. Methods Genomic deletion and amplification were analyzed with cBioportal online tools. Relative expression of Cyclin Dependent Kinase Inhibitor 2A (CDKN2A) was analyzed by both real‐time polymerase chain reaction (PCR) and Western blot. The abundance of methylthioadenosine phosphorylase (MTAP) and epithelial‐mesenchymal transition markers were analyzed by real‐time PCR. Cell proliferation was determined by cell counting kit‐8 method and cell viability was measured with 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay. The cell migration and invasion were measured with transwell chamber assay, and migrative capacity was further evaluated by wound healing assay. Results We found the frequent loss of CDKN2A was associated with its downregulation in lung cancer, and siRNA‐mediated CDNKN2A knockdown significantly stimulated cell proliferation, invasion, and migration. Mechanistically, we unraveled that MTAP, which was positively correlated with CDKN2A, predominantly mediated the antitumoral function of CDKN2A in lung cancer. Conclusion Our study consolidated the involvement of CDKN2A‐MTAP signaling in the context of lung cancer