Breaking the Hoff/Le Bel rule by an electron-compensation strategy: the global energy minimum of NGa4S4.

In tetracoordinate chemistry, there is an attractive scientific problem of how to make the planar configuration more stable than the tetrahedral configuration. For tetracoordinate nitrogen, the abundant studies indicate that the planar tetracoordinate nitrogen (ptN) is far less stable than the tetrahedral tetracoordinate nitrogen (ttN). Herein, we introduced four S atoms to the unstable ptN-NGa4+ and stable ttN-NGa4+ by following an electron-compensation strategy. Surprisingly, ptN-NGa4S4+ is more stable than ttN-NGa4S4+. Thermodynamically, ptN-NGa4S4+ is the global energy minimum, which is 46.7 kcal mol-1 lower in energy than ttN-NGa4S4+. Dynamically, the BOMD simulations indicated that ptN-NGa4S4+ has excellent dynamic stability at 4, 298, 500 and 1000 K, but the ttN-NGa4S4+ is isomerized at 1000 K. Electronically, the HOMO-LUMO gap of ptN-NGa4S4+ (6.91 eV) is much wider than that of ttN-NGa4S4+ (5.25 eV). Moreover, AdNDP analyses showed that the eight 2c-2e Ga-S σ-bonds eliminated the 4s2 lone pair/4s2 lone pair repulsion between the four Ga atoms and provided a strong spatial protection for ptN-NGa4S4+; and that the four 3c-2e Ga-S-Ga π back-bonds could compensate electrons for Ga, weakening the electron-deficiency of Ga. Simultaneously, the double 6σ/2π aromaticity further enhanced the stability of ptN-NGa4S4+. Thus, as the dynamically stable global energy minimum displaying double aromaticity, ptN-NGa4S4+ will be more promising than ttN-NGa4S4+ in gas phase generation.

Study on the Microstructure of Mg-4Zn-4Sn-1Mn-xAl As-Cast Alloys.

In this study, the microstructure of the Mg-4Zn-4Sn-1Mn-xAl (x = 0, 0.3 wt.%, denoted as ZTM441 and ZTM441-0.3Al) as-cast alloys was investigated using scanning electron microscopy (SEM), focused-ion/electron-beam (FIB) micromachining, transmission electron microscopy (TEM), and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). The analysis results revealed that the microstructure of the ZTM441 and ZTM441-0.3Al as-cast alloys both mainly consist of the α-Mg matrix, skeleton-shaped MgZn2 eutectic texture, block-shaped Mg2Sn, and Zn/Sn-rich nanoscale precipitate bands along the grain boundary and the interdendrite. Nanoscale α-Mn dispersoids formed in the grain in the ZTM441 alloy, while no α-Mn formed in the ZTM441-0.3Al alloy instead of nanoscale Al3Mn2 particles. In the ZTM441 as-cast alloy, part of the Zn element is dissolved into the α-Mn phase, and part of the Mn element is dissolved into the MgZn2 phase, but in the ZTM441-0.3Al alloy, there are no such characteristics of mutual solubility. Zn and Mn elements are easy to combine in ZTM441 as-cast alloy, while Al and Mn are easy to combine in ZTM441-0.3Al as-cast alloy. The Mg-Zn phases have not only MgZn2-type crystal structure but also Mg4Zn7- and Mg149Zn-type crystal structure in the ZTM441-0.3Al as-cast alloy. The addition of Al changes the combination of Mn and Zn, promotes the formation of Al3Mn2, and the growth of the grain.

Alternative splicing of IRF3 plays an important role in the development of hepatocarcinoma.

Alternative splicing is a process causing mRNA translation to produce different proteins, and it is crucial for the development of tumours. In this study, we constructed a prognostic model related to alternative splicing events in hepatocarcinoma using bioinformatics analysis, including the alternative splicing of CSAD, AFMID, ZDHHC16, and IRF3. The model is an independent prognostic factor and can accurately predict a patient's prognosis. IRF3 is a transcription factor related to the immune response. Its alternative splicing can affect the expression of various genes related to prognosis and plays an essential role in the tumour microenvironment. We also verified the expression of IRF3 exon skipping isoform in hepatocarcinoma at the mRNA level. In conclusion, we discovered that the alternative splicing of IRF3 is essential for the development of hepatocarcinoma. This study provides new insight into the development of treatments for hepatocarcinoma.

Human peritoneal tight junction, transporter and channel expression in health and kidney failure, and associated solute transport.

Next to the skin, the peritoneum is the largest human organ, essentially involved in abdominal health and disease states, but information on peritoneal paracellular tight junctions and transcellular channels and transporters relative to peritoneal transmembrane transport is scant. We studied their peritoneal localization and quantity by immunohistochemistry and confocal microscopy in health, in chronic kidney disease (CKD) and on peritoneal dialysis (PD), with the latter allowing for functional characterizations, in a total of 93 individuals (0-75 years). Claudin-1 to -5, and -15, zonula occludens-1, occludin and tricellulin, SGLT1, PiT1/SLC20A1 and ENaC were consistently detected in mesothelial and arteriolar endothelial cells, with age dependent differences for mesothelial claudin-1 and arteriolar claudin-2/3. In CKD mesothelial claudin-1 and arteriolar claudin-2 and -3 were more abundant. Peritonea from PD patients exhibited increased mesothelial and arteriolar claudin-1 and mesothelial claudin-2 abundance and reduced mesothelial and arteriolar claudin-3 and arteriolar ENaC. Transperitoneal creatinine and glucose transport correlated with pore forming arteriolar claudin-2 and mesothelial claudin-4/-15, and creatinine transport with mesothelial sodium/phosphate cotransporter PiT1/SLC20A1. In multivariable analysis, claudin-2 independently predicted the peritoneal transport rates. In conclusion, tight junction, transcellular transporter and channel proteins are consistently expressed in peritoneal mesothelial and endothelial cells with minor variations across age groups, specific modifications by CKD and PD and distinct associations with transperitoneal creatinine and glucose transport rates. The latter deserve experimental studies to demonstrate mechanistic links.Clinical Trial registration: The study was performed according to the Declaration of Helsinki and is registered at www.clinicaltrials.gov (NCT01893710).

Self-Construction of Efficient Interfaces Ensures High-Performance Direct Ammonia Protonic Ceramic Fuel Cells.

Direct ammonia protonic ceramic fuel cells (PCFCs) are highly efficient energy conversion devices since ammonia as a carbon-neutral hydrogen-rich carrier shows great potential for storage and long-distance transportation when compared with hydrogen fuel. However, traditional Ni-based anodes readily suffer from severe structural destruction and dramatic deactivation after long-time exposure to ammonia. Here a Sr2 Fe1.35 Mo0.45 Cu0.2 O6-δ (SFMC) anode catalytic layer (ACL) painted onto a Ni-BaZr0.1 Ce0.7 Y0.1 Yb0.1 O3- δ (BZCYYb) anode with enhanced catalytic activity and durability toward the direct utilization of ammonia is reported. A tubular Ni-BZCYYb anode-supported cells with the SFMC ACL show excellent peak power densities of 1.77 W cm-2 in wet H2 (3% H2 O) and 1.02 W cm-2 in NH3 at 650 °C. A relatively stable operation of the cells is obtained at 650 °C for 200 h in ammonia fuel. Such achieved improvements in the activity and durability are attributed to the self-constructed interfaces with the phases of NiCu or/and NiFe for efficient NH3 decomposition, resulting in a strong NH3 adsorption strength of the SFMC, as confirmed by NH3 thermal conversion and NH3 -temperature programmed desorption. This research offers a valuable strategy of applying an internal catalytic layer for highly active and durable ammonia PCFCs.

The trigger for pancreatic disease: NLRP3 inflammasome.

NLRP3 inflammasome is a multiprotein complex expressed in a variety of cells to stimulate the production of inflammatory factors. Activation of NLRP3 inflammasome depends on a complex regulatory mechanism, and its pro-inflammatory function plays an important role in pancreatic diseases. In this literature review, we summarize the activation mechanism of NLRP3 and analyze its role in each of the four typical pancreatic diseases. Through this article, we provide a relatively comprehensive summary to the researchers in this field, and provide some targeted therapy routes.

18-valence-electron rule lighted planar tetracoordinate carbon and nitrogen: the global energy minima of CAl4Zn and NAl4Zn.

The exploration of planar hypercoordinate carbon (phC) is challenging and significant. It is often puzzling to chemists whether the designed phC species should satisfy the 18-valence-electron rule, an authoritative rule in the phC field. In this study, we introduced a zinc atom into the extremely unstable 16-valence-electron planar tetracoordinate carbon (ptC) species CAl4 and its isoelectronic structure NAl4+ with a planar tetracoordinate nitrogen (ptN), and designed the 18-valence-electron CAl4Zn and NAl4Zn+ possessing a ptC and ptN, respectively. The thermodynamic results indicate that the ptC/N species CAl4Zn and NAl4Zn+ are the global energy minima, and also showed that the 18-valence-electron rule is more appropriate in designing ptC/N species having the CAl4 and NAl4+ skeletons, compared with the 16-valence-electron rule. Simultaneously, the BOMD simulations found that CAl4Zn is dynamically stable. Although NAl4Zn+ was isomerized at 298 and 500 K, it is dynamically viable. The excellent stability may be explained by the perfect electronic structure. First, the HOMO-LUMO gaps became much wider after the introduction of the Zn atom. Second, AdNDP analysis indicated that the introduction of the Zn atom promoted the formation of peripheral Al-Al and Al-Zn covalent bonds, providing a stable and comfortable bonding environment for ptC/N. In addition, the σ and π double aromaticity further stabilized the ptC/N species. Hence, as dynamic global energy minima display σ and π double aromaticity, the ptC/N species CAl4Zn and NAl4Zn+ are promising in gas phase generation.

Association between trans fatty acids and COVID-19: A multivariate Mendelian randomization study.

Traditional observational studies have suggested a potential association between trans fatty acids (TFAs), which are considered to be health-damaging fatty acids, and coronavirus disease 2019 (COVID-19). However, whether there is a causal relationship between them is currently unclear. We aimed to investigate the causal link between genetically determined TFAs and COVID-19. We performed univariate and multivariate Mendelian randomization (MR) studies using summary statistics from the European Pedigree TFAs (n = 8013), COVID-19 susceptibility (n = 159 840), COVID-19 hospitalization (n = 44 986), and COVID-19 severity (n = 18 152) genome-wide association studies (GWAS). The inverse variance weighted (IVW) method was used as the primary MR analysis, and several other methods were used as supplements. In univariate MR analysis, higher levels of circulating trans, cis-18:2 TFAs were positively associated with a higher COVID-19 hospitalization rate (p < 0.0033; odds ratio [OR] = 1.637; 95% confidence interval [CI]: 1.116-2.401) and COVID-19 severity (p < 0.0033; OR = 2.575; 95% CI: 1.412-4.698). Furthermore, in multivariate MR analysis, trans, cis-18:2 had an independent and significant causal association with a higher COVID-19 hospitalization rate (p = 0.00044; OR = 1.862; 95% CI = 1.316-2.636) and COVID-19 severity (p = 0.0016; OR = 2.268; 95% CI = 1.361-3.779) after the five TFAs were adjusted for each other. Together, our findings provide evidence that trans, cis-18:2 TFAs have an independent and robust causal effect on COVID-19 hospitalization and severity.

Genetic instability-related lncRNAs predict prognosis and influence the immune microenvironment in breast cancer.

Genome instability is a hallmark of cancer, and the function of lncRNAs in regulating genomic stability has been gradually characterized. However, the prognostic value of lncRNAs related to genetic instability has not been found in breast cancer. Here we constructed a genetic instability-related lncRNA model including U62317.4, SEMA3B-AS1, MAPT-AS1, AC115837.2, LINC01269, AL645608.7, and GACAT2. This model can evaluate the risk and predict the survival outcomes of patients. Further analysis showed that the differentially expressed genes between the high- and low-risk groups were enriched in immunity and cornified envelope formation pathways. In addition, M2 macrophages infiltrated more obviously in the high-risk group. In summary, lncRNAs related to genetic instability may influence the development of breast cancer through immune infiltration and keratinization. This study provides a wider insight into breast cancer development and treatment.

Evaluation of the local decoupling of livestock and cropland in the Huang-Huai-Hai region.

Decoupling livestock and cropland production at regional scale have poor resource-use efficiency and detrimental effects on environment in China. It is therefore necessary to identify the decoupled livestock and cropland production system and make recommendations to recouple livestock and cropland. This study used the indexes of land carrying capacity (LCC), animal manure absorption capacity (AMAC), and risk warning value (R) to evaluate the coupling between cropland and livestock at the local scale in the Huang-Huai-Hai region. The decoupling of cropland and livestock in the case of Beijing (SY_BJ) was found assessed with lower theoretical value of LCC and higher theoretical value of AMAC compared with local actual situation, categorized as grade IV with a high R value (above 1). Contrary results were found that the livestock and cropland production systems were coupled at the local scale in the cases located in Hebei and Shandong Provinces, categorized as grade I or II. Two measures were used to optimize the decoupled case by adjusting the ratio of manure to fertilization or reducing breeding quantity. The decoupled case of SY_BJ could be optimized by adjusting the ratio of manure to fertilization (95.34% based on nitrogen and 81.97% based on phosphorus, respectively). The breeding quantity in this case should be reduced by at least 46% to recouple the livestock and cropland at the local level to manage nutrient surpluses from livestock and poultry breeding.

Precipitation Behavior of Mg-7Gd-3Y-2Zn-0.5Zr Alloy during Isothermal Aging.

Precipitate phases in an Mg-7Gd-3Y-2Zn-0.5Zr alloy aged isothermally at 240 °C were examined using high-resolution transmission electron microscopy (TEM) and high-angle annular dark-field scanning TEM. The two types of precipitation sequence that involve Mg-Gd and long period stacking ordered (LPSO) type were found. The LPSO type sequence consisted of the precipitation of γ'', γ', 14H-LPSO/18R-LPSO. The Mg-Gd type precipitation sequence involved the formation of ß'(b.c.o.) and ß1(f.c.c.). The sequence, morphology, distribution, and crystal structure of these precipitates formed during isothermal aging were investigated. The results indicated that the priority precipitation of Mg-Gd and LPSO type sequences during aging can be affected by Nd, which has a higher diffusion coefficient than Gd and Y. The dislocation structures and strengthening mechanism were also discussed.

Beyond the Intention: Individual-Level Determinants and Intergenerational Differences of Floating Populations' Actual Settlement Choices in Dongguan, China.

The migration process and patterns of floating populations have received continuing attention from scholars and policymakers. In China, however, studies have been focused on the settlement intention of floating populations based on sampling surveys and yielded inconsistent findings. Drawing upon 18,178,167 authentic individual samples of floating populations in Dongguan city, this study contributes to the literature by examining the effect of individual characteristics on the actual resident actions of floating populations, and revealing both the heterogeneity and continuity of their urban residence among four generations (i.e., during the 1960s, 1970s, 1980s, and 1990s). The results show that the proportion of actual resident actions is lower than that reported by previous studies on settlement intentions, and that male, married, middle-aged, more educated, and long-residing members are more likely to choose to stay in Dongguan. Compared to their predecessors, the 1990 cohort reveals significant heterogeneities in their actual settlement choices. The study draws broad implications from the analysis, calling for the equalization of public welfare in Chinese cities and the encouragement of floating populations to sustain long-term residence in the destination cities.

Bio-Inspired Passion Fruit-like Fe3O4@C Nanospheres Enabling High-Stability Magnetorheological Performances.

Magnetorheological (MR) fluids have been successfully utilized in versatile fields but are still limited by their relatively inferior long-term dispersion stability. Herein, bio-inspired passion fruit-like Fe3O4@C nanospheres were fabricated via a simple hydrothermal and calcination approach to tackle the settling challenge. The unique structures provide sufficient active interfaces for the penetration of carrier mediums, leading to preferable wettability between particles and medium oils. Compared with the bare Fe3O4 nanoparticle suspension, the resulting Fe3O4@C nanosphere-based MR fluid exhibits desirable stability and relatively low field-off viscosity even at a high particle concentration up to 35 vol %.

Peripheral Dopamine Controlled by Gut Microbes Inhibits Invariant Natural Killer T Cell-Mediated Hepatitis.

Neurotransmitters have been shown to regulate immune responses, and thereby are critically related to autoimmune diseases. Here we showed that depletion of dopaminergic neurons significantly promoted activation of hepatic iNKT cells and augmented concanavalin A (Con A)-induced liver injury. The suppressive effect of dopamine on iNKT cells was mediated by D1-like receptor-PKA pathway. Clearance of gut microbiota by antibiotic cocktail reduced synthesis of dopamine in intestines and exacerbated liver damage, and that could be restored by recovery of gut microbiota or replenishment of D1-like receptor agonist. Our results demonstrate that peripheral dopamine controlled by gut microbes inhibits IL4 and IFNγ production in iNKT cells and suppresses iNKT cell-mediated hepatitis. Together, we propose a gut microbe-nervous system-immune system regulatory axis in modulating autoimmune hepatitis.

Memory Follicular Helper Invariant NKT Cells Recognize Lipid Antigens on Memory B Cells and Elicit Antibody Recall Responses.

Invariant NKT (iNKT) cells have been shown to help B cells in a cognate or noncognate manner; however, whether cognate iNKT cell help induces B cell memory responses remains controversial, and the underlying mechanisms are still unclear. In this study, we demonstrated that, in the absence of follicular helper T cells, cognate iNKT cell help could promote B cell memory responses in mice that were dependent on the formation of memory follicular helper iNKT (iNKTFH) cells and their interactions with memory B cells in recall responses. Generation of memory iNKTFH cells required lipid Ag presentation by dendritic cells but not by B cells. Upon rechallenge, memory iNKTFH cells recognized lipid Ags presented by memory B cells, which recalled iNKTFH effector cells and elicited B cell memory responses. However, LPS, which promoted the synthesis of self-lipids, failed to elicit recall responses in the absence of exogenous lipid Ags.

The mutual restraint effect between the expansion of Alternanthera philoxeroides (Mart.) Griseb and cadmium mobility in aquatic environment.

Alternanthera philoxeroides (Mart.) Griseb is one of the most malignant weeds in its invision habitats. While in the cadmium-contaminated aquatic environment, does A. philoxeroides possess good tolerance and adaptability? To demonstrate the effects of cadmium on A. philoxeroides in the polluted water bodies, a hydroponic stress experiment was conducted over a gradient of Cd concentrations (0, 2.5 and 5mg/l) in triplicate. The seedlings were cultured in a greenhouse and harvested on days 0, 10, 20, 30 and 40, respectively. The results showed the effects of mutual restraint between Cd and A. philoxeroides. The A. philoxeroides seedlings were enriched with large amounts of Cd, and the toxicity of Cd inhibited the rapid growth of A. philoxeroides and induced the rapid degradation of chlorophylls in its tissues. Furthermore, the use of iron plaque effectively immobilized Cd of 1123-2883mg/kg·DW on the root surface, thus it decreased the transferability of Cd in the aquatic environment. Due to its extensive adaptability, good Cd tolerance and the immobilization of Cd predominantly in the roots (the highest Cd concentration enriched was 7588.65±628.90mg/kg·DW in roots). A. philoxeroides effectively restrained the translocation of Cd and partitioned Cd in the roots within water bodies. CAPSULE: The antagonistic effect exists between the invasion of A. philoxeroides and cadmium mobility in aquatic environments.