Al12Co4: a pioneering heterometallic aluminum oxo cluster with surface-exposed Co sites for the oxygen evolution reaction.

We report an unprecedented heterometallic aluminum oxo cluster (AlOC) containing four surface-exposed CoII sites, designated as Al12Co4, protected by four t-butylcalix[4]arene (TBC[4]) molecules. The Al12Co4 nanocluster represents a significant advancement on multiple innovative fronts. First, it stands as an pioneering example of an AlIII-based metallocalixarene nanocluster. It is also the first instance of heterometallic AlOCs shielded by macrocyclic ligands. Notably, this cluster also holds the distinction of being the highest nuclearity Al-Co bimetallic nanocluster known to date. Additionally, by depositing Al12Co4 on carbon nanotubes (CNTs) as a supported catalyst, we investigated its electrocatalytic performance for the oxygen evolution reaction in alkaline media. To reach a 10 mA cm-2 current density in alkaline solution, the Al12Co4@CNT electrode needs overpotential as low as 320 mV.

Heterometallic Polyoxotitanium Clusters as Bifunctional Electrocatalysts for Overall Water Splitting.

Incorporating heterometal into titanium-oxygen clusters (TOCs) is an effective way to improve its catalytic activity. Herein, we synthesize three novel heterometallic TOCs with the formula of [Ti6Cu2O7(Dmg)2(OAc)4(iPrO)6][H2Ti6Cu2O7(Dmg)2(OAc)4(iPrO)8] ({Ti6Cu2}), [Ti8Cu2O9(Dmg)2(OAc)2(iPrO)12] ({Ti8Cu2}), and [Ti10Co2O6(Dmg)2(Pdc)4(iPrO)18Cl3] ({Ti10Co2}, DmgH2 = dimethylglyoxime; PdcH2 = pyridine-2,3-dicarboxylic acid) using dimethylglyoxime and different carboxylates as the synergistic ligands. By depositing the clusters {Ti6Cu2} and {Ti10Co2} on carbon cloth as electrodes, we investigated the electrocatalytic performance of TOCs for full water splitting for the first time. To reach a 10 mA cm-2 current density in an alkaline solution, the {Ti10Co2}@CC electrode needs an overpotential as low as 120 and 400 mV for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER), respectively. In addition, full water-splitting equipment with {Ti10Co2}@CC as a cathode and an anode need only 1.67 V to deliver a current density of 10 mA cm-2. Our work confirmed the potential of noble metal-free TOCs as bifunctional cluster-based electrocatalysts for water splitting, and their activities can be tuned by doping with different metal ions.

Current Situation and Influencing Factors of Traditional Chinese Medicine Nursing Clinic in Henan Province.

Objective: To explore the current situation and influencing factors of traditional Chinese medicine (TCM) nursing clinic in Henan Province. A self-made questionnaire was made and entered into the questionnaire star. In August 2020, through "the snowball sampling method," the nursing branch of Henan Society of Traditional Chinese Medicine was used to calculate the sample size that would be further used for this study. Results: Of the 370 medical institutions in 17 district-level cities in our province, 47 have set up TCM nursing clinics, accounting for 12.70%. From the perspective of regional distribution, there are 14 TCM nursing clinics in Zhengzhou, 8 in Luoyang, 6 in Kaifeng, 4 in Shangqiu, 3 in Jiyuan, and 3 in Zhoukou. The number of TCM nursing clinics in Jiaozuo City, Xinxiang City, Anyang City, Hebi City, Puyang City, Zhumadian City, and Nanyang City is relatively small, and there are no TCM nursing clinics in Pingdingshan City, Sanmenxia City, and Xinyang City. Among the 47 medical institutions offering TCM nursing clinics, there are 38 TCM hospitals, 5 integrated traditional Chinese and Western medicine hospitals, 3 Western medicine hospitals, and 1 ethnic medicine hospital. Among them, 31 medical institutions are tertiary care hospitals and 16 are secondary care hospitals. First-class and undetermined medical institutions do not set up TCM nursing clinics. (1) Management mode: among the 47 medical institutions, 26 medical institutions have separate nursing units, which are managed by the nursing department head nurse, and 13 medical institutions are managed by the director head nurse of the department. (2) Performance management: of the 47 medical institutions that set up TCM nursing clinics, 18 adopted independent accounting, 21 adopted secondary distribution of departmental performance, and 7 adopted average awards and other methods. (3) The process of seeing a doctor: there are three kinds of medical procedures: 124 medical institutions are treated by TCM nursing outpatients by hanging the consultation number of doctors in various departments. 210 medical institutions are treated by traditional Chinese medicine nursing outpatient nurses by hanging the consultation number of traditional Chinese medicine nursing outpatient doctors. Thirty-five medical institutions are retreated by hanging the number of nurses in the nursing clinic of TCM. (4) Allocation of human resources: in the survey of the total number of nurses in TCM nursing clinics in 74 medical institutions, the largest number of nurses was 46 in one of the TCM nursing clinics. In terms of personnel qualification requirements, 43 medical institutions put forward requirements for nurses' qualifications. Among them, 39 medical institutions have requirements for nurses' professional titles, 38 medical institutions have requirements for nurses working years, and 22 medical institutions have more specific requirements for nurses. For example, nurses are required to be the backbone of TCM nursing that includes specialist nurses, nurses who graduated from TCM colleges, and nurses who have obtained hospital assessment and certification. In terms of working years, 87.96% of medical institutions require nursing service of more than 5 years. The average number of TCM nursing technical projects offered by 47 medical institutions is about 10, a maximum of 34 and a minimum of 1. The commonly carried out TCM nursing techniques include scraping, auricular point pressing, cupping, moxibustion, and ear tip bloodletting, and among all of them, scraping technology is most important and 40 medical institutions offer this technology, followed by auricular point pressing technique, cupping, and moxibustion. Conclusion: The construction of TCM nursing clinics in Henan Province has initially formed a scale, and all kinds of medical institutions at all levels should further strengthen the construction of TCM nursing clinics in all other provinces.

Self-Assembly of Chiral Ferrocene-Functionalized Polyoxotitanium Clusters for Photocatalytic Selective Sulfide Oxidation.

Here, we systematically studied the self-assembly behavior of chiral polyoxytitanium clusters for the first time. Through the cooperative assembly of ferrocenecarboxylic acid and ketoxime ligands, we successfully incorporated the planar chirality of ferrocene (Fc) into the layered {Ti5} building blocks. The resulting {Ti5Fc} clusters can be used as structural units to assemble into large ordered structures in various ways; either a pair of {Ti5Fc} enantiomers are bridged by organic adhesive to form sandwich structures or two homochiral {Ti5Fc} units participate in the assembly to form the large clusters. Depending on the assembly modes, the chirality of {Ti5Fc} can be transferred to large nanoclusters or disappear to form mesostructures. The difference of the assembly modes between the {Ti5Fc} units can also tune the photoelectric activity of the resulting clusters, which has been verified by using {Ti10Fc-6/7} as catalysts for photocatalytic selective sulfide oxidation. This work not only is an important breakthrough in the study of the self-assembly of chiral nanoclusters but also provides an important reference for understanding of chiral transfer on the nanoscale.

Metal-Directed Self-Assembly of {Ti8L2} Cluster-Based Coordination Polymers with Enhanced Photocatalytic Alcohol Oxidation Activity.

Cooperative assembly of the neutral cluster {Ti8O5(OEt)18L2} (L = pyrazine-2,3-dicarboxylic acid) with different metal units of Mn(NO3)2, CuCl2, Zn(OEt)2, Cd(NO3)2, Ce(NO3)3, Lu(NO3)3, and Lu(NO3)2(OEt), or the [Cu2I2] cluster, generates a family of titanium-oxygen cluster (TOC)-based coordination polymers. These one-dimensional (1D) linear structures contain the same {Ti8L2} cluster but with variable bridging metal units. The regulation of the heterometal not only affects the chain geometries of the {MTi8} but also affects the way the 1D chains are stacked in the crystal lattice. Investigation of the catalytic activities toward alcohol oxidation demonstrated the synergetic effect of combining the metal site and the photosensitive {Ti8L2} cluster in the tailored structure. Under light illumination, the {MTi8} with dual catalytic sites shows greatly enhanced catalytic activity in the selective oxidation of alcohols to aldehydes. Because the compositions and structures of {MTi8} are highly tunable, this work spotlights the potential of utilizing such metal-bridged multidimensional Ti-oxo materials for cooperative photoredox catalysis for organic transformation.

Bioinformatics analysis of C3 and CXCR4 demonstrates their potential as prognostic biomarkers in clear cell renal cell carcinoma (ccRCC).

BACKGROUND: The molecular prognostic biomarkers of clear cell renal cell carcinoma (ccRCC) are still unknown. We aimed at researching the candidate biomarkers and potential therapeutic targets of ccRCC. METHODS: Three ccRCC expression microarray datasets (include GSE14762, GSE66270 and GSE53757) were downloaded from the gene expression omnibus (GEO) database. The differentially expressed genes (DEGs) between ccRCC and normal tissues were explored. The potential functions of identified DEGs were analyzed by Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG). And then the protein - protein interaction network (PPI) was established to screen the hub genes. After that, the expressions of hub genes were identified by the oncomine database. The hub genes' prognostic values of patients with ccRCC were analyzed by GEPIA database. RESULTS: A total of 137 DEGs were identified by utilizing the limma package and RRA method, including 63 upregulated genes and 74 downregulated genes. It is found that 137 DEGs were mainly enriched in 82 functional terms and 24 pathways in accordance with the research results. Thirteen highest-scoring genes were screened as hub genes (include 10 upregulated genes and 3 downregulated candidate genes) by utilizing the PPI network and module analysis. Through integrating the oncoming database and GEPIA database, the author found that C3 and CXCR4 are not only overexpressed in ccRCC, but also associated with the prognosis of ccRCC. Further results could reveal that patients with high C3 expression had a poor overall survival (OS), while patients with high CTSS and TLR3 expressions had a good OS; patients with high C3 and CXCR4 expressions had a poor disease-free survival (DFS), while ccRCC patients with high TLR3 expression had a good DFS. CONCLUSION: These findings suggested that C3 and CXCR4 were the candidate biomarkers and potential therapeutic targets of ccRCC patients.

Accurate assembly of ferrocene-functionalized {Ti22Fc4} clusters with photocatalytic amine oxidation activity.

We report here the synthesis of a ferrocene-functionalized {Ti22Fc4} cluster with a 'dimer-of-clusters' topology, which represents the largest Ti-oxo cluster (TOC) modified with organometallic groups ever reported. The exact assembly path of {Ti22Fc4} can be inferred from its two substructures, {Ti11Fc2} and {Ti5Fc}, which can also be synthesized independently through subtle changes in reaction conditions. Furthermore, we used these clusters as photocatalysts, and have studied, for the first time, the photocatalytic activity of TOCs in the oxidative coupling of amines.

Chlamydia psittaci infection increases mortality of avian influenza virus H9N2 by suppressing host immune response.

Avian influenza virus subtype H9N2 (H9N2) and Chlamydia psittaci (C. psittaci) are frequently isolated in chickens with respiratory disease. However, their roles in co-infection remain unclear. We tested the hypothesis that C. psittaci enhances H9N2 infection through suppression of host immunity. Thus, 10-day-old SPF chickens were inoculated intra-tracheally with a high or low virulence C. psittaci strain, and were simultaneously vaccinated against Newcastle disease virus (NDV). Significant decreases in body weight, NDV antibodies and immune organ indices occurred in birds with the virulent C. psittaci infection, while the ratio of CD4+/CD8+ T cells increased significantly compared to that of the lower virulence strain. A second group of birds were inoculated with C. psittaci and H9N2 simultaneously (C. psittaci+H9N2), C. psittaci 3 days prior to H9N2 (C. psittaci/H9N2), or 3 days after H9N2 (H9N2/C. psittaci), C. psittaci or H9N2 alone. Survival rates were 65%, 80% and 90% in the C. psittaci/H9N2, C. psittaci+H9N2 and H9N2/C. psittaci groups, respectively and respiratory clinical signs, lower expression of pro-inflammatory cytokines and higher pathogen loads were found in both C. psittaci/H9N2 and C. psittaci+H9N2 groups. Hence, virulent C. psittaci infection suppresses immune response by inhibiting humoral responses and altering Th1/Th2 balance, increasing mortality in H9N2 infected birds.

Whole-Genome Sequences of Chlamydia psittaci Strain HJ, Isolated from Meat Pigeons with Severe Respiratory Distress and High Mortality.

The obligate intracellular Gram-negative bacterium Chlamydia psittaci causes systemic disease in psittacine birds, domestic poultry, and wild fowl. Importantly, C. psittaci may cause pneumonia, encephalitis, endocarditis, and even death in humans. The potential of pigeons as a source of human psittacosis is supported worldwide by relatively high seroconversion rates in the birds. This study reports the whole-genome sequencing of C. psittaci strain HJ, isolated from meat pigeons suffering from severe pneumonia and high mortality in 2013 in Hebei, China.

First principles study on the electronic properties of Zn(64)Sb(64-x)Te(x) solid solution (x = 0, 2, 3, 4).

The electronic properties of Te doped-ZnSb systems are investigated by first-principles calculations. We focus on the Zn(64)Sb(64-) (x)Te(x) systems (x = 0, 2, 3, 4), which respond to the 0, 1.56at%, 2.34at% and 3.12at% of Te doping concentration. We confirm that the amount of Te doping will change the conductivity type of ZnSb. In the cases of x = 2 and 3, we find that the Te element in ZnSb introduces some bands originating from Te s and p orbits and a donor energy level in the bottom of the conduction band, which induce the n-type conductivity of ZnSb. From these findings for the electronic structure and the conductivity mechanism, we predict that Te doping amounts such as 1.56at% and 2.34at% can be considered as suitable candidates for use as donor dopant.

GENETICS OF PRECALLING PERIOD IN THE ORIENTAL ARMYWORM, MYTHIMNA SEPARATA (WALKER) (LEPIDOPTERA: NOCTUIDAE), AND IMPLICATIONS FOR MIGRATION.

Migration in insects usually occurs prereproductively so the precalling period, between emergence and the first release of pheromone, determines the number of nights over which females of migrants such as Mythimna separata can express their migratory potential. Precalling periods (PCP's) ranged from 3 to 21 nights in F1 females from insects collected in the field in eastern China. As technical problems precluded the use of a sib-analysis design, the genetic basis of this variation was investigated by analysis of the correlation between daughters' and mother's PCP's and by selection in isofemale lines followed by reciprocal crosses. The results of these analyses indicated that PCP is strongly influenced by genes located on the X chromosome, inherited from the male parent in Lepidoptera. Genetic regulation of migratory potential, of which PCP is a crucial component, can be expected to evolve in tropical species such as Mythimna separata, whose larval habitats are associated with unpredictable tropical rainfall. This species has no preimaginal diapause but makes regular seasonal incursions every spring and early summer to high temperate latitudes at which it cannot overwinter. Where migrants are carried by winds, as occurs in these migrations, the predominantly poleward winds at this time of year must create a genetic cline across latitude, in which migratory potential of the summer populations founded by the migrants increases with increasing latitude. We suggest that X-linkage of genes influencing PCP may reduce the genetic load associated with this polymorphism by reducing the frequencies of inappropriate PCP genotypes in these summer populations. Thus, in autumn when winds are predominantly northerly, fewer individuals at any latitude will lack the capability to make the return journey southward. Some support for this model is provided by the observed distributions of PCP's of F1 females from moths collected in the field in central and northern eastern China. If X-linkage of genes influencing PCP contributes to the stability of these migratory cycles, it can be expected in other species with similar migratory strategies.