CO2 Cleavage Reaction Driven by Alkylidyne Complexes of Group 6 Metals and Uranium: A Density Functional Theory Study on Energetics, Reaction Mechanism, and Structural/Bonding Properties.

Designing novel catalysts is essential for the efficient conversion of metal alkylidyne into metal oxo ketene complexes in the presence of CO2, which to some extent resolves the environmental concerns of the ever-increasing carbon emission. In this regard, a series of metal alkylidyne complexes, [b-ONO]M≡CCH3(THF)2 ([b-ONO] = {(C6H4[C(CF3)2O])2N}3-; M = Cr, Mo, W, and U), have been comprehensively studied by relativistic density functional theory calculations. The calculated thermodynamics and kinetics unravel that the tungsten complex is capable of catalyzing the CO2 cleavage reaction, agreeing with the experimental findings for its analogue. Interestingly, the uranium complex shows superior catalytic performance because of the associated considerably lower energy barrier and larger reaction rate constant. The M≡C moiety in the complexes turns out to be the active site for the [2 + 2] cyclic addition. In contrast, complexes of Cr and Mo could not offer good catalytic performance. Along the reaction coordinate, the M-C (M = Cr, Mo, W, and U) bond regularly transforms from triple to double to single bonds; concomitantly, the newly formed M-O in the product is identified to have a triple-bond character. The catalytic reactions have been extensively explained and addressed by geometric/electronic structures and bonding analyses.

Relativistic DFT Probe for Reaction Energies and Electronic/Bonding Properties of Polypyrrolic Hetero-Bimetallic Actinide Complexes: Effects of Uranyl endo-Oxo Functionalization.

A series of hetero-bimetallic actinide complexes of the Schiff-base polypyrrolic macrocycle (L), featuring cation-cation interactions (CCIs), were systematically investigated using relativistic density functional theory (DFT). The tetrahydrofuran (THF) solvated complex [(THF)(OUVIOUIV)(THF)(L)]2+ has high reaction free energy (ΔrG), and its replacement with electron-donating iodine promotes the reaction thermodynamics to obtain uranyl iodide [(I)(OUVIOUIV)(I)(L)]2+ (UVI-UIV). Retaining this coordination geometry, calculations have been extended to other An(IV) (An = Th, Pa, Np, Pu), i.e., for the substitution of U(IV) to obtain UVI-AnIV. As a consequence, the reaction free energy is appreciably lowered, suggesting the thermodynamic feasibility for the experimental synthesis of these bimetallic complexes. Among all UVI-AnIV, the electron-spin density and high-lying occupied orbitals of UVI-PaIV show a large extent of electron transfer from electron-rich Pa(IV) to electron-deficient U(VI), leading to a more stable UV-PaV oxidation state. Additionally, the shortest bond distance and the comparatively negative Eint of the Pa-Oendo bond suggest more positive and negative charges (Q) of Pa and endo-oxo atoms, respectively. As a result of the enhanced Pa-Oendo bond and strong CCI in UVI-PaIV along with the corresponding lowest reaction free energy among all of the optimized complexes, uranyl species is a better candidate for the experimental synthesis in the ultimate context of environmental remediation.

Main-Group Metals Stabilized Polypyrrolic Uranyl(V) Complexes via Cation-Cation Interaction with the Uranyl exo-Oxo Atom: A Relativistic Density Functional Theory Study.

To explore the innovative uranyl(V) complexes by deeply understanding their coordination stability, relativistic density functional theory calculations have been performed to investigate the experimentally reported [(py)(R2AlOUVO)(py)(H2L)] [R = Me (1), iBu (2)] and [{(py)3MOUVO}(py)(H2L)] [M = Li (3), Na (4), K (5)] and their uranyl(VI) counterparts. Structural and topological analyses along with transformation-reaction energies and redox potentials were systematically studied. Geometrical and quantum theory of atoms in molecules analyses implied a linear U-Oexo-M feature in 1-3 and a bent one in 4 and 5. The calculated free energies (ΔrG) of reactions transforming 1/2 into 3/4/5 confirmed a higher stability of the latter ones, which were further corroborated by their reduction potentials (E0). The E0 value of 5 versus uranyl(VI) is close to its experimental value, particularly in solvation with spin-orbit coupling. The highest occupied and lowest unoccupied molecular orbitals of uranyl(V) and uranyl(VI) have predominant U(5fδ) character. Compared to mononuclear uranyl(VI), the coordination of aluminum and alkali metals to uranyl exo-oxo significantly contributes to the stabilization of uranyl(V) by altering the E0 value from -1.59 to -0.85, -0.91, -1.33, -1.50, and -1.46 V, respectively. The calculation results show a more positive E0 than that of the precursor 6VI/6 without exo-oxo coordination. The calculated E0 values of 3-5 are certainly more negative than those of 1 and 2. The alkali metals were found to activate U═O bonds more easily/readily than aluminum by coordination to the exo-oxo atom. In brief, the uranyl exo-oxo cation-cation-interaction enhanced the reduction ability from its uranyl(VI) analogue and raised the stability of the UV center.

lncRNA TUG1 modulates proliferation, apoptosis, invasion, and angiogenesis via targeting miR-29b in trophoblast cells.

BACKGROUND: Pre-eclampsia (PE) is regarded as the leading cause of maternal and neonatal morbidity and mortality. Nevertheless, the potential mechanism for the regulation of trophoblast behaviors and the pathogenesis of PE remain largely elusive. Recently, accumulating evidence emphasized that aberrant expression of long non-coding RNAs (lncRNAs) functions as imperative regulators in human diseases, including PE. Thus, identifying PE-related specific lncRNAs to uncover the underlying molecular mechanism is of much significance. However, the functional roles and underlying mechanisms of lncRNAs in PE progression remain unclear. METHOD: Placenta tissues obtained from patients with PE and healthy pregnant women were performed to measure TUG1 expression by qRT-PCR analysis. Transient transfections were conducted to alter TUG1 expression. Cell Counting Kit-8 (CCK-8) and flow cytometry assays were carried out to assess cell proliferation and apoptosis, respectively. Transwell and tube formation assays were performed to measure the capacity of cell invasion and angiogenesis. Moreover, the luciferase reporter assay was subjected to verify the binding relationship between TUG1 and miR-29b. Western blot analysis was performed to detect the expression of key proteins in the PI3K/AKT and ERK pathway. RESULTS: Here, we identified a lncRNA, TUG1, which was notably decreased in placental samples of PE patients. Functional experiments of loss- or gain-of-function assays also verified that ectopic expression of TUG1 promoted cell proliferation, invasion, and angiogenesis, but negatively regulated cell apoptosis, whereas TUG1 inhibition presented the opposite effects. Furthermore, mechanistic researches revealed that TUG1 could act as a molecular sponge for miR-29b, thus regulating MCL1, VEGFA, and MMP2 to modulate PE development. CONCLUSIONS: Taken together, our findings demonstrated that TUG1 exerts as a critical role in PE progression, which might furnish a novel therapeutic marker for PE treatment.

Influence of fetal Leydig cells on the development of adult Leydig cell population in rats.

Leydig cells are the main endogenous testosterone synthesis cells in the body. Testosterone is an essential hormone in males that affects metabolism, emotion, and pubertal development. However, little is known about the development of Leydig cells and relationship between fetal Leydig cells (FLCs) and adult Leydig cells (ALCs). The aims of this study were to investigate the effect of (FLCs) on ALC development. Our study showed that FLCs in neonatal rat testis can be eliminated by 100 mg/kg ethane dimethane sulfonate (EDS) treatment without affecting the health of newborn rats. Immunohistological results showed that eliminating FLCs led to early re-generation of the ALC population (progenitor Leydig cells [PLCs] and ALCs) accompanied at first by increased and then by decreased serum testosterone, indicating that ALCs which appeared after neonatal EDS treatment were degenerated or had attenuated functions. Our results showed that FLCs were eliminated 4 days after EDS treatment, the ALC population regenerated by 21 days, and serum testosterone levels dramatically decreased at 56 days. Collectively, our results indicate that the ablation of FLCs in neonatal rat results in abnormal development of ALCs. Our study further indicates that abnormal development of Leydig cells in the fetal stage leads to steroid hormone disorders, such as testosterone deficiency, in the adult stage. Therefore, studies of Leydig cell development are important for understanding the pathogenesis of testosterone deficiency or pubertas praecox.

A relativistic DFT probe of polypyrrolic macrocyclic diuranium(III) complexes with terminal solvents and iodines.

Relativistic density functional theory finds that two isomers of a diuranium(III) complex of a polypyrrolic macrocycle (H4L) feature active sites on uranium moieties, allowing for their potential application in activating industrially and economically important small molecules. To address this, a series of adducts [(X)nU2(L)]((2-m)+) (X = THF, I(-) and HI; n = 1 and 2; m = 0, 1 and 2) have been examined. The coordination from X to the exposed uranium(s) changes the general geometry and electronic structure slightly. Thermodynamic calculations reveal that iodine termination is energetically favored over THF/HI coordination. Graphical abstract Scalar and spin-orbit coupling relativistic DFT calculation reveals that the active sites on the uranium moieties of [U2(L)](2+) lead to formation of adducts [(THF)nU2(L)](2+), [InU2(L)]((2-n)+) and [(HI)nU2(L)](2+) (n = 1 and 2). Coordination to the exposed uranium(s) changes geometrical and electronic properties slightly, but iodine termination is the most energetically favored.

[Effects of Sialidase Inhibitor on Proliferation and Apoptosis of Endometrial Cancer Cells].

OBJECTIVES: To explore the effects of sialidase inhibitor on the proliferation and apoptosis of endometrial cancer Ishikawa cells. METHODS: Ishikawa cells were cultured and divided into 2 groups: control group and sialidase inhibitor N-Acetyl-2, 3-dehydro-2-deoxyneuraminic acid (DANA) treated group. After the sialidase activity was compared between the two groups, the expression level of matrix metalloproteinases (MMPs), proliferating cell nuclear antigen (PCNA), apoptosis rate and proliferation ability were detected by immunofluorescence staining, flow cytometry or MTT assay. RESULTS: With the treatment of DANA, the activity of sialidase in the cell culture supernatant was suppressed while MMPs expression levels and apoptosis rate of Ishikawa cells were decreased. The expression level of PCNA and cell proliferation showed no statistical differences in two groups. CONCLUSIONS: Sialidase could affect the invasive ability and apoptosis rate of Ishikawa cells, but it seems no effect on cell proliferation.

[Treatment of nonalcoholic steatohepatitis by Jianpi Shugan Recipe: a multi-center, randomized, controlled clinical trial].

OBJECTIVE: To evaluate the efficacy and safety of Chinese medicine (CM) intervention in the treatment of nonalcoholic steatohepatitis (NASH) from liver enzyme (ALT), imaging (the liver/spleen CT ratio) and syndrome scores, and to establish standard methods for diagnosis and therapeutic efficacy evaluation with characteristics of CM. METHODS: A multi-center, stratified randomized, parallel controlled, blindness-method evaluated, superiority trial was performed. Totally 204 patients were randomly allocated into two groups, 102 patients in the experimental group (treated with CM) and 102 patients in the control group [treated with Western medicine (WM)]. The alanine aminotransferase (ALT), liver/spleen CT ratio, and clinical symptoms were observed in both groups. RESULTS: Of the randomly allocated 204 cases from 4 hospitals, 3 patients were rejected, and 25 were lost. Totally 176 cases con- formed to the plan with complete follow-ups. After 3 months of treatment, syndrome scores and the improvement of partial clinical symptoms (fatigue and sallow complexion) were superior in the experimental group to those in the control group (P < 0.05). After 3 months of follow-up, the syndrome scores and improvement of partial clinical symptoms (fatigue and sallow complexion) were superior in the experimental group to those in the control group (P < 0.05). There was no statistical difference in improving liver enzymes or the liver/spleen CT ratio between the two groups (P > 0.05). There were 4 adverse reactions/adverse events in the two groups in the process of treatment, mainly covering drug-induced liver injury, diarrhea, and epigastric distension. Adverse reactions had nothing to do with CM treatment. CONCLUSIONS: Jianpi Shugan Recipe had obvious efficacy in treatment of NASH. It could remove the liver fat and play a role in anti-inflammation and liver protection. It also could improve the indices of liver enzymes and the liver/spleen CT ratio effectively, which was superior to Polyene Phosphatidylcholine Capsule (PPC) in improving clinical symptoms, especially for such symptoms as fatigue and sallow complexion.

[Effects of carbon disulfide on cardiovascular system of workers occupationally exposed to carbon disulfide].

OBJECTIVE: To study the effects of long-term exposure to carbon disulfide (SC(2)) on cardiovascular system of workers. METHODS: The concentrations of CS(2) were detected in the representative workshops with different exposure levels. The indicators related to cardiovascular system were tested in 633 workers occupationally exposed to CS(2), which included blood pressure, electrocardiogram, blood routine (blood RT), cholesterol (TCHO), triglyceride (TG) and so on. The data were analyzed by chi-square test and multiple logistic regression analysis. RESULTS: The exposure concentration of CS(2) for 389 workers was less than or equal to 5 mg/m(3), which for other 244 workers was higher than 5 mg/m(3). The maximum exposure concentration of CS(2) was 15.73 mg/m(3). There were no significant effects of CS(2) on the electrocardiogram, red blood cells, white blood cells, blood platelet, TCHO and TG of workers. However, the positive effects of CS(2) on blood pressure and negative effects of CS(2) on hemoglobin were found. The rates of high TCHO, TG and hypertension in male workers were significantly higher than those in female workers (P < 0.05). The rates of high TCHO, hypertension and sinus arrhythmia in older workers (≤ 30 years old) were significantly higher than those in young workers (> 30 years old) (P < 0.05). The rate of sinus arrhythmia in workers with 1 - 10 working years was significantly higher than that in workers with more than 10 working years (P < 0.05). The rate of hypertension in workers with 1 - 10 working years was significantly lower than that in workers with more than 10 working years (P < 0.05). CONCLUSION: There were no significant effects of CS(2) exposure on the indexes of cardiovascular system of workers.

Identification of a novel mutation in a pseudohypoparathyroidism family.

Pseudohypoparathyroidism type Ia (PHP Ia) is defined as a series of disorders characterized by multihormone resistance in end-organs and Albright hereditary osteodystrophy (AHO) phenotype. PHP Ia is caused by heterozygous inactivating mutations in GNAS, which encodes the stimulatory G-protein alpha subunit (Gsa). A patient with typical clinical manifestations of pseudohypoparathyroidism (PHP) (round face, short stature, centripetal obesity, brachydactyly, and multi-hormone resistance: parathyroid hormone (PTH), thyroid-stimulating hormone (TSH), and gonadotropins) presented at our center. The sequence of the GNAS gene from the patient and her families revealed a novel missense mutation (Y318H) in the proband and her mother. An in vitro Gsa functional study showed that Gsa function was significantly impaired. These results stress the importance of GNAS gene investigation.

[Relationship between job burnout and quality of life of factory staff].

OBJECTIVE: To investigate the status of job burnout and the quality of life of factory staff and analyze the their relationship. METHODS: Questionnaires were administered to investigate the status of job burnout and quality of life of all the staff in three randomly selected state factories, and then the methods of canonical correlation and hierarchical linear regression analysis were used to analyze the relationship between job burnout and quality of life. RESULTS: Job burnout and quality of life were somewhat different among staff in factories of different demography character. Emotional exhaustion was negatively associated with mental component summary (MCS). The predictive variables of physical component summary (PCS) were age, educational attainment, emotional exhaustion and professional efficacy and the standard partial regression coefficients of the four variables were -0.101, 0.055, -0.294, -0.058 respectively (P < 0.05). Educational level positively predicted the physical component summary, whereas age, emotional exhaustion and professional efficacy predicted physical component summary negatively. The predictive variables of mental component summary were emotional exhaustion, cynicism and professional efficacy and the standard partial regression coefficients of the three scale of job burnout were -0.546, -0.075, -0.184 (P < 0.05). All the three scales of job burnout predicted the mental component summary negatively. The emotional exhaustion was the most predictive variable for both the physical component summary and the mental component summary. CONCLUSION: Job burnout is the important risk factor of quality of life of factory staff, especially influencing the staff's metal health significantly.