Photocatalytic Hydrosilylation over Pt@UiO-66-NH2: Enhanced Activity and Polymerization Kinetics.

Metal-organic frameworks (MOFs) have shown great research and application value in various types of hydrosilylation reactions. However, studies on photocatalysis-induced hydrosilylation using MOFs are extremely rare. Metal nanoparticles (MNPs)@MOFs are extensively studied for their excellent structural tunability and photocatalytic activity, but there are few reports on their application in photocatalytic hydrosilylation. Here, a novel photocatalyst consisting of platinum (Pt) nanoparticles immobilized in a MOF framework is synthesized and used for photocatalytic hydrosilylation. The effects of various factors on hydrosilylation conversion are investigated, including catalyst concentration, substrate ratio, and irradiation intensity. Furthermore, the photoreactivity of the synthesized Pt catalyst is evaluated in the presence of different concentrations of 2-chlorothixanthone as a photosensitizer. It is noteworthy that the conversion of the reaction increases with increasing catalyst concentration or photosensitizer concentration, whereas increasing the polymethylhydrosiloxane content does not lead to a significant increase in conversion. This study demonstrates the potential of MNPs@MOFs as efficient photocatalysts for photoinduced hydrosilylation reactions and paves the way for future applications in this area.

Understanding the selection of catalytic pathway on graphene-supported nitrogen coordinated Ru-atom by ab initio molecular dynamics simulation.

CONTEXT: In the paper, the ORR/OER on graphene-supported nitrogen coordinated Ru-atom (Ru-N-C) is simulated. We discuss nitrogen coordination influences electronic properties, adsorption energies, and catalytic activity in a single-atom Ru active site. The over potentials on Ru-N-C are 1.12 eV/1.00 eV for ORR/OER. We calculate Gibbs-free energy (ΔG) for every reaction step in ORR/OER process. In order to gain a deeper understanding of the catalytic process on the surface of single atom catalysts, the ab initio molecular dynamics (AIMD) simulations show that Ru-N-C has a structural stability at 300 K and that ORR/OER on Ru-N-C can occur along a typical four-electron process of reaction. AIMD simulations of catalytic processes provide detailed information about atom interactions. METHODS: In this paper, we use density functional theory (DFT) with PBE functional to study the electronic properties and adsorption properties of graphene-supported nitrogen coordinated Ru-atom (Ru-N-C) Gibbs-free energy and Gibbs-free energy for very reaction step. The structural optimization and all the calculations are carried out by Dmol3 package, adopting the PNT basis set and DFT semicore pseudopotential. Ab initio molecular dynamics simulations (AIMD) were run for 10 ps. The canonical (NVT) ensemble, massive GGM thermostat, and a temperature of 300 K are taken into account. The functional of B3LYP and the DNP basis set are chosen for AIMD.

ATP2B3 Inhibition Alleviates Erastin-Induced Ferroptosis in HT-22 Cells through the P62-KEAP1-NRF2-HO-1 Pathway.

Ferroptosis participates in the occurrence and development of neurological disorders. Modulating ferroptosis may have therapeutic potential in nervous system diseases. Therefore, TMTbased proteomic analysis in HT-22 cells was performed to identify erastin-induced differentially expressed proteins. The calcium-transporting ATP2B3 (ATP2B3) was screened as a target protein. ATP2B3 knockdown markedly alleviated the erastin-induced decrease in cell viability and elevated ROS (p < 0.01) and reversed the up-regulation of oxidative stress-related proteins polyubiquitin-binding protein p62 (P62), nuclear factor erythroid 2-related factor2 (NRF2), heme oxygenase-1 (HO-1), and NAD(P)H quinone oxidoreductase-1 (NQO1) protein expression (p < 0.05 or p < 0.01) and the down-regulation of Kelch-like ECH-associated protein 1(KEAP1) protein expression (p < 0.01). Moreover, NRF2 knockdown, P62 inhibition, or KEAP1 overexpression rescued the erastin-induced decrease in cell viability (p < 0.05) and increase in ROS production (p < 0.01) in HT-22 cells, while simultaneous overexpression of NRF2 and P62 and knockdown of KEAP1 partially offset the relief effect of ATP2B3 inhibition. In addition, knockdown of ATP2B3, NRF2, and P62 and overexpression of KEAP1 significantly down-regulated erastin-induced high expression of the HO-1 protein, while HO-1 overexpression reversed the alleviating effects of ATP2B3 inhibition on the erastin-induced decrease in cell viability (p < 0.01) and increase in ROS production (p < 0.01) in HT-22 cells. Taken together, ATP2B3 inhibition mediates the alleviation of erastin-induced ferroptosis in HT-22 cells through the P62-KEAP1-NRF2-HO-1 pathway.

Chronic Corticosterone Exposure Suppresses Copper Transport through GR-Mediated Intestinal CTR1 Pathway in Mice.

Numerous studies have discovered that chronic stress induces metabolic disorders by affecting iron and zinc metabolism, but the relationship between chronic stress and copper metabolism remains unclear. Here, we explore the influence of chronic corticosterone (CORT) exposure on copper metabolism and its regulatory mechanism in mice. Mice were treated with 100 µg/mL CORT in drinking water for a 4-week trial. We found that CORT treatment resulted in a significant decrease in plasma copper level, plasma ceruloplasmin activity, plasma and liver Cu/Zn-SOD activity, hepatic copper content, and liver metallothionein content in mice. CORT treatment led to the reduction in duodenal expression of copper transporter 1 (CTR1), duodenal cytochrome b (DCYTB), and ATPase copper-transporting alpha (ATP7A) at the mRNA and protein level in mice. CORT treatment activated nuclear glucocorticoid receptor (GR) and down-regulated CRT1 expression in Caco-2 cells, whereas these phenotypes were reversible by an antagonist of GR, RU486. Chromatin immunoprecipitation analysis revealed that GR bound to the Ctr1 promoter in Caco-2 cells. Transient transfection assays in Caco-2 cells demonstrated that the Ctr1 promoter was responsive to the CORT-activated glucocorticoid receptor, whereas mutation/deletion of the glucocorticoid receptor element (GRE) markedly impaired activation of the Ctr1 promoter. In addition, CORT-induced downregulation of Ctr1 promoter activity was markedly attenuated in Caco-2 cells when RU486 was added. These findings present a novel molecular target for CORT that down-regulates intestinal CTR1 expression via GR-mediated trans-repression in mice.

Chronic Psychological Stress Disrupts Iron Metabolism and Enhances Hepatic Mitochondrial Function in Mice.

To explore the changes in iron metabolism and mitochondrial function exposed to chronic psychological stress, seventy-five male mice aged 5 ~ 6 weeks were randomly sorted into 2 groups: control group and chronic psychological stress group. Mice were conducted by communication box to induce psychological stress for 21 consecutive days. The results showed that chronic psychological stress led to a significant reduction in average daily gain (P < 0.01) and the final weight (P < 0.05). Chronic psychological stress greatly increased plasma and duodenal iron level (P < 0.05), whereas markedly decreased hepatic iron content in mice (P < 0.05). Increasing expression of duodenal DCYTB and FPN (P < 0.05) was observed in mice exposed to chronic psychological stress. Moreover, chronic psychological stress greatly enhanced hepatic TFR1, FTL, and FPN protein expression (P < 0.05) in mice. Additionally, chronic psychological stress enhanced the levels of hepatic NADH, NAD + , ATP, mtDNA content, mtDNA-encoded genes, and the activity of mitochondrial complex I and II (P < 0.05). Taken together, chronic psychological stress impairs growth, disrupts iron metabolism, and enhances hepatic mitochondrial function in mice. These results will provide new insights for understanding the mechanisms of iron metabolism and mitochondrial function during chronic psychological stress.

Role and mechanism of miR-335-5p in the pathogenesis and treatment of polycystic ovary syndrome.

Polycystic ovary syndrome (PCOS) is a common endocrine disorder of unknown etiology that occurs in women of reproductive age. Despite being considered to affect up to one-fifth of women in this cohort, the condition lacks generally accepted diagnostic biomarkers and options for targeted therapy. Hereby, we analyzed the diagnostic, therapeutic, and functional potential of a recently discovered miR-335-5p that was observed to be reduced in the follicular fluid (FF) of PCOS patients as compared with healthy women. We found miR-335-5p to be significantly decreased in the serum and FF samples of PCOS patients (n = 40) vs healthy women (n = 30), as well as in primary human granulosa cells (hGCs), and in 3 different hormonally induced PCOS-like murine models vs. wild-type (WT) mice. The level of circulating miR-335-5p was found to significantly correlate with the impaired endocrine and clinical features associated with PCOS in human patients. Ovarian intrabursal injection of the miR-335-5p antagomir in WT mice ovaries induced a PCOS-like reproductive phenotype. Treatment with the miR-335-5p agomir rescued the dihydrotestosterone-induced PCOS-phenotype in mice, thereby providing a functional link between miR-335-5p and PCOS. We identified SP1 as a miR-335-5p target gene by using the dual-luciferase reporter assay. Both the luciferase reporter assay and chromatin immunoprecipitation assay showed that SP1 bound to the promoter region of human CYP19A1 and inhibited its transcription. miR-335-5p increased the production of estradiol via the SP1/CYP19A1 axis in hGCs, thereby suggesting its mechanistic pathway of action. In conclusion, these results provide evidence that miR-335-5p may function as a mediator in the etiopathogenesis of PCOS, as well as has the potential as both a novel diagnostic biomarker and therapeutic target for PCOS.

Effects of Curcumin on the Egg Quality and Hepatic Lipid Metabolism of Laying Hens.

Curcumin, the major active compound of turmeric, has shown potential benefits for poultry health and production in various studies. However, its specific role in enhancing the egg quality and liver health of laying hens, as well as its underlying mechanisms, have yet to be determined. Here, a total of 600 Su Qin No.1 Laying hens, aged 55 weeks and with similar laying rates, were randomly placed into five groups, with 10 replicates of 12 hens each. Curcumin doses of 0, 100, 200, 400, and 800 mg/kg were added to the basal diet to form the experimental groups. After an 8-week feeding period, no significant changes were observed in the production performance of laying hens due to curcumin supplementation. However, additional tests revealed that a 200 mg/kg curcumin supplementation improved albumen height, yolk color, Haugh unit, and eggshell thickness, while reducing the thin albumen's weight and proportion. This was accompanied by a significant down-regulation of the mRNA expression level of the Prolactin Receptor (Prlr) in the oviduct magnum. Furthermore, the number of hepatic lipid droplets and the hepatic triglyceride (TG) content, as well as malondialdehyde (MDA) levels were significantly reduced, indicating improved hepatic lipid metabolism and oxidative status. This was accompanied by a significant reduction in the expressions of sterol regulatory element binding protein-1 gene (Srebp-1), fatty acid synthase gene (Fasn), as well as fatty acid synthase (FASN), which are closely related to fatty acid synthesis in the liver. Overall, these findings suggest that curcumin supplementation at a dosage of 200 mg/kg could lead to significant improvements in egg quality and hepatic lipid metabolism.

One-step spray coating strategy toward a highly uniform large-area CsPbBr3@PMMA composite film for backlit display.

The large-scale and continuous production of CsPbBr3@PMMA composite film is realized by the in-situ ultrasonic spray coating method at room temperature. Through embedding CsPbBr3 nanocrystals into the hydrophobic polymer framework, the as-fabricated films (20 cm × 20 cm) exhibit uniform green emissions with a relatively high PLQYs of 76%, and could maintain 80% PL intensity after 3 months storage under ambient conditions. Assembling the green-emissive CsPbBr3@PMMA film and the red-emissive KSF@PMMA film with blue LED chip, a high-performance LCD is obtained, reaching a higher saturation with 126% and 94% color gamut of NTSC and Rec.2020, respectively. This work demonstrates that ultrasonic spray coating technique could be widely used in the large-scale fabrication of uniformly high-quality perovskite films for backlight application.

Deletion of Letmd1 leads to the disruption of mitochondrial function in brown adipose tissue.

Human cervical cancer oncogene (HCCR-1), also named as LETMD1, is an LETM-domain containing outer mitochondrial membrane protein which plays an important role in carcinogenesis. The present study found that the loss of Letmd1 in mice led to severe abnormities, such as brown adipose tissue (BAT) whitening, impaired thermogenesis of both BAT and beige fat, cold intolerance, diet-induced obesity, glucose intolerance and insulin resistance. Mechanically, the deletion of Letmd1 in BAT caused decreased level of both mitochondrial and intracellular Ca2+. The reduced intracellular Ca2+ could suppress the fission of mitochondria and ultimately lead to the disruption of BAT thermogenesis by regulating mitochondrial structures and functions. This study indicates that LETMD1 played a crucial role in BAT thermogenesis and energy homeostasis through regulating mitochondrial structures and functions, which provides a novel insight into therapeutic target exploration from oncogenes for metabolic disorders.

Selenoviologen-Appendant Metallacycles with Highly Stable Radical Cations and Long-Lived Charge Separation States for Electrochromism and Photocatalysis.

Two coordinated metallacycles (rhomboid for M1, hexagonal for M2) with selenoviologens (SeV2+ ) pendants were synthesized via coordination-driven hierarchical self-assembly. M1/M2 with rigid and discrete metallacyclic cores showed tunable optoelectronic properties due to strong π-π stacking and push-pull electron structures. Femtosecond transient absorption (fs-TA) revealed that the formation of macrocyclic structure can not only enhance the stability of radical cation, but also improve the efficiency of intramolecular charge transfer and produce a long-lived charge separation state. The electrochromic performances of M1/M2-based devices were exhibited to show decent radical stabilization. By using M1/M2 as the photocatalyst, the improved catalytic efficiency (>80 %) of visible-light-induced cross-dehydrogenative coupling (CDC) reactions was achieved due to the highly stable radical cations and long-lived charge separation states, which were also confirmed by fs-TA.

Accelerated discovery of thermostable high-energy materials with intramolecular donor-acceptor building blocks.

A domain-related data search promoted triazolotriazine-fused energetic scaffold filtration with combinatorial design to alleviate the lack of thermostable high-energy materials; 16 candidates were discovered that may show promising energy and safety performance, as well as excellent thermal stability. Novel fused triazolo-1,2,4-triazine energetic material 7-nitro-3-(1H-tetrazol-5-yl)-[1,2,4]triazolo[5,1-c][1,2,4]triazin-4-amine-2-oxide (Candidate No. 4) with excellent thermal stability, high energy performance and low sensitivity was developed successfully by using a facile N-oxide synthetic method. Our findings may be applicable to a wider range of materials and prove equally powerful for searching for other high-performing energetic materials.

Preparation of Butadiene-Bridged Polymethylsiloxane/Ethylcellulose/1-Carboxymethyl-3-methylimidazolium Chloride Ternary Composite Membranes for Gas Separation.

Excessive CO2 emissions have resulted in global warming and are a serious threat to the life of people, various strategies have been implemented to cut carbon emissions, and one of them is the use of a gas separation membrane to capture CO2 effectively. In this experiment, the butadiene-bridged polymethylsiloxane (BBPMS)/ethyl cellulose (EC)/ionic liquid (IL) ternary composite membranes were prepared by EC as a substrate, BBPMS, and IL as additives in tetrahydrofuran under high-speed stirring and coated on the membrane. The membrane structure was characterized by a Fourier transform infrared spectrometer and scanning electron microscope, and the membrane properties were tested by a membrane tensile strength tester, thermal weight loss analyzer, and gas permeability meter. The results show that the surface of the ternary composite membrane is dense and flat with a uniform distribution, and the membrane formation, heat resistance, and mechanical properties are good. The permeability coefficient of the ternary composite membrane for CO2 reached 1806.03 Barrer, which is 20.00 times higher than that of the EC/IL hybrid matrix membrane. The permeability coefficient of O2 reached 321.01 Barrer, which is 19.21 times higher than that of the EC/IL membrane. When the doping amount of BBPMS is 70-80%, the O2/N2 gas permeation separation of the BBPMS/EC/IL ternary composite membrane is close to the Robertson 2008 curve. It is always known that in the gas separation process the membrane material is the most crucial factor. The success of this experiment points to a new direction for the preparation of new membrane materials.

ortho-Terphenylene Viologens with Through-Space Conjugation for Enhanced Photocatalytic Oxidative Coupling and Hydrogen Evolution.

A series of novel ortho-terphenylene viologen derivatives (o-TPV2+) with through-space conjugation (TSC) via the combination of ortho-terphenylene skeletons with viologen structure is reported. Their optoelectronic properties can be adjusted by N-arylation or N-alkylation reactions. Compared with other viologen derivatives, o-TPV2+ not only exhibits strong photoluminescence but also retards the charge recombination process and stabilizes the diradical state without forming a quinoid structure due to the special TSC effect. Based on their special redox characteristics, o-TPV2+ was applied to the photocatalytic oxidative coupling of benzylamine with 96% yield. In addition, pTA-o-TPV2+ (tethered with p-toluic acid)-modified g-C3N4 was used for visible-light-driven hydrogen production for the first time, exceeding 15 times the rate over unmodified g-C3N4.

Bacteria-Triggered Solar Hydrogen Production via Platinum(II)-Tethered Chalcogenoviologens.

Multifunctional solar energy conversion offers a feasible strategy to solve energy, environmental and water crises. Herein, a series of platinum(II)-tethered chalcogenoviologens (PtL+ -EV2+ , E=S, Se, Te) is reported, which integrate the functions of photosensitizer, electron mediator and catalyst. PtL+ -EV2+ (particularly for PtL+ -SeV2+ )-based one-component solar H2 production could be triggered not only by EDTA, but also by facultative anaerobic and aerobic bacteria relying on a simplified mechanism, along with efficient antibacterial activities. In addition, by using real pool water, PtL+ -SeV2+ achieved multiple functions, including H2 production, antibacterial action and acid removal, which supplied a new strategy to solve various problems in real life via a single system.

Macrophage deletion of Noc4l triggers endosomal TLR4/TRIF signal and leads to insulin resistance.

In obesity, macrophages drive a low-grade systemic inflammation (LSI) and insulin resistance (IR). The ribosome biosynthesis protein NOC4 (NOC4) mediates 40 S ribosomal subunits synthesis in yeast. Hereby, we reported an unexpected location and function of NOC4L, which was preferentially expressed in human and mouse macrophages. NOC4L was decreased in both obese human and mice. The macrophage-specific deletion of Noc4l in mice displayed IR and LSI. Conversely, Noc4l overexpression by lentivirus treatment and transgenic mouse model improved glucose metabolism in mice. Importantly, we found that Noc4l can interact with TLR4 to inhibit its endocytosis and block the TRIF pathway, thereafter ameliorated LSI and IR in mice.

Chronic Variable Stress Induces Hepatic Fe(II) Deposition by Up-Regulating ZIP14 Expression via miR-181 Family Pathway in Rats.

It is well-known that hepatic iron dysregulation, which is harmful to health, can be caused by stress. The aim of the study was to evaluate chronic variable stress (CVS) on liver damage, hepatic ferrous iron deposition and its molecular regulatory mechanism in rats. Sprague Dawley rats at seven weeks of age were randomly divided into two groups: a control group (Con) and a CVS group. CVS reduces body weight, but increases the liver-to-body weight ratio. The exposure of rats to CVS increased plasma aspartate aminotransferase (AST), alkaline phosphatase (ALP) and hepatic malondialdehyde (MDA) levels, but decreased glutathione peroxidase (GSH-Px) activity, resulting in liver damage. CVS lowered the total amount of hepatic iron content, but induced hepatic Fe(II) accumulation. CVS up-regulated the expression of transferrin receptor 1 (TFR1) and ZRT/IRT-like protein 14 (ZIP14), but down-regulated ferritin and miR-181 family members. In addition, miR-181 family expression was found to regulate ZIP14 expression in HEK-293T cells by the dual-luciferase reporter system. These results indicate that CVS results in liver damage and induces hepatic Fe(II) accumulation, which is closely associated with the up-regulation of ZIP14 expression via the miR-181 family pathway.

A Novel Imide-Bridged Polysiloxane Membrane Was Prepared via One-Pot Hydrosilylation Reaction for O2/N2 Separation.

The synthesis of poly(methyhydrosiloxane) (PMHS) and N,N'-bis(3-allyl)pyromellitic diimide was optimized for O2/N2 separation. The membrane exhibits excellent mechanical and thermal properties and shows an O2/N2 selectivity of up to 4.44 with an O2 permeability of 31.0 Barrer; compared with polydimethylsiloxane (PDMS) and pure polyimide (PI) membranes, the separation selectivity shows a 107% increase for PDMS, and the permeation shows a 660% increase for pure PI. The obtained results were well above the ones reported on the literature for similar conditions opening the door for the preparation of a stable polysiloxane (PMHS-I) gas separation membrane with extraordinary O2/N2 separation performance.

α-Lipoic Acid Alleviates Hepatic Lipid Deposition by Inhibiting FASN Expression via miR-3548 in Rats.

Excessive liver lipid deposition is a vital risk factor for the development of many diseases. Here, we fed Sprague-Dawley rats with a control or α-lipoic acid-supplemented diet (0.2%) for 5 weeks to elucidate the effects of α-lipoic acid on preventive ability, hepatic lipid metabolism-related gene expression, and the involved regulatory mechanisms. In the current study, α-lipoic acid supplementation lowered plasma triglyceride level and hepatic triglyceride content. Reduced hepatic lipid deposition was closely associated with inhibiting fatty acid-binding protein 1 and fatty acid synthase expression, as well as increasing phosphorylated hormone-sensitive lipase expression at the protein level in α-lipoic acid-exposed rats. Hepatic miRNA sequencing revealed increased expression of miR-3548 targeting the 3'untranslated region of Fasn mRNA, and the direct regulatory link between miRNA-3548 and FASN was verified by dual-luciferase reporter assay. Taken together, α-lipoic acid lowered hepatic lipid accumulation, which involved changes in miRNA-mediated lipogenic genes.

Preparation and High Performance of Cellulose Acetate Films by Grafting with Imidazole Ionic Liquid.

Cellulose acetate (CA) grafted with imidazole ionic liquids (CA-ILs) was synthesized by reacting CA with imidazole ionic liquids ([HO2CMmim]Cl, [HO2CEtmim]Cl, and [HO2CMmim]Br) by using tetrahydrofuran (THF) as the solvent and pyridine as the catalyst. The CA and CA-IL films were fabricated by using the casting solution method. The CA-IL films exhibited good film forming ability and mechanical properties. The successful grafting of CA with imidazole ionic liquids was confirmed by Fourier transform infrared (FTIR), 1H NMR, scanning electron microscopy (SEM), and elemental analysis, and the grafting degrees were 2.24, 2.45, and 3.30%, respectively. The CO2 permeation properties of the CA-IL films were 65.5, 105.6, and 88.3 Barrer, increased up to 2.0, 3.2, and 2.7 times, respectively, as compared to pure CA (32.6 Barrer). The CO2/CH4 selectivities of the CA-IL films were 15.6, 12.6, and 19.2, increased up to 1.7, 1.4, and 2.1 times, respectively, as compared to pure CA (9.26). Therefore, it can be concluded that the imidazole ionic liquids are immensely useful for improving the gas separation performance of CA films.

Cannabidiol attenuates pulmonary arterial hypertension by improving vascular smooth muscle cells mitochondrial function.

Rationale: Pulmonary arterial hypertension (PAH) is a chronic disease associated with enhanced proliferation of pulmonary artery smooth muscle cells (PASMCs) and dysfunctional mitochondria, and the clinical therapeutic option for PAH is very limited. Recent studies showed that cannabidiol (CBD), a non-psychoactive constituent of cannabinoids, possessed antioxidant effect towards several cardiovascular diseases, whereas the mechanistic effect of CBD in PAH is unknown. Methods: In this study, the effects of CBD in PAH were determined by analyzing its preventive and therapeutic actions in PAH rodent models in vivo and PASMCs' proliferation test in vitro. Additionally, CBD's roles in mitochondrial function and oxidant stress were also assessed in PASMCs. Results: We found that CBD reversed the pathological changes observed in both Sugen-hypoxia and monocrotaline-induced PAH rodent models in a cannabinoid receptors-independent manner. Our results also demonstrated that CBD significantly inhibited the PASMCs' proliferation in PAH mice with less inflammation and reactive oxygen species levels. Moreover, CBD alleviated rodent PAH by recovering mitochondrial energy metabolism, normalizing the hypoxia-induced oxidant stress, reducing the lactate overaccumulation and abnormal glycolysis. Conclusions: Taken together, these findings confirm an important role for CBD in PAH pathobiology.