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As a typical two-dimensional (2D) transition metal disulfide, molybdenum disulfide (MoS2) shows good electrocatalytic activity, and is considered as a promising sensing material due to its adequate exposed active edges. However, 2D sheet-like structural MoS2 tends to aggregate, resulting in a decreased specific surface area. In addition, the poor electronic conductivity of MoS2 limits the electrochemical application. To address these issues, herein, graphene aerogel (GA), with a three-dimensional (3D) nanoarchitecture consisting of a large specific surface area, rapid electron transfer, and excellent electrocatalytic activity, has been employed as a novel framework support for MoS2. Through a facile one-step hydrothermal technique, the peeled MoS2 sheets were incorporated into the GA network. The MoS2/GA composite was investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The composite combined the excellent electrical conductivity and huge effective surface area of GA with the high catalytic activity of the MoS2 nanosheets. Due to these advantages, the MoS2/GA composite was applied as an electrochemical sensing platform for caffeic acid (CA) detection. The sensor performed good selectivity, wide linear range (1.0 nM-10.0 μM), and low limit of detection (LOD, 0.3 nM). Furthermore, the designed sensor represented good reproducibility and stability, and was successfully applied for detecting CA in red wine samples.

Mixed protonic-electronic ceramic lanthanum tungstate membranes of La5.5W1-xMnxO11.25-δ (LWMnx, x = 0.1, 0.15 and 0.2) and La5.5W0.8-yMn0.2MoyO11.25-δ (LWMn0.2Moy, y = 0.1, 0.2, 0.3 and 0.4) were developed in present work. The H2 permeation flux through lanthanum tungstate membrane was increased by substitution of Mn ions into W sites. However, the impurity of La2O3 formed in LWMn0.15 and LWMn0.2 membranes. Introduction of a moderate amount of Mo ions in LWMn0.2 was beneficial to single phase formation and H2 permeation. LWMn0.2Mo0.2 exhibited a pure cubic phase structure without any impurities. LWMn0.2Mo0.2 membrane had a H2 permeation flux about 0.12 mL/min∙cm2 at 1000 °C, which was 1.7 times higher than that through LWMn0.2 membranes.

An efficient aerobic iron-catalyzed annulation of unsaturated carboxylic acids with disulfides has been developed. This procedure proceeds using FeCl3 as the catalyst and KI as an iodine source under an air atmosphere, which provides practical access to a wide range of substituted γ-lactone derivatives. The disclosed method is quite simple, highly atom-economic, environmentally friendly, and tolerates a broad substrate scope.

Two novel metal–organic compounds have been prepared via altering metal ions under the hydrothermal conditions, i.e. [Zn(HL)(4,4′-bipy)(H2O)2]n (1) and [Cd(HL)(4,4′-bipy)]n (2) (4,4′-bipy = 4,4′-bipyridine and H3L = 5-(4-carboxyphenoxy)-isophthalic acid). Moreover, the luminescent performances and stabilities of the two compounds were also investigated. For the prevention and treatment evaluation of compounds 1 and 2 in this present research, serious of biological experiments were performed in this study. Firstly, the non-invasive blood pressure monitoring was used for blood pressure determination. In addition to this, the real time RT-PCR assay was conducted in this study for the assessment of the α receptor expression on the vascular endothelial cells.

Background The levels and ratios of sugar and acid are important contributors to fruit taste. Kumquat is one of the most economically important citrus crops, but the information on the soluble sugar and organic acid metabolism in kumquat is limited. Here, two kumquat varieties, 'Rongan' (RA) and its mutant 'Huapi' (HP), were used to assess the soluble sugar and organic acid accumulation and the related genes. Results Soluble sugars include sucrose, glucose, and fructose while malate, quinic acid, and citrate are the dominant organic acids in the fruits of both kumquat varieties. 'HP' accumulated more sugars but fewer organic acids than those in 'RA'. Transcriptome analysis revealed 63 and 40 differentially expressed genes involved in soluble sugar and organic acid accumulation, respectively. The genes associated with sugar synthesis and transport including SUS, SPS, TST, STP, and ERD6L were up-regulated, while INVs, FRK and HXK genes related to sugar degradation were down-regulated in 'HP' kumquat. For organic acids, the up-regulation of PEPC and NAD-MDH could accelerate malate accumulation. In contrast, high expression of NAD-IDH and GS resulted in citric acid degradation during 'HP' fruit development. Additionally, the PK, PDH, PEPCK, and FBPase genes responsible for the interconversion of soluble sugars and organic acids were also significantly altered in the early development stages in 'HP'. Conclusion The high sugar accumulation in 'HP' fruit was associated with up-regulation of SUS, SPS, TST, STP and ERD6L genes. The PEPCK, PEPC, NAD-MDH, NADP-IDH, GS, and FBPase genes played important roles in acid synthesis and degradation in 'HP' kumquat. These findings provide further information into understanding the mechanisms underlying sugars and organic acid metabolism in citrus. This article is protected by copyright. All rights reserved.

N-Substituted tetrahydroquinoxalines (37 examples) were step-economically obtained in good yield (

A transient numerical model was applied to simulating the axial-directional crystallization purification (ADCP) process of gallium (Ga) raw material at different coolant temperatures (Tc), and the evolutions of melt/crystal (m/c) interface shape, temperature distribution and thermal stresses were simulated and analyzed. The results showed that the m/c interface shape, temperature distribution, and thermal stress in the Ga material were determined by the Tc in the crystallizer during the ADCP process. The temperature gradient and thermal stress in the grown Ga crystal increased with decreasing Tc. At Tc=15 °C, the m/c interface shape was flat, and the temperature gradient was ideal. Therefore, the Ga materials with lower thermal stresses and suitable m/c interface shape, and an ideal efficiency of impurity removal were obtained. The purity of Ga reached 6N standard by using ADCP process repeated 6 times at Tc of 15 °C. The results of the simulation showed good agreement with the experimental results.

Two coordination polymers (CPs), [Mn(bipmo)(pbtda)(H2O)] n (1), {[Cd(bipmo)(btda)]·2(H2O)]} n (2), (bipmo = bis(4-(1H-imidazol-1-yl)phenyl)methanone, H2pbtda = 2-phenylbutanedioic acid, H2btda = butanedioic acid), were synthesized by solvothermal methods. The products have been characterized by elemental analyses, IR spectroscopy, and single-crystal X-ray diffraction. The topological structure of 1 is based on 2-nodal nets with the Schläfli symbol {63}{69·8}, while that of 2 features a system with a sixfold penetration with the Schläfli symbol {66}.

Single atom catalysts (SACs) are of great importance for oxygen reduction, a critical process in renewable energy technologies. The catalytic performance of SACs largely depends on the structure of their active sites, but explorations of highly active structures for SAC active sites are still limited. Herein, we demonstrate a combined experimental and theoretical study of oxygen reduction catalysis on SACs, which incorporate M-N3 C1 site structure, composed of atomically dispersed transition metals (e.g., Fe, Co, and Cu) in nitrogenated carbon nanosheets. The resulting SACs with M-N3 C1 sites exhibited prominent oxygen reduction catalytic activities in both acidic and alkaline media, following the trend Fe-N3 C1 > Co-N3 C1 > Cu-N3 C1 . Theoretical calculations suggest the C atoms in these structures behave as collaborative adsorption sites to M atoms, thanks to interactions between the d/p orbitals of the M/C atoms in the M-N3 C1 sites, enabling dual site oxygen reduction.

The purpose of this study was to explore the protective effect of BW373U86 (a δ-opioid receptor (DOR) agonist) on ischemia–reperfusion (I/R) injury in rat cardiomyocytes and its underlying mechanism. Primary rat cardiomyocytes were cultured and pretreated with BW373U86 for intervention. The cardiomyocytes were cultured under the condition of 94% N2 and 5% CO2 for 24 h to perform hypoxia culture and conventionally cultured for 12 h to perform reoxygenation culture. The cell viability of cardiomyocytes was detected by an MTT assay (Sigma–Aldrich). The autophagy lysosome levels in cardiomyocytes were evaluated by acidic vesicular organelles with dansylcadaverine (MDC) staining (autophagy test kit, Kaiji Biology, kgatg001). The protein expression levels of LC3, p62, and factors in the PI3K/Akt/mTOR signaling pathway were detected by Western blot. Pretreatment with BW373U86 could improve the cell viability of cardiomyocytes with hypoxia–reoxygenation (H/R) injury (p < 0.05). Interestingly, after coculture of BW373U86 and PI3K inhibitor (3-methyladenine), the protein expression levels of p-Akt in cardiomyocytes were markedly increased in comparison with those in the BW373U86 group (p < 0.05). However, there were no significant differences in the protein expression levels of mTOR between the coculture group and the BW373U86 group (p > 0.05). BW373U86 upregulated autophagy to protect cardiomyocytes from H/R injury, which may be related to the PI3K/Akt/m TOR pathway.

A three-dimensional (3D) two-fold interpenetrated coordination polymer, {[Cd(bipmo)(bpda)]·1.25(H2O)} n (1), (bipmo = bis(4-(1H-imidazol-1-yl)phenyl)methanone, H2bpda = 1,1ʹ-biphenyl-2,2ʹ-dicarboxylic acid), was synthesized by a solvothermal method. It has been characterized by elemental analyses, infrared (IR) spectroscopy, and single-crystal X-ray diffraction. The topological structure of 1 consists of uninodal dia nets with two-fold penetration. The thermal stability and the luminescence properties of complex 1 were investigated.

Ammonia (NH3) is essential for modern agriculture and industry and is a potential energy carrier. NH3 is traditionally synthesized by the Haber–Bosch process at high temperature and pressure. The high-energy input of this process has motivated research into electrochemical NH3 synthesis via nitrogen (N2)–water reactions under ambient conditions. However, the future of this low-cost process is compromised by the low yield rate and poor selectivity, ascribed to the inert N≡N bond and ultralow solubility of N2. Obtaining NH3 directly from non-N2 sources could circumvent these challenges. Here we report the eight-electron direct electroreduction of nitrate to NH3 catalysed by copper-incorporated crystalline 3,4,9,10-perylenetetracarboxylic dianhydride. The catalyst exhibits an NH3 production rate of 436 ± 85 μg h−1 cm−2 and a maximum Faradaic efficiency of 85.9% at −0.4 V versus a reversible hydrogen electrode. This notable performance is achieved by the catalyst regulating the transfer of protons and/or electrons to the copper centres and suppressing hydrogen production. Electrochemically reducing nitrogen-containing molecules could provide less energy-intense routes to produce ammonia than the traditional Haber–Bosh process. Here the authors use a catalyst comprising Cu embedded in an organic molecular solid to synthesize ammonia from nitrate ions.

Interleukin-5 (IL-5) is manifested as its involvement in the process of atherosclerosis, but the mechanism is still unknown. In this study, we explored the effect of IL-5 on lipid metabolism and its underlying mechanisms in THP-1-derived macrophages. The quantitative polymerase chain reaction (qPCR) and western blot analysis results showed that IL-5 significantly up-regulated ATP-binding cassette transporter A1 (ABCA1) expression in a dose-dependent and time-dependent manner. [3H]-labeled cholesterol was used to assess the levels of cholesterol efflux, and the results showed that IL-5 increased ABCA1-mediated cholesterol efflux. A high-performance liquid chromatography assay indicated that cellular cholesterol content was decreased by IL-5 treatment in THP-1-derived macrophages. The selective inhibitor and small interfering RNA were used to block the Janus kinase (JAK)/signal transducer and activator of transcription 3 (STAT3) pathway. The results of the qPCR and western blot analysis showed that IL-5 activated JAK2/STAT3 pathway to up-regulate ABCA1 expression. Meanwhile, IL-5 reduced the expression level of miR-211. Furthermore, we found that JAK2 is a target gene of miR-211 and miR-211 mimic inhibited the expression of JAK2 and reduced the levels of p-STAT3 and ABCA1 as revealed by luciferase reporter assay, qPCR and western blot analysis. In summary, these findings indicated that IL-5 promotes ABCA1 expression and cholesterol efflux through the miR-211/JAK2/STAT3 signaling pathway in THP-1-derived macrophages.

High-efficiency pour point depressants (PPDs) for diesel fuel were obtained using a series of tetradecyl methacrylate-N-α-methacrylamide copolymers (C14MC-NMLR) with different molar ratios synthesized through radical polymerization of tetradecyl methacrylate (C14MC) and various forms of N-α-methacrylamide (NMLR, R = -phenyl, -naphthyl, -cyclohexyl, -14a, -16a, -18a). The copolymers were characterized by Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance, and thermogravimetric analysis. Results showed that diesel treated with C14MC-NML-phenyl (9:1) and C14MC-NML-14a (6:1) presented better cold flow properties at 2000 ppm, and the reductions in cold filter-plug point (ΔCFPP) and solid point (ΔSP) were (23 and 10 °C) and (22 and 11 °C) at 2000 ppm, respectively. The depressive effects further improved after compounding. When they were combined at a 1:4 mass ratio, PPDC-6 presented the best depressive effects, and the ΔCFPP and ΔSP reached 25 and 11 °C at 1000 ppm dosage and 28 and 15 °C at 2000 ppm dosage, respectively. Additionally, the crystallization behavior and crystal morphology of each treated diesel were explored.

The classes, structures, and distributions of heteroatom compounds in asphaltenes from medium/low temperature coal tar (LCT) were characterized by using positive-ion electrospray ionization (ESI) F...

To explore the relationship between serum high-density lipoprotein cholesterol (HDL-C) levels and the presence and severity of pulmonary arterial hypertension (PAH). A total of 177 patients with PAH and 103 patients without pulmonary hypertension (PH) were enrolled in this study. All patients underwent right heart catheterization (RHC) for diagnosing and assessing the severity of PAH. Demographics, comorbidities, and laboratory data including serum HDL-C levels were collected. Plasma HDL-C levels in patients with PAH were significantly lower compared with patients without PH (1.08 ± 0.36 vs 1.49 ± 0.36, p

Radionuclide therapy is an important form of tumor internal radiation therapy (IRT), but its curative effect is restricted by the low radiation intensity and poor targeting ability of nuclides, which hampers efficient killing of DNA. Moreover, the limited penetration depth and nonuniform dose distribution of rays result in “blind” regions with residual living cancer cells, which increases the risk of tumor metastasis. Herein, we developed a new strategy to tactfully incorporate IRT with immunotherapy to achieve highly efficient synergistic therapy. Specifically, gold nanoparticles (AuNPs) co-modified with radioactive iodine-131 and the twin arginine translocation (TAT) peptide (131I-AuNPs-TAT) were constructed, in which TAT-guided nuclei targeting provided highly concentrated β-rays to the most radiosensitive DNA. Meanwhile, β− electrons dashed on AuNPs with a sudden drop in speed can transform into low-dosage X-ray bremsstrahlung radiation. X-rays have a longer penetration depth than β-rays and are able to induce a strong immune response, thus eliminating the area that is blind to short-range β-rays resulting from the limited dose distribution. This method, named “internal radio-immunity therapy (IRIT)”, is a unique approach that combines IRT with immunotherapy to not only enhance radiotherapeutic efficacy but also broaden the clinical applications of 131I, thereby demonstrating great potential for scientific research and clinical applications.

The interfacial coupling effect plays a crucial role in tailoring the photoelectrochemical performance of heterostructured photocatalysts. However, it is an urgent need but challenging to intensify the interfacial coupling effect of heterojunctions. Herein, we proposed the surface precleaning of n-type TiO2via a facile low-temperature hydrogenation to facilitate strong coupling with p-type Bi2O3 (Bi2O3/c-TiO2) and thus disruptively accelerate the electron transfer and electron–hole pair separation. The comparative studies of uncleaned Bi2O3/TiO2 and Bi2O3/c-TiO2 heterostructures by X-ray photoelectron spectroscopy revealed an unneglected valence change and thus a highly strong coupling effect between Bi2O3 and the cleaned TiO2 originating from a possible weakening role of the nitrogen species adsorbed on the surface of pristine TiO2 for the interfacial coupling effect. When integrated into a photoelectrochemical sensor, Bi2O3/c-TiO2 presented both significantly high detection photocurrent response and selectivity for organics in a buffer solution. The current response of the as-built Bi2O3/c-TiO2 was two-fold higher than that of uncleaned Bi2O3/TiO2 and was even almost five-fold that of bulk TiO2. We believe that this work will provide new perspectives and insights into the construction of efficient heterojunctions for impressive applications in photoelectrochemical detection.

Two mononuclear tetra-coordinated cobalt(II) complexes with molecular formula [Co(L)2(SCN)2] (L = 1-methylbenzimidazole (mbim), 1; L = 1-methyl-2-aminobenzimidazole (mabim), 2) were prepared and characterized by IR, EA, and single crystal X-ray diffraction. The central Co(II) ion is tetrahedrally coordinated by two nitrogen atoms of benzimidazole-based ligands and two nitrogen atoms of two thiocyanato ligands. In the crystal structure of 1 and 2, molecules are linked through intermolecular hydrogen bonds and π···π interactions forming a 3D network.

A cobalt coordination polymer, {[Co(L1)2(H2O)2] · (HCOO)2 · H2O}n, where L1 is a bis(4-(1H-imidazol-1-yl)phenyl)methanone, has been synthesized and characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The crystal crystallizes in the triclinic sp. gr. $$P\bar {1}$$ with the unit cell parameters a = 7.9504(6), b = 10.0231(7), c = 13.3129(8) A, and α = 88.399(5)°, β = 75.310(6)°, γ = 79.179(6)°, Z = 1. The Co2+ ion has a distorted octahedral environment with two O atoms from two water molecules and four N atoms from four L1 ligands. A thermal stability of polymer has been discussed.

A zinc coordination polymer with V-shaped ligands, [L1Zn(npa)]n (L1 = bis(4-(2'-methylimidazol)phenyl)sulfone, H2npa = 4-nitrophthalic acid) has been synthesized under solvothermal conditions. The structure has been determined by single-crystal X-ray diffraction analysis and characterized by IR spectra, and elemental analyses. In crystal adjacent [Zn2(npa)2] units linked by four bridging ligands L1 form 2D layers, which are entangled between each other giving inclined interpenetration with the angle of 52.9°, thus resulting in a complicated 3D unique network. Moreover, luminescent properties of the title compound have been investigated.

Enantioselective total syntheses of 12 amicoumacin-type natural products are accomplished with a palladium(II)-catalyzed C-H alkylation as the key step to furnish the 3,4-dihydroisocoumarin scaffold. The target chemicals are assembled in a convergent protocol by merging 3,4-dihydroisocoumarin derived amine part with categories of acid segments that are efficiently prepared by chemoselective catalytic oxidation of chiral 1,2-dihydroxyethylfuran-2(5H)-ones. Afterward, the cytotoxicity of amicoumacins on five cancer cell lines and one normal cell line is investigated.

Traditional Chinese medicine prescriptions are widely believed to exert therapeutic benefits via a multiple-component and multiple-target mode. The systemic profiling of their in vitro chemicalome and in vivo metabolome is of great importance for further understanding their clinical value. Herein, an integrated strategy using ultra-performance liquid chromatography coupled with quadruple time-of-flight mass spectrometry was proposed to profile the chemicalome and metabolome of Chai-Gui Decoction. Particularly, an approach combined mass defect filter, characteristic product ion filter, and neutral loss filter was adopted to identify metabolites in plasma, urine, bile, and feces by MetabolitePilot. Consequently, a total of 174 constituents were identified or tentatively characterized and 70 metabolites that related to 21 representative structural components were matched in rat biofluids. Among them, 19 prototypes and 7 metabolites that contributed to flavonoids, monoterpenes, and phenylpropanoids were detected distribution in brain, heart, kidney, liver, lung or spleen. This study provided a generally applicable approach to comprehensive investigation on chemicalome and metabolome of traditional Chinese medicine prescriptions, and offered reasonable guidelines for further screening of quality control indicators of Chai-Gui Decoction.

The proposed structures of parvistemoamide have been achieved by macrolactamization, but none of the characterization data of synthetic samples matched with those of the natural sample. The transformation of the highly strained 10-membered lactam ring in parvistemoamide into the pyrrolo[1,2-a]-azepine nucleus in stemoamide is accomplished for the first time by either transannular cyclization or Pilli's transformation. This research may promote the total synthesis of other more complex stemoamide-type or medium-sized-ring-containing Stemona alkaloids.

Introduction The key transformed T cell transcription factor recombination activation gene protein 2 (RAG2) is regulated during inflammation to allow for the acquisition of effector T cells functions. The present study was designed to investigate whether stress signals elicited by leonurine (LEO) could lead to the degradation of RAG2 through v-akt murine thymoma viral oncogene homolog (AKT) signaling in lung fibrosis. Methods A total of 120 female mice were randomly divided into five groups (Group I–V): Normal group, bleomycin (BLM), BLM+LEO 50 mg/kg/d, BLM+LEO 100 mg/kg/d, and BLM+LEO 50 mg/kg/d+LY294002. Hematoxylin-eosin, Masson’s, and terminal deoxynucleotidyl transferase dUTP nick-end labeling staining were performed to observe the pathomorphological changes. The expression of CD3+, TGF-β, RAG2, and Bcl proteins was examined by immunodetection, while that of E-cadherin (ECAD), AKT, TGF-β1, alpha-actin-2, Bax, and RAG2 was detected by Western blot analysis. Results The level of T lymphocytes was reduced sharply in LEO-treated mice as compared to the other groups. The AKT signal was greatly inhibited in the BLM group and activated with LEO treatment on day 14. In addition, RAG2 was attenuated by LEO on day 14 and day 28. LY294002 could reverse the expression of AKT and RAG2 on day 28. Remarkably, the low dose of LEO has a greater protective efficacy as compared to the high-dose LEO group in terms of pulmonary fibrosis, T cell inactivation, and apoptosis in alveolar cells. Conclusion The results of the present study suggested that LEO has a protective effect on lung fibrosis with possible mechanisms of attenuating apoptosis and inflammation via the upregulation of the AKT signal in transformed T cells by suppressing the expression and activity of RAG2.

Summary Rh-catalyzed, highly enantioselective (up to 99.8% ee) synthesis of aliphatic sulfonyl fluorides was accomplished. This protocol provides a portal to a class of novel 2-aryl substituted chiral sulfonyl fluorides, which are otherwise extremely difficult to access. This asymmetric synthesis has the feature of mild conditions, excellent functional group compatibility, and wide substrate scope (51 examples) generating a wide array of structurally unique chiral β-arylated sulfonyl fluorides for sulfur(VI) fluoride exchange (SuFEx) click reaction and drug discovery., Graphical Abstract, Highlights • Enantioselective synthesis of di(hetero)arylalkyl sulfonyl fluorides were achieved • These novel SuFEx Clickable molecules will play significant roles for drug discovery • The asymmetric C-C bond construction is a new portal to chiral sulfonyl fluorides • This protocol feathers with mild condition, wide scope, and excellent compatibility, Catalysis; Organic Chemistry; Stereochemistry

The cyanide ligand can act as a strong σ-donor and an effective π-electron acceptor that exhibits versatile bridging abilities, such as terminal, μ2-C:N, μ3-C:C:N and μ4-C:C:N:N modes. These ligands play a key role in the formation of various copper(I) cyanide systems, including one-dimensional (1D) chains, two-dimensional (2D) layers and three-dimensional (3D) frameworks. According to the literature, numerous coordination polymers based on terminal, μ2-C:N and μ3-C,C,N bridging modes have been documented so far. However, systems based on the μ4-C:C:N:N bridging mode are relatively rare. In this work, a novel cyanide-bridged 3D CuI coordination framework, namely poly[(μ2-2,2′-biimidazole-κ2 N 3:N 3′)(μ4-cyanido-κ4 C:C:N:N)(μ2-cyanido-κ2 C:N)dicopper(I)], [Cu2(CN)2(C6H6N4)] n , (I), was synthesized hydrothermally by reaction of environmentally friendly K3[Fe(CN)6], CuCl2·2H2O and 2,2′-biimidazole (H2biim). It should be noted that cyanide ligands may act as reducing agents to reduce CuII to CuI under hydrothermal conditions. Compound (I) contains diverse types of bridging ligands, such as μ4-C:C:N:N-cyanide, μ2-C:N-cyanide and μ2-biimidazole. Interestingly, the [Cu2] dimers are bridged by rare μ4-C:C:N:N-mode cyanide ligands giving rise to the first example of a 1D dimeric {[Cu2(μ4-C:C:N:N)] n+} n infinite chain. Furthermore, adjacent dimer-based chains are linked by μ2-C:N bridging cyanide ligands, generating a neutral 2D wave-like (4,4) layer structure. Finally, the 2D layers are joined together via bidentate bridging H2biim to create a 3D cuprous cyanide network. This arrangement leads to a systematic variation in dimensionality from 1D chain→2D sheet→3D framework by different types of bridging ligands. Compound (I) was further characterized by thermal analysis, solid-state UV–Vis diffuse-reflectance and photoluminescence studies. The solid-state UV–Vis diffuse-reflectance spectra show that compound (I) is a wide-gap semiconductor with band gaps of 3.18 eV. The photoluminescence study shows a strong blue–green photoluminescence at room temperature, which may be associated with metal-to-ligand charge transfer.

We discovered that with the promotion of sulfuryl fluoride, the carbonyl groups of amides performed as nucleophiles while the hydroxyl groups of alcohols were activated to functionalize as electrophiles. This study displayed that the amide C-N bonds could be easily cleaved with delicate nucleophiles to form the ester C-O bonds at room temperature without using transition metals. The broad substrate scope and excellent functional group compatibility were proved with 44 examples in up to 99% yields.

Objectives Cerebral vasospasm after subarachnoid haemorrhage (SAH) is associated with cerebrovascular contractile receptor upregulation resulted from haemolysis in the subarachnoid space. This study developed a new magnesium-rich artificial cerebrospinal fluid (MACSF) formula and investigated its effects on receptor-mediated contraction in rat basilar arteries. Methods Clear and haemorrhagic cerebrospinal fluid (CSF) were collected from patients with hydrocephalus or SAH. MACSF was freshly prepared using clinical intravenous injections. Rat basilar arteries were segmented and incubated with clear CSF, haemorrhagic CSF or MACSF. The contractile responses were studied by myograph. The messenger ribonucleic acid (mRNA) and protein expression of 5-hydroxytryptamine 1B (5-HT1B), endothelin subtype B (ETB) and endothelin subtype A (ETA) receptors were evaluated by real-time polymerase chain reaction (PCR) and Western blot analyses. Results Haemorrhagic CSF exposure shifted the contractile curves induced by 5-hydroxytryptamine (5-HT), sarafotoxins 6c (S6c) and endothelin-1 (ET-1) leftward with increased maximal contraction values. Furthermore, mRNA and protein expression were markedly elevated for 5-HT1B, ETB and ETA receptors on arteries exposed to haemorrhagic CSF. However, the contractile responses to 5-HT, S6c or ET-1 and expression of 5-HT1B, ETB and ETA receptors in rat cerebral arteries exposed to MACSF remained unaffected compared to those exposed to clear CSF. Besides, unlike normal saline which can inactive in-vitro vessels, MACSF can maintain their physiological activity. Conclusion Haemorrhagic CSF induces upregulation of 5-HT1B, ETB and ETA receptors in rat cerebral arteries. However, MACSF can maintain in-vitro rat basilar arteries in good physiological activity and normal expression of contractile 5-HT and ET receptors.

Hydrogen adsorption/desorption behavior plays a key role in hydrogen evolution reaction (HER) catalysis. The HER reaction rate is a trade-off between hydrogen adsorption and desorption on the catalyst surface. Herein, we report the rational balancing of hydrogen adsorption/desorption by orbital modulation using introduced environmental electronegative carbon/nitrogen (C/N) atoms. Theoretical calculations reveal that the empty d orbitals of iridium (Ir) sites can be reduced by interactions between the environmental electronegative C/N and Ir atoms. This balances the hydrogen adsorption/desorption around the Ir sites, accelerating the related HER process. Remarkably, by anchoring a small amount of Ir nanoparticles (7.16 wt%) in nitrogenated carbon matrixes, the resulting catalyst exhibits significantly enhanced HER performance. This includs the smallest reported overpotential at 10 mA cm−2 (4.5 mV), the highest mass activity at 10 mV (1.12 A mgIr−1) and turnover frequency at 25 mV (4.21 H2 s−1) by far, outperforming Ir nanoparticles and commercial Pt/C., Hydrogen adsorption/desorption behavior plays a key role in hydrogen evolution reaction catalysis. Here, the authors demonstrate the rational balancing of hydrogen adsorption/desorption by orbital modulation for significantly enhanced hydrogen evolution performance.

A simple, practical and gram-scale process for direct transformation of primary alcohols or silyl ethers to ammonium salts was developed. This method has the feathers of easy work-up (a simple filtration), mild condition, high yield, great practicality and robustness. And the application of the ammonium salts in Suzuki coupling reaction was also accomplished.

A versatile protocol for the direct thiolation of an inert sp2 C–H bond is presented via a catalytic amount of copper catalysis, by switching related Bronsted bases and regulating the reaction time...

Currently, exosome-enclosed microRNAs (miRs) in exhaled breath have potential for biomarker discovery in patients with pulmonary diseases. This study was performed to investigate the roles of M2 macrophage-derived exosomes expressing miR-328 in pulmonary fibrosis (PF). Microarray-based analysis was used to screen differentially expressed genes (DEGs) and regulatory miRs in PF. The miR-target relationship between FAM13A and miR-328 was confirmed. The expression of FAM13A and miR-328 was measured in PF rats, and gain- and loss-of-function assays were conducted to determine the regulatory effects of FAM13A and miR-328 on PF. In addition, exosomes derived from M2 macrophages were isolated and then cocultured with pulmonary interstitial fibroblasts to identify the role of these exosomes in PF. Furthermore, the effects of M2 macrophage-derived exosomes overexpressing miR-328 on pulmonary fibroblast proliferation and the progression of PF were assessed in vivo. miR-328 might perform a vital function in PF by regulating FAM13A. FAM13A expression was downregulated while miR-328 expression was upregulated in rats with PF, and a miR-target relationship between miR-328 and FAM13A was observed. Additionally, miR-328 overexpression and FAM13A silencing each were suggested to promote pulmonary interstitial fibroblast proliferation and the expression of Collagen 1A, Collagen 3A and α-SMA. Then, in vitro experiments demonstrated that M2 macrophage-derived exosomes overexpressing miR-328 contributed to enhanced pulmonary interstitial fibroblast proliferation and promoted PF. Furthermore, in vivo experiments confirmed the promotive effects of M2 macrophage-derived exosomes overexpressing miR-328 on the progression of PF. Collectively, the results showed that M2 macrophage-derived exosomes overexpressing miR-328 aggravate PF through the regulation of FAM13A., Lung disease: Small RNAs promoting pulmonary fibrosis Studies in rats suggest that microRNAs, small molecules of ribonucleic acid, released by macrophage cells of the immune system can promote pulmonary fibrosis (PF), the formation of scar tissue in lungs. Gao-Feng Zhao, Li-Hua Xing and colleagues at The First Affiliated Hospital of Zhengzhou University in China investigated the role of microRNAs in rats with a form of PF that serves as a model for the disease in humans. Their findings confirm that specific microRNAs released in tiny membrane-bound sacs called exosomes interact with and inhibit a gene whose activity is known to be disrupted in PF. The protein encoded by this gene mediates crucial molecular signaling events in lung cells. Developing drugs that interfere with the activity of the microRNAs is a potential new treatment approach for PF.

Constructing efficient catalysts for the N2 reduction reaction (NRR) is a major challenge for artificial nitrogen fixation under ambient conditions. Herein, inspired by the principle of "like dissolves like", it is demonstrated that a member of the nitrogen family, well-exfoliated few-layer black phosphorus nanosheets (FL-BP NSs), can be used as an efficient nonmetallic catalyst for electrochemical nitrogen reduction. The catalyst can achieve a high ammonia yield of 31.37 μg h-1 mg-1 cat. under ambient conditions. Density functional theory calculations reveal that the active orbital and electrons of zigzag and diff-zigzag type edges of FL-BP NSs enable selective electrocatalysis of N2 to NH3 via an alternating hydrogenation pathway. This work proves the feasibility of using a nonmetallic simple substance as a nitrogen-fixing catalyst and thus opening a new avenue towards the development of more efficient metal-free catalysts.

Two coordination polymers, {[Co(bipmo)(tbip)]·3H2O} n (1) and {[Cd(bipmo)(tbip)]·3H2O} n (2) (bipmo=bis(4-(1H-imidazol-1-yl)phenyl)methanone, H2tbip=5-tert-butylisophthalic acid), were synthesized by solvothermal methods and structurally characterized by elemental analyses, infrared spectroscopy, and single-crystal X-ray diffraction. The results from single-crystal X-ray diffraction data indicate that the solid state structures of 1 and 2 consist of metal-aromatic carboxylate layers, which are pillared by weak interactions to generate a three-dimensional network. The topological structures of 1 and 2 are uninodal nets based on 3-connected nodes with the Schläfli symbol of {63}.

Here, we present an unprecedented pathway to α-sulfenylated carbonyl compounds from commercially available thiols and universally employed TEMPO and its analogues, which act as C3 synthons through skeletal rearrangement under simple and metal-free conditions. Mechanism studies suggest that this reaction involves a consecutive radical oxidation and cation coupling process. TEMPO analogues and thiols serve as oxidants and reductive reagents, respectively, along the radical process, while in the coupling process, the former ones afford C3 synthons to couple with related sulfur sources.

Azepane-based compounds showed a variety of pharmacological properties, and its derivatives possess a high degree of structural diversity, and it is useful for the discovery of new therapeutic agents. The development of new less toxic, low-cost and highly active azepane-containing analogs is a hot research topic in medicinal chemistry. Now, more than 20 azepane-based drugs have been approved by FDA, and widely used to treat various types of diseases. This review highlights the recent developments of azepane-based compounds in a wide range of therapeutic applications, such as anti-cancer, anti-tubercular, anti-Alzheimer's disease, and antimicrobial agents, as well as, histamine H3 receptor inhibitors, α-glucosidase inhibitors, anticonvulsant drugs and other miscellaneous applications. We here briefly describe the structure-activity relationship (SAR) and molecular docking studies of potential bioactive compounds for future discovery of suitable drug candidates. It can serve as an inspiration for new ideas for design and development of less toxic and more powerful azepane-based drugs against numerous devastating diseases.

This work focuses on developing high-efficiency perylene diimide (PDI)-based small molecular nonfullerene acceptors with a simple synthetic strategy. We reported a new electron acceptor, Py-e-PDI, obtained via cross-coupling four PDI units with a planar pyrene core through ethynyl groups. Although the ring-fusion synthetic procedure was omitted, the large planar core and significantly reduced intramolecular steric hindrance endowed this nonfused PDI-tetramer derivative with moderate planarity. Differing from most of the PDI-tetramers with highly twisted geometries, Py-e-PDI could self-assemble into a highly ordered structure. The inverted solar cells with PTB7-Th/Py-e-PDI blends exhibited the best power conversion efficiency of up to 7.59%, which mainly resulted from the combined contribution of complementary absorption with a donor polymer, desirable aggregation and high electron mobility. Most importantly, this result demonstrates that simply planarizing 3D nonfused perylene diimide based acceptors is effective to improve the performance of the corresponding non-fullerene (NF) acceptors.

The construction of para-amino-arylfluorosulfates was achieved through installation of fluorosulfate (–OSO2F) functionality into aromatic C(sp2)–H bonds by the reaction of N-arylhydroxylamine with sulfuryl fluoride (SO2F2). This method provides a mild process for the preparation of broadly applicable fluorosulfate moieties without the requirement of phenols or transition metals.

The multidrug-resistant Staphylococcus aureus (MRSA) is one of the most prevalent human pathogens involved in many minor to major disease burdens throughout the world. Inhibition of biofilm formation is an attractive strategy to treat diseases associated with MRSA infection. In the present investigation, a series of functional group diverse (hetero)aryl fluorosulfonyl analogs were designed, synthesized and tested as antibacterial agents against Staphylococcal spp., and as anti-biofilm candidates. Compounds 8, 15, and 67 were found to possess potent in vitro antibacterial activity among this class of sulfonyl fluorides (MIC = 0.818 ± 0.42, 0.840 ± 0.37 and 0.811 ± 0.37 μg/mL respectively). The analogs 8, 15, 36, and 67 exhibited outstanding anti-biofilm properties compared to other available synthetic antibiotics. The efficacy of synthetic analogs displayed membrane-damaging effect and they are also validated by cellular content release assay. The insight physiological changes were explored by studying the intracellular redox activities through changing cyclic voltammetric (CV) method. The compounds 8, 15, 22, 32, 36, 51, and 67 were found to participate in the interfering in the electron transport chain (ETC) of MRSA. The analogs 8, 15, and 67 possess great potentiality for discovery and development of anti-staphylococcal drugs to treat the MRSA infections.

A nickel coordination polymer with V-shaped ligands, {[(L1)2Ni(H2O)2] · 2(C8H5O4)}n, (L1 = 4-(1H-imidazol-1-yl)phenyl)methanone) has been synthesized under the solvothermal conditions. The structure has been determined by the single-crystal X-ray diffraction analysis and characterized by the infrared spectroscopy and elemental analysis. The crystal is crystallized in the monoclinic sp. gr. P21/c with the unit cell parameters a = 15.6387(3) A, b = 8.0526(2) A, c = 24.4791(6) A, and β = 129.2350(10)°, Z = 2. The adjacent [Ni(H2O)2] units are linked by two bridging L1 ligands to form 1D looped chains, which are extended by the hydrogen bonds to yield a 3D framework.

The 1,5-benzodiazepines are important skeletons frequently contained in medicinal chemistry. Herein, we described an unexpected tandem cyclization/transfer hydrogenation reaction for obtaining chiral 2,3-disubstituted 1,5-benzodiazepines. The enolizable aryl aldehydes were chosen as substrates to react with symmetric and unsymmetric