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The application of a C(vinyl), C(aryl)-palladacycle from vinyl-containing substrates is challenging due to the interference of a reactive double bond in palladium catalysis. This Letter describes a [4 + 2] or [4 + 3] cyclization based on a C(vinyl), C(aryl)-palladacycle by employing α-oxocarboxylic acids as the insertion units under a palladium/air system. The reaction proceeded through the key vinyl C-H activation and dual decarboxylation sequence, forming phenanthrenes and cyclohepta[1,2,3-de]naphthalenes regioselectively in good yields. The synthetic versatility of this protocol is highlighted by the gram-scale synthesis and synthesizing functional material molecule.

Organic molecules are promising electrode materials for green and sustainable rechargeable electrochemical energy storage due to their tunable theoretical capacity and environmental friendliness. However, the commercialization of organic electrode materials is impeded by high solubility in electrolytes and inherently low electronic conductivity. Herein, a series of bipolar organic molecules, [5,10,15,20-tetra(ethynyl)porphinato] M(II) (MTEPP, M= Cu, Zn, Mg, 2H), is proposed as new cathode for highly stable dual ion charge storage. The stacking property of the porphyrin molecules is significantly influenced by complex ions and the mixed valence state of cation (Cu+ and Cu2+) renders better charge storage performance in functionalized porphyrin cathode. Reversible capacity of 219 mAh g−1 is obtained for CuTEPP cathode based on a four-electrons transfer and it can be stably cycled up to 1000 times in lithium based organic batteries. Ex-situ spectroscopies as well as simulation studies evidence the multiple electron transfer and the charge storage sites. Highly reversible capability (> 160 mAh g−1) and stable cyclability (> 300 cycles) is also achieved as cathode in both sodium and potassium based organic cells. This study offers a new approach for developing ultrastable and universal organic cathode for electrochemical energy storage.

The reaction mechanism of the isomerization of glucose to fructose and further dehydration of fructose to 5-hydroxymethylfurfural (5-HMF) in subcritical water was investigated by the dispersion-corrected density functional theory (DFT-D) method with Dmol3 package in Materials Studio. The implicit solvent model was used to evaluate the bulk solvation under the conductor-like screening model (COSMO) approach, in which a dielectric constant (ɛ) of 27 was used to represent the subcritical water at 523.15 K. The explicit solvent model was adopted with a hybrid micro-solvation-continuum approach, to indicate the micro-solvation by explicit H2O molecules and the bulk solvation with ɛ = 27. The calculation results indicate that explicit H2O molecules participate in the reaction and catalytically promotes the proton transfer processes, suggesting that the explicit solvent model is preferable to the implicit solvent model to represent the conversion of 5-HMF in subcritical water. The isomerization of glucose to fructose is exothermic by 5.26 kcal/mol, where the isomerization of open-chain glucose to enol form is the rate-determining step, with the activation energy of 33.89 kcal/mol; the free energy of transition state configuration depends upon both the difficulty in α–H extraction of open-chain glucose and the stability of formed carbocation. In contrast, the hydration of fructose to 5-HMF is exothermic by 12.93 kcal/mol and the first hydration is the rate-determining step, with the activation energy of 50.59 kcal/mol; the free energy of transition state configuration is determined by the stability of carbocation formed by the dehydration of protonated OH group at C(2) site of fructose. This work discloses the promoting effect of Bronsted base on the isomerization of glucose to fructose and that of Bronsted acid on the dehydration of fructose to 5-HMF, which may provide certain clues to the modification of catalytic sites and the selection of solvent in the conversion of glucose to 5-HMF.

A palladium-catalyzed domino Heck cyclization/Hiyama cross-coupling has been achieved for the synthesis of (hetero)aryl-functionalized azaindoline derivatives bearing all-carbon quaternary centers in 46–85% yields. The synthetic versatility of this protocol has been highlighted by the gram-scale synthesis and modification of aryl-containing complex bioactive molecules.

Depression is a severe mental disorder. Unfortunately, more than half of patients with major depression disorder cannot achieve remission after initial treatment with an antidepressant. Geniposide, a bioactive iridoid glycoside isolated from Gardenia jasminoides Ellis, can ameliorate depressive-like behaviors in mice. However, the underlying mechanism is still not very clear. The pharmacological methods including ELISA, immunofluorescence, and Western blot were used to investigate the role of geniposide on chronic unpredictable mild stress (CUMS)-induced depression mice. In this study, we found that geniposide could inhibit CUMS-induced depressive-like behaviors in mice. Geniposide is able to reduce the levels of ceramide and lower the activity of acid sphingomyelinase (ASM) in hippocampus; besides, ASM inhibitor (amitriptyline) can decrease the concentration of ceramide and ameliorate depressive-like behaviors of mice. Moreover, geniposide can also alleviate CUMS-induced hippocampal neuronal apoptosis and increase the phosphorylated form of PI3K, Akt, and GSK3β. Additionally, PI3K inhibitor (LY294002) can also abolish the neuroprotective effect of geniposide on hippocampal neurons in vitro. These results indicate that geniposide exert a potential antidepressant-like effect on CUMS mice, and its effect might be associated with activated PI3K/Akt/GSK3β signaling, reduced the level of ceramide and hippocampal neuron apoptosis.

Hydrazide–hydrazone derivatives have been utilized in molecular switches, sensing, metallo assemblies, drugs and other applications. The hydrazide–hydrazone functional group contains the –CO–NH–NCH– moiety that yields the hydrazide–hydrazone group its physical, chemical and biochemical properties; however, the application in security protection has not been explored before. Herein, the 2-(ortho-), 3-(meta-), 4-(para-) substituted pyridine conjugated to 2,6-dihydroxybenzoic acid, which containing hydrazide–hydrazone as photoswitch linker were designed and synthesized (3a–3c). Interestingly, when irradiating the ortho-substituted pyridine of molecule 3a with a light of 365 nm, obvious emission intensity enhancements were detected. However, 3a–3c before irradiation and 3b–3c after irradiation show no fluorescence. UV-vis, fluorescence, 1H NMR and Fourier transform infrared spectra and density functional theory calculations were carried out, which revealed that the hydrazide–hydrazone derivative of 3a could undergo a characteristic E to Z photoisomerization after light irradiation for 365 nm. The Z isomer of 3a may have additional intramolecular hydrogen bonds to restrict the motions of the molecule, thus increasing the fluorescence intensity of 3a. The experimental and molecular calculation results agreed and thus demonstrated the first example of invisible ink based on the hydrazide–hydrazone motif.

In comparison with green and red OLEDs, which have been well developed with satisfactory electroluminescence (EL) performances, high-efficiency blue OLEDs still need further exploration. Herein, by reasonably strengthening the rigidity of molecules, three new sky-blue thermally activated delayed fluorescence molecules based on electron-withdrawing acridone and electron-donating acridine derivatives are designed and synthesized. Their crystal and electronic structures, thermal stabilities, electrochemical behaviors and photophysical properties are systemically investigated. The results show that these molecules have high thermal and electrochemical stabilities and exhibit aggregation-induced emission and eminent sky-blue delayed fluorescence with emission peaks at 480–502 nm and high fluorescence quantum yields of 78–94% in doped films. Their OLEDs exhibit sky-blue EL emissions with peaks at 482–492 nm, and achieve excellent external quantum efficiencies of 21.8–26.8%. These results indicate that the new sky-blue delayed fluorescence molecules hold good potential as light-emitting materials for OLEDs.

Alleviating cardiac dysfunction improves the prognosis of heart failure patients. Lycorine is an alkaloid with several beneficial biological properties. Here, we used mice to evaluate the effect of lycorine on cardiac dysfunction elicited by isoproterenol. Mice were divided into four groups: control, lycorine, isoproterenol, and isoproterenol + lycorine. Mice in the combined group were treated daily with 10 mg/kg isoproterenol intraperitoneally for 2 weeks and 5 mg/kg lycorine was given simultaneously intraperitoneally for 4 weeks. Cardiac structure and function were assessed by echocardiography, hematoxylin and eosin staining, and Masson’s trichrome staining. Isoproterenol-induced cardiac dysfunction and histopathological injury that was significantly improved by treatment with lycorine. Western blotting and the quantitative real-time polymerase chain reaction were used to explore the molecular mechanisms of these effects. Levels of the inflammatory cytokines, interleukin (IL)-1β, IL-6, and tumor necrosis factor-α, were increased by treatment with isoproterenol; these increases were significantly reduced by lycorine, with involvement of the NF-κB signaling pathway. The fibrotic factors, collagen I and collagen III, were increased by isoproterenol and decreased by treatment with lycorine through inhibiting activation of the Smad signaling pathway. In addition, lycorine alleviated oxidative stress as evidenced by a reduction in total reactive oxygen species in the isoproterenol + lycorine group compared to the isoproterenol group. Lycorine exerted an anti-apoptotic effect as evidenced by upregulating Bcl-2 and downregulating Bax. Overall, our findings demonstrate that lycorine protects against cardiac dysfunction induced by isoproterenol by inhibiting inflammation, fibrosis, oxidative stress, and apoptosis.

A formal [6 + 1] annulation reaction through sequential Michael addition/palladium-catalyzed alpha-arylation of ketones has been developed. This approach provides an efficient route enabling rapid access to diverse acylated caprolactams by the double C–C bond formation of the same site from methyl ketones. In addition, the reaction features a broad substrate scope, good functional group tolerance, easy scale-up of reaction and useful transformations of the products.

Chiral iodoarenes have been steadily increasing in importance in recent years, especially in enantioselective synthesis and catalysis. Since the development of the concept of chiral iodine(I/III) catalysis, the use of various chiral aryliodine frameworks has been explored in this area. This short review gives an overview of the use of chiral hypervalent iodine(I/III) reagents based on the 2-iodoresorcinol core with two attached two lactic side chains bearing ester or amide groups for the catalytic enantioselective dearomatization of phenol compounds, asymmetric oxidation of alkenes, and enantioselective α-functionalization of carbonyl compounds highlighting the excellent reactivities in terms of yield and enantioselectivity.1 Introduction2 Enantioselective Dearomatization of Phenol Derivatives3 Asymmetric Oxidation of Alkenes4 Enantioselective α-Functionalization of Carbonyl Compounds5 Conclusion and Outlook

Background Colorectal cancer (CRC), a type of highly occurred intestinal cancer at present, is prone to metastasis at the later stage of chemotherapy. Looking for the anti-metastatic agents from natural compounds attracted much concern. Here, it aims to demonstrate whether oxymatrine, an anti-cancer natural compound, has anti-metastatic activity and its potential significance in clinic. Materials and methods Wound healing assay and transwell assay were for evaluating the effect of oxymatrine on cell migration and invasion in vitro. Anti-metastatic action in vivo was determined by hepatic metastasis of colorectal cancer cells in mice. Results Oxymatrine can significantly inhibit cancer cell migration and invasion in vitro. The production of ATP, pyruvate, and lactate was suppressed in CRC cells under the treatment of oxymatrine, as well as the glucose consumption. Meantime, extracellular acidification rates (ECR) were evidently attenuated although the oxygen consumption rates (OCR) were not affected. Both clued that oxymatrine inhibition of metastasis is possibly related to blocking aerobic glycolysis. Subsequent results indicated that pyruvate kinase M2 (PKM2) not hexokinase (HK) and phosphofructokinase (PFK) were involved in oxymatrine blocking glycolysis as the PKM2 kinase activity and expression were inhibited by oxymatrine and the PKM2 activator, TEPP-46, can reverse in part the effect of oxymatrine induced in CRC cells. Furthermore, this process was also mediated by inhibition of glucose transporter 1 (GLUT1). Finally, the in vivo metastatic model in mice showed both 20 mg/kg and 40 mg/kg oxymatrine significantly inhibit liver metastasis of CRC cells in mice, and PKM2 and GLUT1 expression in liver of the oxymatrine-treated group is declined. Conclusion Oxymatrine exerted anti-metastatic activity dependent on inhibition of PKM2-mediated aerobic glycolysis. It is not only an anti-cancer agent but also a potential anti-metastatic compound with clinical application significance.

Recently in Nature Catalysis, Xiao and colleagues report a universal strategy for constructing strong metal-support interactions (SMSIs) on irreducible oxide carriers via CO2 treatment based on Le Chatelier’s principle. This research provides an approach for the rational design and optimization of supported metal catalysts based on non-reducible oxides.

Visible light-driven C–C bond formation has attracted increasing attention recently, thanks to the advance in molecular photosensitizers and organometallic catalysts. Nevertheless, these homogeneou...

Multifunctional nanoarchitecture (MNA) on catalysts has attracted great attention because of its capability to improve the performance, durability, and resistance to unwanted side reactions. Such structures, however, are conventionally prepared by deposition methods, which inherently suffer from costly and time-consuming drawbacks. Here, we report a simple one-step process to successfully construct a novel MNA with core-shell nanoparticles anchored at the heterointerface of dual-phase oxide substrates through a phase transition and in situ exsolution of perovskite La0.5Sr0.5Fe0.8Ni0.1Nb0.1O3-δ (LSFNNb0.1) in wet H2 (3% H2O) at 800 °C. The core-shell nanoparticles are composed of a Ni-Fe alloy core and a SrLaFeO4-type layered perovskite oxide shell (RP-Ruddlesden-Popper-layered perovskites), which synergistically improves the electrochemical activity and effectively suppresses aggregation and coarsening of the metallic core. The RP phase also covers the surface of perovskite bulk (SP-single perovskite), forming the heterointerface and preventing further decomposition of the SP phase. The RP/SP heterointerface may improve the kinetics of surface exchange of oxygen species, resulting in the enhancement of performance and durability of the reduced LSFNNb0.1 as an anode for solid oxide fuel cells (SOFCs). A doped zirconia electrolyte-supported single cell with the anode achieves the maximum power density (MPD) of 0.83 W cm-2 at 800 °C in wet H2, and the corresponding polarization resistance is as low as 0.15 Ω cm2. This work reveals the formation mechanism of the MNA by investigating the evolution of the crystal structure, composition and morphology of LSFNNb0.1, when changing reducing temperature and time in wet H2 and 5% H2-Ar. The oxygen vacancies and phase transitions are found to play important roles in the formation of the MNA. The construction of MNAs in one step opens a new opportunity to design and prepare high-performance and stable catalysts for applications in energy conversion and storage.

Tooeleite (Fe6(AsO3)4SO4(OH)4·4H2O) is widely precipitated for direct As(III) removal from sulfate-rich industrial effluents. However, whether or not Fe(III)–As(III)–Cl(-I) precipitate is produced in chloridizing leaching media for As immobilization is almost unknown. This work founded the existence of ferric arsenite (hydroxy)chloride as a new mineral for As(III) removal. Its chemical composition and solid characterization were subsequently studied by using scanning electron microscope with an energy dispersive spectrometer (SEM-EDS), X-ray diffraction (XRD), infrared (FT-IR), Raman spectroscopy and thermogravimetric (TG) curve. The results showed the formation of a yellow precipitate after 3-days reaction of Fe(III)/As(III) with molar ratio ≈ 1.7 in chloride solution at pH 2.3 neutralized with NaOH. Compared with tooeleite, chemical analysis and solid characterization indicated that Cl(-I) replaces SO4(-II) producing ferric arsenite hydroxychloride with formula Fe5(AsO3)3Cl2(OH)4·5H2O. This new plate shaped solid showed better crytallinity than tooeleite, although it has similar morphology and characteristic bands to tooeleite. The FT-IR bands at 628, 964 cm−1 and the Raman bands at 448, 610, 961 cm−1 were assigned to Fe–O or As(III)–O–Fe or As(III)–O bending/stretching vibration, indicating that both arsenite and chloride substituted for the position of sulfate for ferric arsenite hydroxychloride produced due to the lack of the SO42− vibrations. Cl-(I) also contributed to increase As removal efficiency in aqueous sulfate media under acidic pH conditions via the probable formation of sulfate-chloride ferric arsenite.

Metal-air batteries (MABs) and reversible fuel cells (RFCs) rely on the bifunctional oxygen catalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Finding efficient bifunctional oxygen catalysts is the ultimate goal and it has attracted a great deal of attention. The dilemma is that a good ORR catalyst is not necessarily efficient for OER, and vice versa. Thus, the development of a new type of bifunctional oxygen catalysts should ensure that the catalysts exhibit high activity for both OER and ORR. Composites with multicomponents for active centers supported on highly conductive matrices could be able to meet the challenges and offering new opportunities. In this Review, the evolution of bifunctional catalysts is summarized and discussed aiming to deliver high-performance bifunctional catalysts with low overpotentials.

The aggregation-induced emission (AIE) mechanism of restriction of double-bond rotation (RDBR) was utilized to design an excellent solid emitter and sensor for the first time. Thus, cis-tetraphenylethylene (TPE) macrocycle diammoniums were synthesized and bound to a DNA chain by its two ammonium arms. The formed TPE dicycle at the cis position restricted the rotation of the double bond in both the ground and excited states, resulting in AIE enhancement, chiroptical performance enhancement, and sensing enhancement.

Nickel cobalt sulfide (NiCo2S4) is a promising battery-type material for electrochemical energy storage. However, the slow charge transfer kinetics and ion diffusion as well as the deficiency of electrochemically active sites hinder the practical application of NiCo2S4. Defect engineering at the atomic level is adopted to improve charge storage kinetics, through the incorporation of P dopants and S vacancies onto the surface of a NiCo2S4 nanotube (P-NiCo2S4−x). Experimental results reveal that the introduction of these defects effectively increases the electrical conductivity and induces the formation of low oxidation state Ni and Co species, accelerating the charge transfer kinetics and enabling rich faradaic redox chemistry. Moreover, the partial substitution of S sites with P improves the covalent nature of P-NiCo2S4−x, facilitating surface electroactivity. The as-prepared P-NiCo2S4−x shows a high specific capacity of 1806.4 C g−1 at 1 A g−1 and a 95.5% capacity retention after 5000 cycles at a high current density of 30 A g−1. Flexible solid-state asymmetric supercapacitors with P-NiCo2S4−x and activated carbon as the positive and negative electrodes, respectively, deliver a high energy density of 68.2 W h kg−1 at 800 W kg−1 and excellent cycling stability. Moreover, the device exhibits good mechanical flexibility with negligible capacitance decay under different bending states.

Naringin is a kind of multi-source food additive which has been explored broadly for its various biological activities and therapeutic potential. In the present study, the protective effect and mechanism of naringin on dextran sulfate sodium (DSS)-induced ulcerative colitis (UC) in mice were investigated. The results showed that naringin significantly alleviated DSS-induced colitis symptoms, including disease activity index (DAI), colon length shortening, and colon pathological damage. The tissue and serum secretion of inflammatory cytokines, as well as the oxidative stress, were decreased accordingly upon naringin intervention. Naringin also decreased the proteins involved in inflammation and increased the expression of tight junction (TJ) proteins. Moreover, naringin increased the relative abundance of Firmicutes/Bacteroides and reduced the content of Proteobacteria to improve the intestinal flora disorder caused by DSS, which promotes the intestinal health of mice. It was concluded that naringin can significantly ameliorate the pathogenic symptoms of UC through inhibiting inflammatory response and regulating intestinal microbiota, which might be a promising natural therapeutic agent for the dietary treatment of UC and the improvement of intestinal symbiosis.

Layered double hydroxides (LDHs) have attracted much attention in supercapacitors because of the high specific surface area and theoretical capacitance. However, the bad cycling stability has always been their Achilles' heel that restrains their further application. In this paper, a small amount of unactive and single-valence element zinc, which has no contribution to the capacitance of electrodes, was first doped into NiCo-LDHs through two consecutive electrodeposition processes only within 30 min. With a polyaniline (PANI) nanolayer as the interlayer, an ultrathin NiCoZn-LDH nanoplate network was well-anchored on the carbon cloth surface. The slight Zn2+ doping dramatically enhanced the cycling performance of LDHs with little capacitance decay. Zn2+ doping enhanced the cyclic structural stability of NiCoZn-LDHs, while the PANI layer strengthened the interface interaction between LDHs and the current collector. By controlling the doping content of Zn2+ at 2.9%, the composite electrode achieved the best performance with a high specific capacitance of 1749 F g-1 and an ultralong life span with 89% capacitance retention after 40,000 charge-discharge cycles. This work offers a novel strategy to fast build LDH-based supercapacitors with both high specific capacitance and cycling performance.

Adiponectin is an important adipocytokine and plays the roles in multiple metabolic processes via binding its receptors - AdipoR1 and AdipoR2, which has also been found to participate in the regulation of the reproductive system of animals, in particular by influencing the secretion of ovarian steroid hormones. To further investigate the expression of adiponectin and its receptors in follicles after in vitro incubation, and their role in the steroid synthesis of laying hens’ ovaries, we performed qRT-PCR and ELISA to detect the expressions of AdipoQ, AdipoR1, and AidpoR2, and determined the key genes involved in steroidogenesis and the secretion of estradiol (E2) and progesterone (P4) through the in vitro activation of adiponectin (AipoRon) and overexpression or knockdown of AdipoR1 and AdipoR2. Our results revealed that adiponectin and its receptors wildly exist in follicles and granulosa cells, and AdipoRon (5 and 10 µg/mL) had no effect on granulosa cell proliferation and apoptosis but significantly stimulated the secretion of adiponectin and its receptors in granulosa cells after incubation for 24 h. Furthermore, AdipoRon could significantly stimulate the secretion of P4 and inhibit E2 level compared to those of the control group through modulating the key genes expression of steroidogenesis (CYP19A1, StAR, CYP11A1, FSHR, and LHR). The secretion of E2 was also decreased in granulosa cells by the treatments of overexpression and knockdown of AdipoR1/2, however, there was no difference in terms of the level of P4 and StAR expression between them if there was overexpression or knockdown of AdipoR1/2. In addition, it was shown that the secretion of E2 only exhibits a marked drop if co-processing 10 µg/mL AdipoRon and pGMLV AdipoR2 compared to single treatments. Taken together, the study highlighted the role of adiponectin and its receptors in the regulation of steroid synthesis and secretion in ovarian granulosa cells in laying hens.

The rhizome of Polygonatum cyrtonema (Polygonati Rhizoma) is widely consumed as medicine-homology-food in Asia for its tonic effect, which can be enhanced by traditional steam-sun drying for nine cycles. However, the multi-constituents variation in this process was unclear, and the necessity of nine cycles should be further discussed. In this study, the multiple constituents, including saccharides, amino acids, nucleosides and bases, lipids, saponins, homoisoflavones and cinnamamides, in P. cyrtonema treated with sun drying, heated air drying, each cycle of steam-heated air drying, infrared drying and microwave drying were compared. The results showed that the content of total saccharides increased in samples from one to four cycles of steam-heated air drying (365.0 - 945.6 mg/g) and decreased from four to nine (945.6 - 288.0 mg/g). The content of fructose increased in samples from one to six cycles (29.9 - 234.7 mg/g) and decreased from six to nine (234.7 mg/g - 177.7 mg/g). The abundance of most phospholipids and free fatty acids increased continuously from one to nine cycles while most of the amino acids, nucleosides and bases showed continuous declining trend. Principal component analysis showed that the samples treated with one to four cycles were wider in distance than four to nine, indicating the chemical composition tending to be stable after fourth steaming. If taking total saccharides, fructose, and phospholipids as the major quality indicator, four cycles of steam-heated air drying processing should be the ideal postharvest processing method to obtain better taste, flavor and functionality. Samples treated with heated-air drying and infrared drying were far in distance from steaming ones by hierarchical cluster analysis, which means these processing methods were not suitable to replace the traditional steam-sun drying process. Collectively, the above results will not only provide novel processing methods that will obtain the high active ingredients for P. cyrtonema, but also shed light on the optimization of processing technology for the industrial production of medicinal crops which need nine cycles of steam-sun drying processing.

Two new tfmpiq-based bis-cyclometalated iridium(III) complexes, [(tfmpiq) 2 Ir(imdzppo)] ( 2a ) and [(tfmpiq) 2 Ir(idzpo)] ( 2b ) (where tfmpiq = 1-(4-(trifluoromethyl)phenyl)isoquinoline, imdzppo = 2-(imidazo[1,2-a]pyridin-2-yl)phenol, idzpo = 2-(2 H -indazol-2-yl)phenol), have been synthesized and fully characterized. The single crystal structure of 2b has been determined. The relationship between the structures and photophysical properties of both complexes are considered, and the DFT calculations have been used to further support the deduction. These Ir(III) complexes emit red light with quantum yields of 39.9–51.9% in degassed CH 2 Cl 2 solution at room temperature. Also, their emission originates from a hybrid 3 MLCT/ 3 LLCT/ 3 LC excited state. All these results show that iridium(III) complexes 2a - 2b are suitable for red-phosphorescent materials in OLEDs.

Background Coagulopathy is a severe complication of traumatic brain injury (TBI) and can cause secondary injuries and death. Decrease of FVII activity contributes to the coagulopathy and progressive hemorrhagic injury (PHI) in patients with isolated TBI. Some polymorphic loci of coagulation factor VII (FVII) are shown to be essential for FVII activity. However, the relationship between FVII gene polymorphisms and coagulopathy in patients with isolated TBI is still unknown. Therefore, the present study aimed to investigate the relationship between FVII gene polymorphisms and plasma FVIIa levels, and assess whether FVII polymorphisms were associated with TBI-related coagulopathy, PHI, and 6 months GOS in patients with isolated TBI. Methods One-hundred-forty-nine patients with isolated TBI (from East of China) admitted to Huashan Hospital's Neurological Trauma Center from March 2012 to March 2016 were enrolled in this study. The Polymorphism-Polymerase Chain Reaction (PCR) method was used to analyze the five FVII polymorphism loci (-323P0/P10, R353Q, -401G/T, -402G/A, and -670A/C) of these patients. Patients' blood was collected to test the activated partial thromboplastin time, international normalized ratio, platelet, and FVIIa concentrations. Other clinical characteristics were also recorded. Results The minor alleles of three genotypes of -323 P0/P10, R353Q, and -401G/T each independently associated with 23.3%, 28.6%, and 27.6% lower FVIIa levels, respectively. These polymorphisms explained 21% of the total variance of FVIIa levels (adjusted R2:0.206). The genotype of -323P0/P10 was an independent risk factor for coagulopathy (OR = 2.77, p = 0.043) and PHI (OR = 3.47, p = 0.03) after adjustment for confounding factors in the logistic regression model. Polymorphisms of FVII were not independently associated with 6 months Glasgow Outcome Scale (GOS) of isolated TBI patients. Conclusion -323P0/P10, R353Q, and -401 G/T genotypes were associated with FVIIa levels. -323P0/P10 genotype was independently associated with traumatic coagulopathy and PHI in isolated TBI patients.

A palladium-catalyzed domino Heck cyclization/Hiyama coupling reaction by the trapping of the σ-alkylpalladium intermediate with arylsilanes is described. A wide range of aryl-tethered alkenes and arylsilanes are all compatible with the reaction conditions. This approach shows good yields and excellent functional group tolerance, presenting a more practical and sustainable alternative to the conventional domino Heck cyclization/Suzuki coupling reaction.

In this work, lateral-field-excitation (LFE) piezoelectric sensors based on polarity inversion layer are designed and fabricated, then frequency stabilities and sensitivities on electric property changes of liquids are tested. Because the polarity inversion layer can suppress the spurious modes, the stabilities of the LFE devices with a polarity inversion layer are obviously better than that of LFE devices with no polarity inversion layer. On the changes of liquid conductivity and permittivity, the sensitivities of the LFE devices with a polarity inversion layer are 2.4 times and 2.1 times higher than that of LFE devices with no polarity inversion layer, respectively. The polarity inversion layer of the lithium niobate crystal plate can be realized conveniently by heat treatment, therefore, the technology of the polarity inversion layer can play an important role in improving the sensing performances of LFE sensors.

A novel diphenylamine/spiro[fluorene-9,9′-xanthene] (SFX) hybrid (SFX27DPA) was constructed successfully by incorporating diphenylamine into SFX via Pd-catalyzed C N cross-coupling to ingeniously develop state-of-the-art models of solution-processible small molecule host for uncovering the structure-property relationship of molecular structure change in the application of PhOLEDs, which is vital to rational cumulative enhancement in device performance by purposive and feasible structure modifications. SFX27DPA shows outstanding thermal stability (Td, 425 °C) compared to those of SFXDPA ((Spiro[fluorene-9,9′-xanthen]-2-yl)-diphenylamine) (Td, 338 °C) and SFX-Cz ((2-carbazolyl-spiro[fluorene-9,9′-xanthene]) (Td, 345 °C) by increasing the molecular weight but owns weak morphological stability due to its low melting point (Tc, 60.5 °C). The HOMO (−5.28 eV), LUMO (−2.08 eV), and energy gap (Eg, 3.20 eV) were obtained by cyclic voltammetry measurements (CVs). The high T1 (T1, 2.98 eV) and narrow energy gap (Eg, 3.20 eV) are beneficial to achieving high efficient device. The compound not only possesses a high triplet energy level but also exhibits good solubility in common solvents. Two SFX-based compounds (SFX27DPA, SFX-Cz) for red PhOLEDs have been fabricated successfully by solution process for deep researching the relationship between molecular structure and device performance. An enhanced performance of device based on SFX27DPA with maximum external quantum efficiencies (EQEs) of 10.9% under lower driving voltage was obtained compared to that of SFX-Cz-based red PhOLEDs (1.5%). This investigation offers good reference for future molecular design to achieve high performance through accumulative structure modification.

Background In recent years, the incidence of fungal infection has been increasing, often invading one or more systems of the body. However, it is rare for lymph nodes to be invaded without the involvement of other organs. Case summary A 21-year-old man was admitted to hospital for repeated cough for 2 mo and abdominal pain for 1 mo. Physical examination revealed multiple lymph nodes enlargement, especially those in the left neck and groin. CT scan showed multiple lymph nodes enlargement in the chest, especially left lung, abdominal cavity, and retroperitoneum. The first lymph node biopsy revealed granulomatous lesions of lymph nodes, so intravenous infusion of Cefoperazone tazobactam combined with anti-tuberculosis drugs were given. Because fever and respiratory failure occurred 4 d after admission, mechanical ventilation was given, and Caspofungin and Voriconazole were used successively. However, the disease still could not be controlled. On the 11th day of admission, the body temperature reached 40° C. After mycosis of lymph nodes was confirmed by the second lymph node biopsy, Amphotericin B was given, and the patient recovered and was discharged from the hospital. Conclusion No fixed target organ was identified in this case, and only lymph node involvement was found. Caspofungin, a new antifungal drug, and the conventional first choice drug, Voriconazole, were ineffective, while Amphotericin B was effective.

A novel bulky 1,3,4-oxadiazole-based spirocyclic compound 2,5-bis(2-spiro[fluorene-9,9′-xanthene]-7-yl)phenyl)-1,3,4-oxadiazole (D- [2-SFXP]-o-OXD) has been synthesized successfully by incorporating spiro[fluorene-9,9′-xanthene] (SFX) into 2,5-biphenyl-1,3,4-oxadiazole reaction via Suzuki cross-coupling with Pd(PPh3)4 as catalyst. The electrochemical properties of the compound were researched via cyclic voltammetry (CV) and obtained the HOMO, LUMO, and energy gap (Eg, 3.57 eV). The green TADF OLEDs hosted D[2-SFXP]-o-OXD and D[2-SFXP]-o-OXD:mCP by solution-processing techniques with maximum current efficiency (CE) and EQE (external quantum efficiency) of 15.2 cd A−1/4.8% and 25.9 cd A−1/8.5% as the doping concentration increasing from 5% to 10%, respectively. The electroluminescent (EL) spectra are independent of the concentration changes, which exhibits the three dimensional bulky D[2-SFXP]-o-OXD with large steric hindrance could successfully suppress the concentration quenching and excimer emission.

Solubilization of arsenate in guts of deposit-feeders is a key process for their dietary uptake of arsenate from contaminated sediments. The present study explored this digestive solubilization with in vitro extraction experiments that quantified arsenic (As) release from substrates (natural sediment and As-enriched iron oxides) in the presence of various digestive agents (proteins, amino acids and surfactants collected from gut fluid of a sipunculan worm). To investigate potential mechanisms for the influence of digestive agents, analyses determined correlations between As and Fe concentrations, the size distribution of the As bound to the digestive agents, and the adsorption of the digestive agents on the substrates. Both the digestive surfactants and proteinaceous materials increased arsenate mobilization, with the surfactants enhancing the effects of the proteinaceous materials. Arsenate reduction and reductive dissolution of iron oxides were not observed and correlations between the concentrations of released As and Fe were weak. These findings indicate that dissolution release of Fe did not appear to be the main route by which the digestive agents mobilized particle-associated As. Most of the released As (>70%) was distributed in the

The properties from both bulk phases (magnetism and thermal stability) and surface (composition, orientation, and stability) of iron silicide model compounds were evaluated by a theoretical study w...

Graphene or reduced graphene oxide films (rGOFs) can be prepared by a number of methods including chemical vapor deposition (CVD), filtration, and spin-coating for a variety of applications. However, controlling their surface morphologies and microstructures to meet the requirements of specific applications is still a great challenge. Here, controlled microstructure of large-size rGOF with good electrical and thermal conductivities as well as high sorption ability is produced through a heating-assisted spray method. By simply tuning the heating temperature, the smooth surface and close-packed layered structure of rGOF can be changed to rough surface and porous structure. Impressively, the rapid preparation of rGOF with area as large as ∼216 cm2 in only 6 h has been successfully achieved, which is significant since normally it takes several days to prepare a rGOF with small area of ∼10 cm2 by using conventional filtration method. More importantly, our rGOFs show promising applications in oil sorption, supercapacitors, and thermally/electrically conductive films. Environment & Water Industry Development Council (EWI) Ministry of Education (MOE) Nanyang Technological University National Research Foundation (NRF) H.B. and S.W. contributed equally to this paper. This work was supported by the Fundamental Research Funds for the Central Universities (2242017K41006, and 2242016R20013), the National Natural Science Foundation of China (Nos 61274114, 51420105003, and 113279028), China Postdoctoral Science Foundation funded project (Nos 2017M611653), and the “Qianjiang Scholars” program and “Thousand Talent Program” of Zhejiang Province. This work was also supported by MOE under AcRF Tier 2 (ARC 19/15, No. MOE2014-T2-2-093; MOE2015-T2-2-057; MOE2016-T2-2-103) and AcRF Tier 1 (2016-T1-001-147; 2016-T1-002-051), NTU under Start-Up Grant (M4081296.070.500000), and NOL Fellowship Programme Research Grant in Singapore. This research grant is supported by the Singapore National Research Foundation under its Environmental & Water Technologies Strategic Research Programme and administered by the Environment & Water Industry Programme Office (EWI) of the PUB (project No.: 1301-IRIS-47). This research is supported by the National Research Foundation, Prime Minister's Office, Singapore under its Campus for Research Excellence and Technological Enterprise (CREATE) programme.

Organic solar cells (OSCs) have made rapid advances in power conversion efficiency during the past decades, which is boosted partly by the various designs of new materials, especially in donor mate...

Sulfidization of nano-ferrihydrite (nano-Fhy) by S(−II) plays an important role in Fe and As biogeochemistry in wetland soils, sediments, and aquifers. However, during early stages, the changes in speciation and redistribution of adsorbed As remain unclear. This study investigated the reduction and transformation of As-bearing nano-Fhy and subsequent As repartitioning among secondary phases induced by an environmentally relevant concentration of sulfide (S(−II)) (Fe/S ratio = 80, S(−II) concentration = 0.5 mM) at pH 7. Chemical analysis indicated that the mobility of As associated with iron oxyhydroxide minerals was greatly reduced during the transformation of nano-Fhy. The initially adsorbed As was partially (60–90%) transformed to a phosphate-unextractable phase and approximately 50–90% of As(III) was oxidized to As(V) during recrystallization of nano-Fhy to lepidocrocite and goethite. The intermediate Fe species formed during electron (e−) transfer from S(−II) to Fe(III) and subsequent e− transfer between Fe(II) and Fe(III) may be responsible for oxidization of As(III). The S K-edge X-ray absorption near edge structure (XANES) results showed that S(−II) could be oxidized to multiple valence states and its evolution was strongly affected by the concentration and speciation of As. As(III) can inhibit the oxidation of S(−II) to sulfate, whereas the presence of As(V) may promote the oxidation of S(−II) to sulfate compared with the system without As. These findings have important environmental implications for As, Fe, and S redox cycling during early stage sulfidization of nano-Fhy.

The ultrastable metal electrodes that can withstand the mechanical deformations of the soft substrates are always essential for the development of flexible supercapacitors. However, the metal electrode physically deposited on the flexible substrate is rigid and delaminated, and the contact interface is easily degraded under the mechanical cycling. The highly flexible and conductive composites with the intermixed metal–polymer structure as electrodes are key to solving the contact problem. In this work, a universal and facile method for flexible micro-supercapacitors (MSCs) with combination of nickel electroless plating (EN) and reduced graphene oxide (rGO) electrodeposition was presented. The so-called surface exchange and ion exchange (SMIE) technique has been employed to prepare the seed layer, and the electroless plating was conducted to deposit the Ni–P layer. The rGO-coated (GC) layer was then electrodeposited onto the Ni–P layer to form an EN/GC composite structure. EN/GC electrodes with symmetric i...

Chlorination is often adopted in the synthesis of donor materials considering the obvious improvement on efficiency of organic photovoltaic (OPV) device. Thus the chlorination effect was firstly probed based on density functional theory (DFT) calculation, which shows that the chlorinated benzothiadiazole connected with two thiophene rings (BTClTT) fragment although has larger optical bandgap and relatively blue-shifted spectrum, its deeper frontier molecular orbital (FMO) energy level, larger charge transfer distance (DCT) and much more transferred charges (CT), obvious negative natural population analysis (NPA) charges, larger twisted dihedral angles and smaller value of BLA indicate its favorable properties for the application in OPVs. Then, we designed a series of donor materials 2–7 adopting two strategies based on the experimental polymer 1 which contains BTClTT fragment. The calculated physical parameters characterizing OPV performance such as open-circuit voltage (VOC) and absorption-properties manifest that the design through side chains modifications for 2–5 may have slight influence on their cell performance while the backbone replacements for 6 and 7 exhibit prominent enhancement whether on VOC and photon-absorption property or on the charge separation ability. Therefore, our calculations suggest feasible strategies of designing donor materials for the chlorinated BT-based donor materials in OPVs. We hope our work can provide some guidelines for the future study on chlorinated donor materials.

Long-term storage of Fe(III)-As(V) co-precipitate wastes derived from the industrial As removal process poses the risk of secondary arsenic pollution to the local environment. However, its stability in only iron-reducing environment remains unclear. The effect of iron reduction by hydroquinone (QH2) on the stability of co-precipitate at Fe/As molar ratio of 5 was investigated in this study. The results showed that 16.5–93% of Fe(III) reduction in NaOH-neutralized co-precipitate caused 0.1–11% (0.1–8.5 mg L-1) As release and 0.9–46% (2.6–130 mg L-1) Fe(II) release at pH 4 and 6. Most of the As(V) and more than half of the Fe(II) generated by the reductive decomposition of Fe(III)-As(V) co-precipitate were retained in solid phases. Solid characterization and thermodynamic calculation indicated that amorphous Fe3(AsO4)2 was probably the major secondary mineral for As immobilization. At pH 8, 11–39% As and less than 4% Fe(II) were released into solution after 3.6–87% Fe(III) was reduced to Fe(II). Both amorphous Fe3(AsO4)2 and Fe(II,III) (hydr)oxides were responsible for As retention. The solubility of NaOH-neutralized co-precipitates in terms of dissolved As concentration upon Fe(III) reduction at pH 4, 6 and 8 with QH2/Fe(III) mol of 1 was lower than that in oxic environment. It was also lower than the solubility of Ca(OH)2-neutralized co-precipitate after Fe(III) reduction at pH 4 and 6.

It is very attractive yet underexplored to synthesize heterocyclic moieties pertaining to biologically active molecules from biomass-based starting compounds. Herein, we report an electrocatalytic Achmatowicz reaction for the synthesis of hydropyranones from furfuryl alcohols, which can be readily produced from biomass-derived and industrially available furfural. Taking advantage of photo-induced polymerization of a bipyridyl ligand, we demonstrate the facile preparation of a heterogenized nickel electrocatalyst, which effectively drives the Achmatowicz reaction electrochemically. A suite of characterization techniques and density functional theory computations were performed to aid the understanding of the reaction mechanism. It is rationalized that the unsaturated coordination sphere of nickel sites in our electrocatalyst plays an important role at low applied potential, not only allowing the intimate interaction between the nickel center and furfuryl alcohol but also enabling the transfer of hydroxide from nickel to the bound furfuryl alcohol., The synthesis of heterocyclic moieties pertaining to biologically active molecules from biomass-based starting compounds is very attractive yet underexplored. Herein, the authors report an electrocatalytic Achmatowicz reaction for the synthesis of hydropyranones from biomass-derived furfuryl alcohols.

To face the challenge of all-climate application, organic rechargeable batteries must hold the capability of efficiently operating both at high temperatures (>50 °C) and low temperatures (-20 °C). However, the low electronic conductivity and high solubility of organic molecules significantly impede the development in electrochemical energy storage. This issue can be effectively diminished using functionalized porphyrin complex-based organic cathodes by the in-situ electropolymerization of electrodes at elevating temperatures during electrochemical cycling. [5,15-bis(ethynyl)-10,20-diphenylporphinato]copper(II) (CuDEPP)- and 5,15-bis(ethynyl)-10,20-diphenylporphinato (DEPP)-based cathodes are proposed as models, and it is proved that a largely improved electrochemical performance is observed in both cathodes at a high operating temperature. Reversible capacities of 249 and 105 mA h g-1 are obtained for the CuDEPP and DEPP cathodes after 1000 cycles at 50 °C, respectively. The result indicates that the temperature-induced in situ electropolymerization strategy responds to the enhanced electrochemical performance. This study would open new opportunities for developing highly stable organic cathodes for electrochemical energy storage even at high temperatures.

BACKGROUND Ultraviolet (UV) radiation is a key risk factor of environment to contribute photoaging and skin cancer through production of reactive oxygen species (ROS) and inflammatory responses. Astragaloside IV (AS-IV) is an active component from Astragalus membranaceus, and shows various pharmacological effects on inflammation, oxidative stress and apoptosis. However, whether AS-IV shows protective effect on UVB-induced injury in epidermal keratinocytes remain unknown. AIMS To explored the effects of AS-IV on UVB-induced oxidative injury and inflammatory response in human epidermal keratinocytes. METHODS HaCaT keratinocytes were exposed to UVB irradiation, followed by AS-IV incubation. The cell viability, intracellular ROS level, oxidative stress, and apoptosis were determined. The regulatory effects of AS-IV on toll-like receptor 4 (TLR4) pathway in UVB-exposed HaCaT cells were also investigated. RESULTS Astragaloside IV pretreatment (10, 25, 50, 100 and 150 μM) increased cell viability in UVB-exposed HaCaT cells. AS-IV (50 μM) significantly reduced intracellular ROS level and lipid oxidation product malondialdehyde(MDA) content, and increased a ROS-scavenging enzyme superoxide dismutase (SOD) in HaCaT cells with UVB irradiation. In addition, AS-IV pretreatment suppressed apoptosis, increased Bax protein, caspase-3 and 9, and decreased BCL-2 protein in contrast to HaCaT cells with UVB-irradiation. AS-IV suppressed proinflammatory cytokine production, inhibited TLR4 and its downstream signaling molecules NF-κB, iNOS and cyclooxygenase-2 (COX-2) protein expression. We also found that the effects of AS-IV on cell viability and TLR4 expression was reversed by NAC. The protective of AS-IV on UVB-induced damage and TLR4 expression was dependent on ROS, as the increase in viability and decrease in TLR4 protein by AS-IV was significantly attenuated by ROS scavenger NAC (1 mM). CONCLUSION Astragaloside IV prevent UVB-induced oxidative damage and inflammation by inhibiting TLR4 expression.

Objective: To investigate the roles of serum uric acid (UA), bilirubin (BIL), albumin (ALB), and creatinine (CRE) as major intravascular antioxidants, in benign paroxysmal positional vertigo (BPPV).Methods: The serum levels of UA, BIL, ALB, and CRE were retrospectively analyzed in 70 patients with new-onset idiopathic BPPV and 140 age- and sex-matched healthy controls (HCs).Results: Serum UA, BIL, ALB, and CRE levels were significantly lower in the BPPV group than the HC group. Furthermore, serum levels of BIL and ALB were significantly lower in the BPPV group when compared by sex. Multiple stepwise logistic regression revealed that a reduction in serum ALB was independently related to BPPV (odds ratio = 0.688; 95% confidence interval = 0.607– 0.780). Receiver operating characteristic analyses revealed a cut-off value of 45.15 g/L for ALB with a sensitivity of 74.29% (62.97– 83.07%) and specificity of 73.57% (65.71– 80.18%).Conclusions: Serum levels of UA, BIL, ALB, and CRE were lower in BPPV patients, indicating a lower antioxidant status. Furthermore, a reduction in serum ALB was independently associated with BPPV. These results provide insights into the possible roles of oxidative stress in the pathogenesis of BPPV.

A convenient method for the synthesis of aryl-functionalized spirocyclohexadienone scaffolds from alkyne-containing phenol-based biaryls with aryl halides via palladium-catalyzed cyclization/dearomatization/arylation is developed. The approach provides a series of spirocyclohexadienone molecules in moderate to high yields. The reaction occurs chemoselectively through dearomative C-arylation rather than common O-arylation of phenols.

Two undescribed triterpenes, tricholimbrins A and B, three undescribed steroids, tricholimbrins C‒E, one undescribed 4-chromanone derivative, along with 27 known compounds were isolated from fruiting bodies of the mushroom Tricholoma imbricatum. Tricholimbrins A and B are two polycyclic triterpenoids with a carbon degradation, while tricholimbrin C is a ring-rearranged steroid containing an aromatic moiety that might be derived from an ergosterol. Isocyathisterol, 3β,15α-dihydroxyl-(22E,24R)-ergosta-5,8(14),22-trien-7-one, demethylincisterol A3, and volemolide showed cytotoxicities to six human cancer cell lines. 3β-Hydroxyl-(22E,24R)-ergosta-5,8,22-trien-7,15-dione and 3β-hydroxyl-(22E,24R)-ergosta-5,8,22-trien-7-one showed preferable cytotoxicities against HL-60 while chaxine C and volemolide showed preferable cytotoxicities against A-549, with IC50 values less than 10 μM.