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Detrimental tumor microenvironment (TME) relies on distorted tumor vasculature for further tumor expansion. Vascular normalization therapy partly improves TME through vessel repairing, while these therapies enter an unbreakable Mobius ring due to each attempt hindered by pro-angiogenic factors from TME, leading to limited duration and extent of vascular normalization. Here, we developed a nanosystem including FLG and MAR/MPA nanodrugs to regulate both tumor vasculature and TME. FLG nanodrugs were constructed by connecting VEGF/VEGFR2 inhibitory low molecular weight heparin and gambogic acid with F3 peptide decoration for directly regulating on vascular endothelial cells and inducing vascular normalization. Meanwhile, MAR/MPA nanodrugs encapsulating CCL5/CCR5 blocker maraviroc were designed to restrict cytokine functions of angiogenesis and TME deterioration, contributing to vasculature repairing and TME reconstruction. Our results demonstrated this combined nanosystem synergistically induced vascular normalization window lasting 9 days and restored vascular permeability and oxygen supply in Panc-1 tumor. Furthermore, in melanoma, our nanosystem achieved immune improvements with increased infiltration of CD4+ and CD8+T cells in a remodeled TME. The two nanodrugs assisting each other in terms of both vascular repairing and TME improvements successfully reversed the vicious crosstalk to a positive one, achieving overall TME remodeling and promoting therapeutic efficiency.

As a secondary Li-ion battery with high energy density, lithium-sulfur (Li-S) batteries possess high potential development prospects. One of the important ingredients to improve the safety and energy density in Li-S batteries is the solid-state electrolyte. However, the poor ionic conductivity largely limits its application for the commercial market. At present, the gel electrolyte prepared by combining the electrolyte or ionic liquid with the all-solid electrolyte is an effective method to solve the low ion conductivity of the solid electrolyte. We present a cross-linked gel polymer electrolyte with fluoroethylene carbonate (FEC) as a solid electrolyte interface (SEI) film formed for Li-S quasi-solid-state batteries, which can be simply synthesized without initiators. This gel polymer electrolyte with FEC as an additive (GPE@FEC) possesses high ionic conductivity (0.830 × 10-3 S/cm at 25 °C and 1.577 × 10-3 S/cm at 85 °C) and extremely high Li-ion transference number (tLi+ = 0.674). In addition, the strong ability toward anchoring polysulfides resulting in the high electrochemical performance of Li-S batteries was confirmed in GPE@FEC by the diffusion experiment, X-ray photoelectron spectroscopy analysis (XPS), and scanning electron microscopy (SEM) mapping of the S element. Such a high ion conductivity (IC) gel polymer electrolyte enables a competitive specific capacity of 940 mAh/g at 0.2C and supreme cycling performance for 180 cycles at 0.5C, which is far beyond that of conventional poly(ethylene oxide)-based quasi-solid-state Li-S batteries.

Iodine(III)-mediated synthesis of 4-iodo-N-phenylaniline from iodobenzene has been achieved, and the reaction can proceed under mild conditions. A variety of functional groups were well tolerated, providing the corresponding products in moderate to good yields. The remaining iodine group provides an effective platform for converting the products into several valuable asymmetric diphenylamines. Most importantly, this reaction can be easily scaled up to the ten-gram scale, highlighting its synthetic utility. The mechanistic study revealed that the in situ generated aryl hypervalent iodine intermediate is the key factor to realize this para-selective C-H amination reaction.

A novel approach to synthesize 3-methylisoquinolines via a one-pot, two-step, palladium(II)-catalyzed tandem C-H allylation/intermolecular amination and aromatization is reported. A wide series of 3-methylisoquinoline derivatives were obtained directly using this method in moderate to good yields, and we highlight the synthetic importance of this new transformation.

Urea/1-ethyl-3-methylimidazolium chloride (urea-EMIC) was developed to electrodeposit Cu from Cu2O at room temperature. Density, viscosity and conductivity of this urea-EMIC system were obtained. The cyclic voltammograms illustrated that the electroreduction of copper ion (Cu(I) ion) involves a quasi-reversible and one-step single electron transfer process. Chronoamperometric studies showed that the copper electrodeposition proceeds a three-dimensional (3D) progressive model. With an increase in temperature, on voltammograms the onset potentials for copper ion reduction shifted anodically and the diffusion coefficient determined using chronoamperometry increased from 5.40 × 10−11 m2 s−1 at 333 K to 1.02 × 10−10 m2 s−1 at 363 K. Also, potentiostatic electrolysis was conducted on tungsten substrates at − 0.65 V (vs. Ag) and 363 K. Then spherical metallic copper electrodeposits were obtained.

The thermal-condensation method is widely used for the synthesis of K-doped g-C3N4 photocatalysts, but the presence of organic byproducts in the resultant products is often overlooked in previous reports. Here, we demonstrated the universal presence of organic byproducts in K-doped g-C3N4 synthesized by typical thermal condensation of KOH/melamine, KOH/dicyandiamide, or KOH/urea. Taking the K-doped g-C3N4 photocatalysis for the degradation of dimethyl phthalate as an example, the negative influence of the organic byproducts on K-doped g-C3N4 photocatalysis was confirmed. Specifically, the organic byproducts can be gradually dissolved into the photocatalytic system of K-doped g-C3N4 as new and stable pollutants. Based on the solubility investigations on the byproducts in several solvents, hot-water washing was demonstrated to be a relatively effective approach to remove the organic byproducts from K-doped g-C3N4. The formation of organic byproducts during the synthesis of K-doped g-C3N4 could be ascribed to the fact that the presence of K salts in melamine, dicyandiamide, or urea molecules results in their insufficient thermal condensation into expected g-C3N4. The present work provides objective information about the K-doped g-C3N4 photocatalysts and reminds researchers about the influence of the organic byproducts on the applications of the other impurity-doped g-C3N4 photocatalysts.

To electrochemically extract Pb from PbO at room temperature, a new electrolyte, urea−1-ethyl-3- methylimidazolium fluoride (urea−[EMIM]F), was synthesized to dissolve PbO. Afterwards, the electrochemical behavior of Pb in this electrolyte was studied. The density, viscosity and conductivity of this electrolyte were investigated before electroextraction. The electrochemical behavior of Pb in the urea−[EMIM]F system was recorded via cyclic voltammograms, chronoamperometry and potentiostatic electrolysis. The results illustrate that Pb can be electrochemically extracted from PbO in this system at room temperature and that Pb reduction involves a quasireversible process and follows a one-step and two-electron transfer process. The reduction of Pb proceeds with a three-dimensional (3D) progressive model. With an increase in temperature, the onset potentials for Pb reduction shift anodically. The diffusion coefficient of Pb(II) is determined to be 6.88×10−10 cm2/s at 353 K. Additionally, spherical Pb particles are obtained after electrodeposition in the urea−[EMIM]F system via potentiostatic electrolysis.

Polycyclic aromatic hydrocarbons (PAHs) are regarded as promising electrochemiluminescent (ECL) emitters owing to their high quantum efficiency and inexpensive production. Despite the fact that the ECL properties of the pure PAH microcrystal (such as rubrene microcrystals, Rub MCs) have gained extensive attention, it is a challenge in controlling the morphology and size to reduce the inner filter effect. Herein, an advanced ECL emitter of palladium nanoparticle-functionalized hollow PAH-metal nanocubes was prepared by an in situ redox deposition method (the resultant nanocomposites were abbreviated as Pd-Rub-Ag@Au nanocubes). Specifically, the rubrene-decorated Ag@Au nanocubes (Rub-Ag@Au nanocubes) were prepared using the Ag@Au nanocubes as a template and a rubrene cation radical (Rub•+) as a reductant, and then Pd nanoparticles (Pd NPs) were in situ reduced on the surface of Rub-Ag@Au nanocubes. Impressively, compared with the Rub MCs, Pd-Rub-Ag@Au nanocubes showed uniform size and significantly enhanced ECL efficiency and intensity in the aqueous media. As a proof-of-concept, the Pd-Rub-Ag@Au nanocube-based ECL biosensing platform combined with a multisite-anchored DNA nanomachine was constructed for ochratoxin A (OTA, a type of mycotoxin) detection. The DNA nanomachine covered with high-density recognizing sequences could operate toehold-mediated strand displacement amplification on the sensing platform and promote the movement efficiency and velocity greatly. Due to the advanced performance of Pd-Rub-Ag@Au nanocubes and high recognition efficiency of the DNA nanomachine, the proposed biosensor for OTA detection can achieve a detection limit of 4.7 fg/mL ranging from 0.01 to 100 pg/mL, which offers an ingenious method for the further application of PAHs.

Ultradeep carbonate gas reservoirs are a major resource of interest in clean energy development, and complex pore structures and reservoir conditions with high-temperatures and pressures are great ...

A ternary biochar/vanadium pentoxide/graphite like carbon nitride (BC/V2O5/g-C3N4 denoted BC/VO/CN) composite was prepared by a simple hydrothermal method and its photocatalytic performance was investigated under simulated solar irradiation. The BC/VO/CN was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, UV-vis diffuse reflectance spectroscopy, and photoluminescence spectroscopy. Within the BC/VO/CN composites VO nanoparticles were highly crystalline and intertwined with the lamellas of CN, resulting in the formation of well-defined Z-type heterostructures. The photocatalytic activity was evaluated using Rhodamine B as a model pollutant. Under simulated solar (230–780 nm) irradiation the as-prepared BC/VO/CN hybrid materials demonstrated highly improved photocatalytic activity compared to CN, VO and VO/CN. The cause of the solar enhancement could be ascribed to the formation of Z-type heterojunctions between VO and CN, which promoted faster electron–hole separation and more efficient charge transfer. BC, as an electron transfer medium, accelerated the transfer of photogenerated charge carriers and inhibited their recombination.

Herein we disclose a novel radical-mediated [3 + 2]-cycloaddition reaction of alkenes under photochemical conditions. A set of rationally designed bromodifluoromethyl alkynyl ketones were prepared and applied in the cascade reaction. The protocol features broad functional group tolerance and excellent regio- and stereo-selectivity. Both activated and unactivated alkenes were suitable substrates. The transformation gives rise to a variety of valuable α,α-difluorocyclopentanones bearing a tetra-substituted E-alkene.

One polysaccharide, designated as WPEP-A, was isolated from Passiflora edulis Sims peel and its hypoglycemic effects on diabetic db/db mice were evaluated. Physicochemical characterization showed that WPEP-A was composed of galactose, glucose, xylose, rhamnose, galacturonic acid and glucuronic acid with a molecular weight of 9.51 × 104 Da. We observed an inhibition in weight gain and blood glucose levels. Glucose tolerance and insulin tolerance improved after the administration of WPEP-A. In addition, our data showed increased antioxidant enzyme activities. Furthermore, the levels of serum insulin and triglyceride decreased with the recovery of liver damage. Meanwhile, positive changes in short chain fatty acid content were observed, and the mRNA levels of glucagon-like peptide 1 receptor, glucagon and prohormone convertase 3 were up-regulated in the intestinal tract. In summary, our results showed that WPEP-A had hypoglycemic activity and improved intestinal function in diabetic mice, which may contribute to the attenuation of the hypoglycemia effects.

By a bifunctional organic ligand 2-(benzimidazol-1-yl)terephthalic acid (H2bitp) featuring both imidazol-carboxylate groups, two new Cu(II)-containing coordination polymers (CPs) with the chemical ...

Current yeast metabolic engineering in isoprenoids production mainly focuses on rewiring of cytosolic metabolic pathway. However, the precursors, cofactors and the enzymes are distributed in various sub-cellular compartments, which may hamper isoprenoid biosynthesis. On the other side, pathway compartmentalization provides several advantages for improving metabolic flux toward target products. We here summarize the recent advances on harnessing sub-organelle for isoprenoids biosynthesis in yeast, and analyze the knowledge about the localization of enzymes, cofactors and metabolites for guiding the rewiring of the sub-organelle metabolism. This review may provide some insights for constructing efficient yeast cell factories for production of isoprenoids and even other natural products.

Decidualization is essential for successful pregnancy in rodents and primates. Although L-Tryptophan and its metabolites are essential for mammalian pregnancy, the underlying mechanism is poorly defined. We explored effects of tryptophan and kynurenine on human in vitro decidualization in human endometrial stromal cell line and primary endometrial stromal cells. Tryptophan significantly stimulates the expression of prolactin and insulin growth factor binding protein 1, reliable markers for human decidualization. When stromal cells are treated with tryptophan, tryptophan hydroxylase-1 remains unchanged, but indoleamine 2,3-dioxygenase 1 is significantly increased, suggesting tryptophan is mainly metabolized through kynurenine pathway. Kynurenine significantly stimulates insulin growth factor binding protein 1 expression. Aryl hydrocarbon receptor and its target genes (P450 1A1 and P450 1B1) are significantly increased by tryptophan and kynurenine. The induction of tryptophan and kynurenine on insulin growth factor binding protein 1 is abrogated by CH223191, an aryl hydrocarbon receptor inhibitor. Cytochrome P450 1A1 and P450 1B1 catalyze the oxidative metabolism of estradiol to catechol estrogens (2-hydroxy estradiol and 4-hydroxy estradiol), respectively. Insulin growth factor binding protein 1 is up-regulated by 2-hydroxy estradiol and 4-hydroxy estradiol. Interferon-γ significantly induces the expression of indoleamine 2,3-dioxygenase 1, aryl hydrocarbon receptor and insulin growth factor binding protein 1. All the data are also verified in primary human stromal cells. Our data indicate that Interferon-γ-induced kynurenine pathway promotes human decidualization via aryl hydrocarbon receptor signaling.

Bilayer barium titanate (BaTiO3, BTO)/bismuth ferrite (BiFeO3, BFO) capacitive devices were fabricated and systematically analyzed from the aspects of thin-film material crystallography and electrical characterization. The tetragonal phase (T) of BTO with the reducing thickness (150 nm) was demonstrated through carefully adjusting the conditions of sputtering process and post-thermal treatments. The thickness dependence of polarization, energy density, permittivity, and leakage current was investigated in the BTO/BFO bilayer system. It showed that 150-nm BFO film is an optimal thickness, which led to the substantial increase in energy density up to 920 mJ/cm3 with the charge/discharge efficiency of 79.7% at 10 V. The permittivity of 150-nm BFO bilayer device was found to be 258, which is much higher than the single -layer BFO and other BTO/BFO devices with different BFO thicknesses. Leakage current could be reduced by three orders with the increasing thickness of BFO layer from 30 to 225 nm. In addition, the leakage current of BTO/BFO bilayer capacitors was 102 times lower than BFO single layer with the same total thickness. The result showed that the leakage current of BFO material could be significantly reduced in the bilayer system. The performance of BTO/BFO bilayer capacitors indicates that it is a promising technique for the implementation of nanoscale, lead-free, and nonelectrochemical thin-film energy storage-related applications.

The first synthesis of benzyne-derived stable zwitterions is reported. Benzynes generated in situ from 2-(trimethylsilyl)aryl triflates undergo a multicomponent reaction with phosphines and CO2 to produce the stable 1,5-zwitterionic species in moderate to excellent isolated yields, which provides a novel method for the preparation of phosphonium inner salts under mild and transition-metal-free conditions.

Dielectric properties of oxyfluorosilicate (OFS) glasses have been characterized using Terahertz (THz)-time domain spectroscopy in the sub-THz region as well as optical reflection measurement. OFS glass containing 20 mol% of Nb2O5, which is termed ZNbKLSNd glass, has the highest refractive index of 3.70 in the sub-THz region. The THz and optical refractive indices of various silicate oxide glasses, including OFS glasses, have been confirmed to be correlated by a unified relationship utilizing a parameter defined by the ratio of ionic to electronic polarizability. Additionally, the frequency dependence of the THz dielectric constant has been interpreted by a single oscillator model for all silicate oxide glasses including OFS glasses. On the basis of the present unified dielectric model, the very high refractive index of ZNbKLSNd glass has been attributed to the lowering of oscillator resonance wavelength originated from the incorporation of Nb2O5 intermediate network former.

Described herein is a radical-mediated vinylation of the remote C(sp3)–H bonds of propargylic alcohols. A variety of widely available reagents, such as acetonitrile, ethers, aliphatic alcohols, and simple alkanes, serve as both the solvent and coupling partner. The transformation proceeds via sequential vinyl radical-mediated HAT and intramolecular vinyl migration, in which two inert C(sp3)–H bonds and one C–C bond are homolysed. The reaction also features broad functional group tolerance, good regio-/chemo-selectivity, and synthetic step-economy.

Glucocorticoids (GCs) are essential for mouse embryo implantation and decidualization. Excess GCs are harmful for mouse embryo implantation and decidualization. 11β-Hydroxysteroid dehydrogenases type I and II (Hsd11b1/Hsd11b2) are main enzymes for regulating local level of GCs. Hsd11b2 acts as the placental glucocorticoid barrier to protect the fetus from excessive exposure. Although effects of GCs on the fetus and placenta in late pregnancy have been extensively studied, the effects of these adrenal corticosteroids in early pregnancy are far less well defined. Therefore, we examined the expression, regulation and function of Hsd11b1/Hsd11b2 in mouse uterus during early pregnancy. We found that Hsd11b2 is highly expressed in endometrial stromal cells on days 3 and 4 of pregnancy and mainly upregulated by progesterone (P4). In both ovariectomized mice and cultured stromal cells, P4 significantly stimulates Hsd11b2 expression. P4 stimulation of Hsd11b2 is mainly mediated by the Ihh pathway. The uterine level of corticosterone (Cort) is regulated by Hsd11b2 during preimplantation. Embryo development and the number of inner cell mass cells are suppressed by Cort treatment. These results indicate that P4 should provide a low Cort environment for the development of preimplantation mouse embryos by promoting the expression of uterine Hsd11b2.

Plant diseases seriously affect crop yield and quality and are difficult to control. Marine natural products (MNPs) have become an important source of drug candidates with new biological mechanisms. Marine natural product essramycin (1) was found to have good anti-tobacco mosaic virus (TMV) and anti-phytopathogenic fungus activities for the first time. A series of essramycin derivatives were designed, synthesized, and evaluated for their bioactivity. Most of these compounds exhibited antiviral effects that are greater than that of the control ribavirin. Compounds 7e and 8f displayed antiviral activities that are greater than that of ningnanmycin (the most widely used antiviral agent at present), thus emerging as novel antiviral lead compounds. As the lead compound, 7e was selected for further antiviral mechanism research. The results indicated that 7e could inhibit virus assembly and promote 20S disk protein aggregation. Fungicidal activity tests against 14 kinds of phytopathogenic fungi revealed that essramycin analogues displayed broad-spectrum fungicidal activities. Compound 5b displayed more than 50% inhibition rate against most of the 14 kinds of phytopathogenic fungi at 50 μg/mL. The current research lays a solid foundation for the application of essramycin alkaloids in crop protection.

The wild Chinese grapevines (Vitis spp.) show varying levels of resistance to powdery mildew caused by Erysiphe necator that is an economically important disease of cultivated grapevines (Vitis vinifera). However, little information is available regarding the cytological mechanisms of powdery mildew resistance in these wild relatives. Here, we studied the cytological responses of three wild Chinese grapevine accessions after they were infected with E. necator (En) NAFU1 in comparison to the susceptible V. vinifera cv. 'Thompson Seedless' grape. The hyphal growth and sporulation of En NAFU1 were significantly restricted in wild species compared to 'Thompson Seedless', which appears to be associated with early cell wall deposition at the attempt sites, encasement of haustoria, and hypersensitive response-like cell death of penetrated epidermal cells. Moreover, endogenous free salicylic acid (SA) was more abundant in wild Chinese Vitis species than in 'Thompson Seedless' under pathogen-free condition. During En NAFU1 colonization, SA conjugates accumulated higher in wild grapevines than in 'Thompson Seedless'. In addition, the species-specific expression patterns of defense-associated genes during En NAFU1 colonization indicated that mechanisms underlying powdery mildew resistance are divergent among different wild Chinese Vitis species. These results contribute to understanding of mechanisms underlying defense responses of wild Chinese Vitis species against powdery mildew.

Chlorination has been intensively investigated for use in water disinfection and pollutant elimination due to its efficacy and convenience; however, the generation and transportation of chlorine and hypochlorite are energy-consuming and complicated. In this study, a novel binary photosensitizer consisting of anthraquinone-2-sulfonate (AQ2S) and graphene was synthesized via a π-π stack adsorption method; this compound could allow for the chlorination of organic pollutants using on-site chlorine generation. In this photosensitive degradation process, sulfapyridine (SPY) was selected as a model pollutant and was decomposed by the reactive species (Cl2•-, Cl• and O2•-) generated during the photosensitive oxidation of chloride. The synthesized AQ2S/graphene exhibited superior activity, and the degradation rate of SPY was over 90 % after 12 h of visible light irradiation with a kinetic constant of 0.2034h−1. Results show that 20 mg AQ2S/GR at a 21 % weight percentage of AQ2S in a pH 7 SPY solution with 1 mol/L Cl− achieved the highest kinetics rate at 0.353 h−1. Free radical trapping experiments demonstrated that Cl2•- and O2•- were the dominant species involved in SPY decomposition under solar light. The reusability and stability of this composite were verified by conducting a cycle experiment over five successive runs. The capacity of photodegradation still remained over 90 % after these 5 runs. The current study provides an energy-efficient and simple-operational approach for water phase SPY control.

Few studies have addressed the impact of diagnostic urine metabolites and the clinical outcomes associated with genitourinary urothelial (GU) cancer to date. Furthermore, longitudinal analysis of the dynamics of urine metabolites contributing to the detection of GU cancer has not yet been fully investigated; therefore, the discovery of novel diagnostic urine biomarkers is of enormous interest. We explored the correlation of the urine metabolomic profiles to GU cancers. The aqueous metabolites of the GU cancer and the control were also identified and analyzed through high-resolution1H nuclear magnetic resonance (NMR) spectroscopy. Compared with the control, the urine metabolites of the tumor were studied in relation to changes over time in a linear mixed model for repeated measures. The urine metabolites of sixty-three (44 male and 19 female) patients with GU cancers were systemically analyzed. The urine metabolite profile in GU cancer was significantly higher than those in the control group (p

Fabrication of easily recyclable photocatalyst with excellent photocatalytic activity for degradation of organic pollutants in wastewater is highly desirable for practical application. In this study, a novel ternary magnetic photocatalyst BiVO4/Fe3O4/reduced graphene oxide (BiVO4/Fe3O4/rGO) was synthesized via a facile hydrothermal strategy. The BiVO4/Fe3O4 with 0.5 wt% of rGO (BiVO4/Fe3O4/0.5% rGO) exhibited superior activity, degrading greater than 99% Rhodamine B (RhB) after 120 min solar light radiation. The surface morphology and chemical composition of BiVO4/Fe3O4/rGO were studied by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV visible diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy. The free radicals scavenging experiments demonstrated that hole (h+) and superoxide radical (O2•−) were the dominant species for RhB degradation over BiVO4/Fe3O4/rGO under solar light. The reusability of this composite catalyst was also investigated after five successive runs under an external magnetic field. The BiVO4/Fe3O4/rGO composite was easily separated, and the recycled catalyst retained high photocatalytic activity. This study demonstrates that catalyst BiVO4/Fe3O4/rGO possessed high dye removal efficiency in water treatment with excellent recyclability from water after use. The current study provides a possibility for more practical and sustainable photocatalytic process.

The direct incorporation of a trifluoromethyl group on an aromatic ring using a radical pathway has been extensively investigated. However, the direct highly para-selective C-H trifluoromethylation of a class of arenes has not been achieved. In this study, we report a light-promoted 4,5-dichlorofluorescein (DCFS)-enabled para-selective C-H trifluoromethylation of arylcarbamates using Langlois reagent. The preliminary mechanistic study revealed that the activated organic photocatalyst coordinated with the arylcarbamate led to para-selective C-H trifluoromethylation. Ten-gram scale reaction performs well highlighting the synthetic importance of this new protocol.

Hematite (α-Fe2O3) is a promising candidate for NH3 selective catalytic reduction (NH3-SCR) of NOx due to its good sulfur resistance. However, the activity of pure α-Fe2O3 is very low. In this work, α-Fe2O3 obtained excellent N2 selectivity and medium–high temperature activity via a simple surface sulfation method. The α-Fe2O3-350 (sulfated at 350 °C) sample showed an NO conversion rate of ~ 100% in the range of 275–350 °C and exhibited excellent H2O and SO2 resistance ability at 300 °C. Furthermore, pure α-Fe2O3 was used as a model catalyst to fully uncover the effect of sulfation on FeOx-based catalysts in NH3-SCR reactions. Structural characterization indicated that the degree of surface sulfation of the catalyst would be deepened with increasing temperature, and the states of sulfate species on α-Fe2O3 changed from surface sulfates to bulk-like sulfates. Although sulfation treatment reduced the redox properties of α-Fe2O3, it significantly increased its surface acidity and thus the activity. Excessive bulk-like sulfates induced a decrease in activity. Sulfation inhibited the adsorption of NOx on the α-Fe2O3 catalyst surface and reduced the thermal stability of nitrates at medium–high temperature. Thus, the Langmuir-Hinshelwood (L-H) mechanism was inhibited, and the reaction mainly followed the Eley-Rideal (E-R) mechanism.

Uric acid (UA), as the final product of purine metabolism, exists in urine and serum, which plays an important role in human metabolism, immunity and other functions. The sensitive, efficient, and rapid detection of UA has far-reaching significance in clinical diagnosis and disease prevention. Herein, a novel coordination polymer constructed by dual-ligand was successfully prepared, which exhibited excellent thermal and water stability. The polymer was interlaced by coordination bonds and hydrogen bonds to form an infinitely extended three-dimensional framework, which showed a rare and novel topological structure. The complex selectively recognized UA through significant fluorescence quenching response in the presence of various interferences. The excellent detection sensitivity (the limited detection of 1.2 μM), outstanding anti-interference ability and remarkable recyclability marked the complex to be a promising sensor material towards UA. In addition, the detection mechanism of UA by the complex was investigated in detail by combining density functional theory (DFT) and a variety of other analytical methods.

An innovative approach is developed to utilize the frass of mealworms (Tenebrio molitor Linnaeus 1758) for producing dye-removal biochar. Agricultural waste wheat straw (WS) was tested as feedstock versus wheat bran (WB) to rear mealworms for the production of insect biomass. Mealworms on WS grew at a slightly slower rate than those grown on WB for 32 days with ∼40% lignin removed at 25 °C. Biochars were generated using the frass of mealworms via pyrolysis. The best adsorption performance for three dyes, especially malachite green, a cationic dye, was the biochar of WS frass at 800 °C; it had better capacity (1738.6 mg/g) compared with the frass fed with bran, raw WS and raw WB as well as those reported in the literature. Adsorption of malachite green fits the Langmuir isotherm and the pseudo second order kinetic model, mainly due to chemisorption and electrostatic interaction. Our results demonstrated that the WS can be utilized to rear mealworms, and that frass of mealworms is an excellent raw material for generating high-efficiency bioadsorbents.

Ten new cucurbitane triterpenoids, hemsleyacins A–J (1–10), together with three known cucurbitane triterpenoids, dihydrocucurbitacin F (11), scandenogenin D (12), and jinfushanencin F (13), were separated from ethanolic tuber extracts of Hemsleya penxianensis. The absolute configurations of the new compounds were established based on NMR, HRESIMS, and CD spectra. Compounds 7 and 10–12 were evaluated in terms of their antifeedant activity against Plutella xylostella larvae. The result showed that compound 10 exhibited potent antifeedant activity against P. xylostella larvae after 48 h of treatment. Furthermore, the MTT test showed that compound 11 exhibited potent inhibition toward the UMUC-3 and T24 cell lines with IC50 values of 29.12 and 35.62 μM, respectively, compared to the positive control cisplatin IC50 values of 8.27 and 13.72 μM. Western blot analysis revealed that compound 11 treatments substantially inhibited the phosphorylation of IκBα.

Temperate mixed forests, along with other high latitudinal ecosystems, are more vulnerable to global warming in comparison with warm sites, because of the slower carbon (C) turnover and higher soil organic carbon (SOC) accumulation. Lignin and cellulose are two major components of plant litter, and usually make contributions to the recalcitrant and labile SOC pool, respectively. Because the chemical composition of SOC plays key role in regulating the bioavailability of soil C pool, understanding the relationship between soil lignin or cellulose content and temperature are of great significance in evaluating the feedbacks between SOC pool and the future scenarios of global warming. The biological degradation of soil lignin or cellulose is mainly dependent on soil enzymatic activities, and thus, the response of ligninolytic and cellulolytic enzymes to increased temperature would determine C release under future warming scenarios. However, the responses of the soil lignin/cellulose content and the activity of cellulolytic and ligninolytic enzymes to increased mean annual temperature (MAT) have rarely been studied, and the factors driving these changes are not fully understood. Latitudinal gradients are often used for monitoring global-warming-related problems, because of its natural gradients of temperature. In this study, we demonstrate the latitudinal pattern of lignin/cellulose content and the activities of cellulose- and lignin- degrading enzymes in a temperate Broad-leaved Korean pine mixed forests distributed along a latitudinal gradient (with MAT ranging from −1.9 to 5.1 °C) in northeastern China. The linear mixed model revealed that soil lignin content was negatively correlated with MAT (Slope = −7.604, t = −2.608, P = 0.011), whereas soil cellulose content showed no response to increased MAT. The activity of soil polyphenol oxidase (PPO), one of the enzymes catalyze lignin decomposition, was higher in high-latitude sites, in contrast, the activity of the cellulase (CEL) complex was higher in low-latitude plots. Structural equation model (SEM) analysis indicates that MAT can directly influence soil lignin or cellulose content, and indirectly through changing NRCB, plant litter C/N, microbial biomass, and degrading enzymatic activities. The value of soil lignin/(lignin + cellulose) ratio and soil lignocellulose index (LCI, lignin/(lignin + holocellulose) ratio), varied between 0.8–0.9, and 0.6–0.8, respectively, indicating that the SOC pool in this temperate ecosystem is dominated by recalcitrant components. The negative correlations between MAT and LCI, soil lignin/(lignin + cellulose), and log (PPO + PER)/log(CEL) (Slope = −0.008, t = −2.363, P = 0.021; Slope = −0.004, t = −3.134, P = 0.003, and Slope = −0.057, t = −4.477, P

The 35S ribosomal DNA (rDNA) units that occur in tandem repeat are separated by an intergenic spacer (IGS) that plays an important role in rRNA transcription. Moreover, IGS is an important molecular marker for evolutionary research in plants. In the present study, the IGS sequence of Erianthus arundinaceus was isolated and sequenced for the first time. Structure analysis indicated the entire IGS sequence of three typical E. arundinaceus genotypes was highly conserved, with approximately 3087 bp and 67.1% mean GC content. The putative transcription termination, and initiation sites as well as a large number of methylation sites were found to be present in the IGS of E. arundinaceus compared to other plants. The phylogenic tree constructed using the E. arundinaceus IGS sequence showed that Miscanthus sinensis var. glaber was genetically close to Saccharum spp. while E. arundinaceus was close to Imperata cylindrica. Moreover, fluorescent in situ hybridization revealed that IGS and pTa71 probes had the same locus at nucleolar organizer regions. Taken together, this work enhances our current understanding of the organization of IGS in E. arundinaceus and provides a molecular evidence for an evolutionary relationship between Saccharum spp., E. arundinaceus, I. cylindrica and M. sinensis var. glaber.

Glucose and xylose co-fermentation is crucial to maximize hydrogen yield from waste lignocellulose. In this study, cell growth, sugar consumption, and hydrogen production profiles of Thermoanaerobacter thermosaccharolyticum W16 feeding with a range of glucose and xylose were experimental investigated coupled with kinetic analysis. Results showed although T. thermosaccharolyticum W16 could use both glucose and xylose for hydrogen production, a maximum cell growth rate of 0.27 g/L/h and hydrogen production rate of 14.53 mmol/L/h was found with glucose as sole substrate, the value was 92.8% and 49.8% higher than using xylose as the only carbon source. Further interpolation analysis and experimental demonstration suggested when glucose content in the mixed substrate higher than 58.2%, the inhibitory effect on xylose utilization was increased, but when glucose concentration fell below 21.7%, its utilization will be subject to a certain degree of feedback inhibition. Coupling experimental results with kinetic analysis in this study provides a powerful evidence to further develop the potential of T. thermosaccharolyticum W16 as a biocatalyst for hydrogen production from lignocellulosic biomass.

White organic light-emitting devices (WOLEDs) were fabricated by using a highly blue fluorescent dye of 4,4’-bis(2,2’-diphenyl vinyl)-1,1’-biphenyl (DPVBi) and a red fluorescent dye of 5H-benzo[ij] quinolizin-9-yl) ethenyl]-4H-pyran-4-ylidene] propane-dinitrile (DCM2), together with a green fluorescent dye of 10-(2-benzothiazolyl)-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H,11H-(1)-benzopyroyran-o(6,7-8-i,j) quinolizin-11-one (C545T). The multilayer WOLEDs does not involve the doping process. The structure of the device is indium tin oxide (ITO)/4,4’,4”-tris{N,-(3-methylphenyl)-N-phenylamin}triphenylamine (m-MTDATA) (55 nm)/ N,N’-bis-(1-naphthyl)-N,N’-diphenyl-1,1’-biph-enyl-4,4’-diamine (NPB) (10 nm)/ DPVBi (8 nm)/ C545T (x nm)/ DPVBi (5 nm)/ DCM2 (y nm)/ tris- (8-hydroxyquinoline) aluminum (Alq3) (60nm)/ LiF (1 nm)/ Al, where the DPVBi is introduced as a spacer. By changing the thicknesses of dual ultrathin layers of C545T and DCM2, the WOLED is obtained. When x=y=0.05, the Commission Internationale de 1’Eclairage (CIE) coordinates of the device change from (0.262 6, 0.351 4) at 4 V to (0.214 7, 0.269 3) at 12 V that are well in the white region. Its maximum luminance is 41400 cd/m2 at 13 V, and the maximum current efficiency and the maximum power efficiency are 7.95 cd/A at 6 V and 5.37 lm/W at 5 V, respectively.

An efficient visible-light photocatalytic protocol for the vicinal heteroarylsulfonylation and oximinosulfonylation of unactivated olefins is described. The addition of sulfonyl radicals to alkenes triggers the intramolecular migration of remote heteroaryl and oximino groups via C C bond cleavage. The transformation features a good functional group tolerance and a broad substrate scope. A variety of valuable heteroaryl- and oximino-substituted alkyl sulfones are obtained under mild conditions in synthetically useful yields.

Intergeneric hybrids between Saccharum spp. and Erianthus arundinaceus and clones derived from these hybrids and backcrosses to Saccharum spp. were used to study the transmission of E. arundinaceus chromosomes by genomic in situ hybridization (GISH). True hybrid progenies were precisely identified using PCR with a primer pair, AGRP52/53. The results showed that AGRP52/53 was an E. arundinaceus-specific primer pair and could be used as molecular marker to assist breeding. EaHN92, a 364 bp E. arundinaceus-specific tandem repeat satellite DNA sequence, was cloned from the E. arundinaceus clone HN92–105 with AGRP52/53, and was localized on sub-telomeric regions of all E. arundinaceus chromosomes. YCE06–61, a BC3 progeny, had 7 E. arundinaceus chromosomes and its progenies had approximately 1–6 E. arundinaceus chromosomes. The number of E. arundinaceus chromosomes in true hybrids appeared as Gaussian distribution in 3 cross combinations. In addition, GISH detected intergeneric chromosome translocation in a few progenies. Hence, screening clones containing approximately 1–2 E. arundinaceus chromosomes without translocation could be used for sorting and sequencing E. arundinaceus chromosomes. This study provides a method for breeders to select true hybrid progenies between Saccharum spp. and E. arundinaceus, which will accelerate this intergeneric hybridization breeding.

Recently, we developed ultrasmall molybdenum disulfide (MoS2) quantum dots for computed tomography (CT) and multispectral optoacoustic tomography (MSOT) imaging-guided photothermal therapy (PTT). B...

Improving the cementitious activity and volume stability of steel slag by thermal reconstruction is an innovative method for efficient utilization of steel slag. In this study, different amounts of CaF2 and CaSO4 were added to steel slag as a mineralizer based on the determining admixtures needed for the reconstruction reaction, and the effects of CaF2 and CaSO4 on the cementitious activity and volume stability of the reconstructed steel slag were investigated. The results show that when the CaF2 content is increased to 5 wt%, the cementitious activity index of the reconstructed steel slag gradually increases to 92%, which is 12% higher than the first level technical requirement specified by the national standards, and the free CaO (f - CaO) and MgO (f-MgO) contents gradually decrease to 0.35 and 0.13 wt%, respectively. With increasing CaSO4 content, the cementitious activity index first increases and then decreases, while the contents of f -CaO and f-MgO show the opposite trend. When the CaSO4 content is 2 wt%, the activity index is 105%,which is 25%higher than the first level technical requirement specified by the national standards, and the f -CaO and f-MgO contents reach minima of 0.44 and 0.35 wt%, respectively.

Electrostatically enhanced thiourea behaves more efficiently than Schreiner's thiourea in the ring-opening aminolysis of styrene oxide with aniline, and the underlying reasons were uncovered by DFT calculations, the distortion/interaction theory, and NBO and QTAIM analyses. Electrostatically enhanced thiourea combines with a substrate much stronger than Schreiner's thiourea, so it activates the substrate more efficiently and thus lowers the activation energy more significantly, leading to a higher reaction rate and a greater conversion.

Three novel meroterpenoids, clavipines A–C (1–3), possessing a benzoquinone fused to an azepine ring and a ten-membered carbocycle with α,β-epoxy/unsaturated-γ-lactone, along with a new natural compound clavilactone F (4) and two known clavilactones D (5) and A (6) were isolated from the basidiomycete Clitocybe clavipes. Their structures with absolute configurations were unambiguously established by extensive spectroscopic analyses, and ECD and X-ray methods. An unusual seven-azepine skeleton was postulated to be formed biosynthetically via a rearrangement of quinone–amino acid conjugates. The biosynthetic origin of meroterpenoids with a benzo-fused 10-membered carbocycle unit was determined by incorporation of 13C-labeled precursors. Compound 1 exhibited significant antiproliferative activity against HepG2 and A549 cells with IC50 values of 4.28 ± 0.26 and 7.49 ± 0.41 μM, respectively.

In this study, the performance of periodate (PI) on sulfadiazine (SDZ) degradation was evaluated using coagulation solid waste fabricated catalyst (CWBC), obtained by simple pyrolysis. SDZ effectively underwent 98.94% remove within 90 min in the CWBC/PI system. Electron transfer was the predominant mechanism due to the development of an electronic cycle among SDZ, CWBC and PI, where the O2•−, PFRs, and the reactive iodine species had minor roles. Density functional theory calculations identified that Fe and N could change the electron configuration and break the chemical inertness of carbonaceous material. As a result, electrons on the carbon matrix of CWBC are inclined to travel through the formed Fe–O covalent bond to PI. Further analysis demonstrated that SO42−, humic acid (HA), as well as anoxic conditions greatly facilitated SDZ degradation. This study provides a facile protocol for converting coagulation waste to an efficient catalyst and provides fundamental insights into the degradation mechanisms of micropollutants by activating PI.

The accurate and rapid quantitative detection of antibodies had a significant influence in controlling and preventing disease or toxin outbreaks. In this work, we first introduce the antibody-powered triplex-DNA nanomachine to release cargo DNA as a substitute target for sensitive electrochemiluminescence (ECL) detection of anti-digoxigenin based on a novel ternary ECL system. It is worth noting that the cargo DNA as a substitute target of antibody can further participate in an enzyme-assisted cycling strand displacement reaction to achieve ECL signal amplification and improve the sensitivity of antibody detection. Additionally, porous palladium nanospheres with a considerable catalytic activity were first applied as a coreaction accelerator to efficiently enhance the intensity of the ECL system of rubrene microblocks as luminophore and dissolved O2 as an endogenous coreactant. With the resultant ternary ECL system as a biosensing platform, a significantly enhanced initial signal was achieved in advance. Then, the ferrocene-labeled quenching probes were employed to reduce initial signal and obtain the low-background signal. Eventually, the cargo DNA made the quenching probes release and recover the signal in the presence of anti-digoxigenin. Thereupon, the wide linear range (0.01-200 nM) and low limit of detection (6.7 pM) were obtained, and this method not only reduces conjugation steps but also provides a sensitive and novel ECL analysis platform for the trace detection of other antibodies and antigen.

Caffeic acid phenethyl ester (CAPE), a bioactive component of propolis, has beneficial effects on cancer prevention. Growth differentiation factor 15 (GDF15) is an antitumor gene of bladder cancer. Therefore, this study investigated the anti-cancer effect of CAPE on bladder carcinoma cells and related mechanisms.The expressions of GDF15, N-myc downstream-regulated gene 1 (NDRG1), and maspin, and the activations of extracellular signal regulated kinase (ERK), c-jun Nterminal kinase (JNK), p38, and 50 adenosine monophosphate-activated protein kinase (AMPK) α1/2 in human bladder cells after gene transfection or knockdown were determined by immunoblot, real-time reverse transcriptase-polymerase chain reaction (RT-qPCR), and reporter assays. The assays of 5-ethynyl-2'-deoxyuridine (EdU), CyQUANT cell proliferation, and Matrigel invasion, and the xenograft animal study were used to assess the cell proliferation, invasion, and tumorigenesis.GDF15 expression in epithelial cells was negatively correlated with neoplasia in vitro. Also, GDF15 exhibits in bladder fibroblasts and smooth muscle cells. CAPE-induced expressions of NDRG1 and maspin decreased cell proliferation and invasion of bladder carcinoma cells in a GDF15-dependent manner in vitro. The xenograft animal study suggesting CAPE attenuated tumor growth in vivo. CAPE increased phosphorylation of ERK, JNK, p38, and AMPKα1/2 to modulate the GDF15 expressions. Pretreatments with ERK, JNK, or p38 inhibitors partially inhibited the CAPE effects on the inductions of GDF15, NDRG1, or maspin. Knockdown of AMPKα1/2 attenuated the CAPE-induced GDF15 expression and cell proliferation in bladder carcinoma cells.Our findings indicate that CAPE is a promising agent for anti-tumor growth in human bladder carcinoma cells via the upregulation of GDF15.

Based on the structure of the natural product cysteine, a series of thiazolidine-4-carboxylic acids were designed and synthesized. All target compounds bearing thiazolidine-4-carboxylic acid were characterized by 1H-NMR, 13C-NMR, and HRMS techniques. The antiviral and antifungal activities of cysteine and its derivatives were evaluated in vitro and in vivo. The results of anti-TMV activity revealed that all compounds exhibited moderate to excellent activities against tobacco mosaic virus (TMV) at the concentration of 500 &mu, g/mL. The compounds cysteine (1), 3&ndash, 4, 7, 10, 13, 20,23, and 24 displayed higher anti-TMV activities than the commercial plant virucide ribavirin (inhibitory rate: 40, 40, and 38% at 500 &mu, g/mL for inactivation, curative, and protection activity in vivo, respectively), especially compound 3 (inhibitory rate: 51%, 47%, and 49% at 500 &mu, g/mL for inactivation, curative, and protection activity in vivo, respectively) with excellent antiviral activity emerged as a new antiviral candidate. Antiviral mechanism research by TEM exhibited that compound 3 could inhibit virus assembly by aggregated the 20S protein disk. Molecular docking results revealed that compound 3 with higher antiviral activities than that of compound 24 did show stronger interaction with TMV CP. Further fungicidal activity tests against 14 kinds of phytopathogenic fungi revealed that these cysteine derivatives displayed broad-spectrum fungicidal activities. Compound 16 exhibited higher antifungal activities against Cercospora arachidicola Hori and Alternaria solani than commercial fungicides carbendazim and chlorothalonil, which emerged as a new candidate for fungicidal research.

Background The purpose of this study was to investigate the relationship between circulating zinc α 2-glycoprotein (ZAG), irisin, betatrophin and adiponectin concentrations and metabolic syndrome (MetS) components and to analyze the effects of blood glucose and insulin on these cytokine concentrations in vivo. Methods A total of 196 young women, including 78 healthy women and 118 women with MetS components, were recruited for this cross-sectional study. An oral glucose tolerance test and euglycemic-hyperinsulinemic clamp (EHC) were performed in healthy subjects and women with MetS components. An ELISA kit was used to measure serum ZAG, irisin, betatrophin, and adiponectin levels, and their relationship with the MetS components was analyzed. Results In women with MetS components, circulating irisin and betatrophin levels were significantly higher than those in the healthy women ((207 (150–248) vs 178 (147–228); P < 0.05) for irisin; (0.51 (0.38–0.63) vs 0.38 (0.23–0.52); P < 0.001) for betatrophin), but circulating ZAG and adiponectin levels were significantly lower (39.8 (26.4–50.4) vs (46.7 (40.6–63.0); P < 0.001) for ZAG; (36.5 (22.0–47.6) vs 41.2 (35.7–54.7); P < 0.01) for adiponectin). FBG, WC, and triglyceride were significantly correlated with the circulating levels of these four cytokines (P < 0.001 or Conclusion Serum ZAG, irisin, betatrophin and adiponectin were associated with MetS and might be biomarkers for screening MetS components.

In this work, we analyzed silicon (Si) ion implanted semi-insulting gallium arsenide substrates (SI-GaAs) by using a terahertz time-domain spectroscopy (THz-TDS) system. The main goal is to determine the ion doping profile via a nondestructive approach by using THz-TDS spectroscopy. This approach will bring a new appliance to replace secondary ion mass spectroscopy (SIMS). For that, we have carried out the ion implantation experiment with an implantation energy of 200 keV at different doses. Then, we analyzed the THz-TDS experimental data of implanted SI-GaAs substrates by the Drude model to achieve depth-dependent dielectric and electrical properties at THz frequencies.

A Cu-catalyzed enantioselective ring-opening alkoxygenation reaction of cyclic diaryliodonium salts and diols in the presence of borinic acids was reported. Tuning structure of borinic acids with six or five-membered ring skeleton could selectively activate 1,2-diols or 1,4-diols. A catalytic cycle through a key ion pair model that accounts for the observed enantioselectivity was proposed.

In this study, an innovative approach was proposed based on the implement of biochar derived from residue cornstalk left after anaerobic bio-hydrogen production (RCA-biochar) to improve direct bio-hydrogen production from anaerobic fermentation of cornstalk. The bio-hydrogen production potential and maximum bio-hydrogen production rate increased from 156.2 to 286.1 mL H2/g substrate and 3.5 to 5.7 mL H2/g substrate/h, respectively, following the added RCA-biochar increased from 2.5 to 15.0 g/L. Cornstalk chemical component analysis showed the cellulose and hemicellulose content decreased by 17.9–33.7% and 14.4–25.2%, and lignin content increased by 20.3–42.8%, respectively, after 96 h anaerobic fermentation with RCA-biochar 2.5–15.0 g/L. Further analyses revealed that RCA-biochar not only provided more specific surface area for hydrogen-producing bacteria attachment, but also promoted the cellulolytic enzyme activity, thereby resulted in increased substrate conversion to bio-hydrogen. The findings obtained in this study may provide supports for effective and sustainable lignocellulosic bio-hydrogen production in the future.

Microbial carriers may co-transport polycyclic aromatic hydrocarbons (PAHs), but lack substantial experimental evidence. Cable bacteria use gliding or twitching motility to access sulfide; hence, they could be important microbial carriers in co-transporting PAHs from the sediment-water interface into suboxic zones. In this study, the effect of cable bacteria on pyrene migration was investigated by connecting or blocking the paths of cable bacteria to the suboxic zones. The results showed that downward migration of pyrene in the connecting groups were significantly higher (17.3-49.2%, p 0.01) than those in the control groups. Meanwhile, significant downward migration of microbial communities in the connecting groups were also observed, including abundant filamentous-motile microorganisms, especially cable bacteria. The adsorption of surrounding particles by cable bacteria were morphologically evidenced. The biomechanical model based on the Peclet number indicated that filamentous-motile microorganisms demonstrated stronger adsorption ability for pyrene than other microorganisms. Supposedly, the downward migration of microbial communities, especially cable bacteria, significantly enhanced pyrene migration, thus influencing the distribution and ecological risk of pyrene in sediments. This study provides new insights into the important roles of motile microorganisms in the migration of PAHs in sediments, shedding lights on guidance for ecological risk assessment of PAHs.