Search

Cation-π interaction is considered one of the strongest noncovalent interactions in aqueous solutions, which endows natural biomolecules (e.g., proteins) with robust wet adhesion and cohesion in hu...

Gestational diabetes mellitus (GDM), a frequently-occurring disease during pregnancy, may cause some adverse healthy outcome of both mother and offspring. However, the knowledge about metabolite alterations during the pathogenesis and development process is limited. Here, a large longitudinal non-targeted metabolomics study of 195 pregnant women (64 women with subsequently developed GDM and 131 healthy controls) was conducted. Each participant provided urine samples at three timepoints during early, middle and late pregnancy, respectively. The metabolic profiles of 585 urine samples (195 × 3) were measured by using ultra-high performance liquid chromatography coupled with Orbitrap high-resolution mass spectrometry. Among the 56 identified metabolites, the levels of eight metabolites increased and three ones decreased in the first trimester, the concentration of one metabolite increased and those of 20 decreased in the second trimester, as well as the levels of five metabolites increased and two decreased in the third trimester. After false discovery rate correction, the levels of valine and 5-acetamidovalerate in GDM group significantly increased in the first trimester, the levels of 1-methylguanine and 1,3-dihydro-(2H)-indol-2-one significantly decreased in the second trimester and three metabolites (threonine, OH-octanedioyl-carnitine and pimelylcarnitine) increased and N-acetyltryptophan decreased in the third trimester, respectively. Six metabolites, such as pantothenic acid and threonine, had significant interaction effects between gestational stage (different trimester) and group (GDM or control). The differential metabolites were involved in “tryptophan metabolism”, “purine metabolism”, “valine, leucine and isoleucine degradation” and other pathways. The findings may provide insights into further pathogenesis study of GDM.

SiOC as an alternative silicon-based material possesses great potential in lithium ion batteries due to its high reversible capacity, tunable chemical component and various synthetic route. However, large-scale production of SiOC powders grinded from SiOC bulks is restricted in commercial application because of the poor electrical conductivity. Herein, three dimensional (3D) lamellar SiOC@C/rGO composite is fabricated through hydrothermal reaction and electrostatic self-assembly process, in which SiOC powders encapsulated by amorphous carbon layers are homogeneously dispersed in graphene sheets. Cfree nanoclusters in SiOC, carbon layers on SiOC surface and graphene supporters in the composite establish the multidimensional interconnected conductive architecture and possess favorable interfacial adhesion. Therefore, SiOC@C/rGO exhibits high specific capacity (676 mAh g−1 at 200 mA g−1) and remarkable rate capability (306.4 mAh g−1 at 4000 mA g−1). The full cell assembled with this anode and LiFePO4 cathode also demonstrates stable voltage platform and good performance for 200 cycles. The excellent performance of SiOC@C/rGO profits from the synergistic effect of robust construction, multidimensional conductive architecture and chemical. Composition The proposed strategy can also be developed to prepare other materials with graphene layer to enhance their electrical conductivity for commercial application.

Mesoporous SmMnO3/CuMnOx catalyst was prepared by a two-step method using flaky CuMnOx with high specific surface and excellent catalytic ability as the carrier, which was further applied to photothermal synergistic degradation of gaseous toluene. Quantitative analysis of O2-TPD and H2-TPR showed that SmMnO3/CuMnOx exhibited abundant of the surface oxygen species and oxygen vacancies content, which enabled it to convert free oxygen to lattice oxygen more quickly during the reaction, and thus improving the reaction process. I-t and photoluminescence experiments demonstrated the improvement of photogenerated electron and hole separation ability of SmMnO3/CuMnOx catalyst. UV–Vis analysis manifested the full spectral range of absorption. XPS analysis verified the unequal positions of valence band of the two materials, which can facilitate the separation of photogenerated electrons from holes and improve the ability of better electron transfer. SmMnO3/CuMnOx catalyst has higher adsorbed oxygen content and light absorption capacity, which is beneficial to the catalytic oxidation. In situ DRIFTs proved that the oxidation reaction on the catalyst followed the Mars-van Krevelen redox cycle. The VOCs test found that SmMnO3/CuMnOx composite catalyst is with lower onset reaction temperature (T90 = 190 °C, T90, corresponding to 90% conversion) and good mineralization (100% at 275 °C).

Previous reports have shown that histone deacetylase inhibitors (HDACi) can alter miRNA expression in a range of cancers. Both the 5p-arm and 3p-arm of mature miRNAs can be expressed from the same precursor and involved in cancer progress. Nevertheless, the detailed mechanism by which vorinostat (SAHA), a HDACi, triggers miR-769-5p/miR-769-3p-mediated suppression of proliferation and induces apoptosis in gastric cancer (GC) cells remains elusive. Here, we showed that the miRNA-seq analysis of GC cells treated with SAHA identified seven differentially expressed miRNAs with both strands of the miRNA duplex. miR-769-5p/miR-769-3p expression was downregulated in GC tissues compared with normal tissues. Functionally, high expression of miR-769-5p/miR-769-3p blocked the malignant abilities of GC cells. Mechanistically, miR-769-5p/miR-769-3p targeted IGF1R and IGF1R overexpression rescued the effects of miR-769-5p/miR-769-3p on GC cells growth and metastasis. Moreover, STAT3 bound to the promoter of miR-769. Furthermore, miR-769-5p/miR-769-3p expression was negatively regulated by the STAT3-IGF1R-HDAC3 complex. Besides, miR-769-5p/miR-769-3p synergized with SAHA to promote GC cells apoptosis. Our studies suggest that miR-769-5p/miR-769-3p acts as a tumor suppressor by the STAT3-IGF1R-HDAC3 complex. Moreover, SAHA triggers miR-769-5p/miR-769-3p-mediated inhibition of proliferation and induces apoptosis in GC cells.

The treatment options for cancer of unknown primary (CUP) are challenging due to the lack of knowledge about the primary sites, often resulting in a poor prognosis. The emerging next-generation sequencing (NGS) technique has provided a reliable approach to facilitate tumor primary site prediction and targetable gene alteration identification for CUP patients. In this report, we described a 63-year-old female patient who experienced recurrent CUP. NGS-based genetic profiling results revealed a pathogenic germline BRCA1 R71K mutation. Accordingly, the patient received the poly(adenosine diphosphate [ADP]-ribose) polymerase (PARP) inhibitor olaparib treatment and demonstrated a favorable response to this treatment. Our case suggests that NGS holds great promise for providing improved diagnosis and treatment options to patients with CUP, warranting further clinical investigation.

The peroxisome proliferator-activated receptor (PPARδ) agonists are reported to improve insulin sensitivity, reduce glucose levels, and alleviate dysfunctional lipid metabolism in animal models of type 2 diabetes mellitus. However, the underlying mechanisms remain incompletely understood. Metabolism plays an essential role in the biological system. Monitoring of metabolic changes in response to disease conditions or drug treatment is critical for better understanding of the pathophysiological mechanisms. In this study, metabolic profiling analysis by gas chromatography-mass spectrometry integrated with targeted analysis by liquid chromatography-mass spectrometry was carried out in plasma samples of db/db diabetic mice after six-week treatment of PPARδ agonist GW501516. GW501516 treatment significantly altered levels of metabolites, such as branched-chain amino acids (BCAAs), BCAA metabolites (3-hydroxyisobutyric acid and 3-hydroxyisovaleric acid), long-chain fatty acids, uric acid and ketone bodies (3-hydroxybutyric acid and 2-hydroxybutyric acid) which are all associated with the impaired systemic insulin sensitivity. The present results indicate the beneficial effect of PPARδ agonist in alleviating insulin resistance of diabetic mice by favorably modulating metabolic profile, thus providing valuable information in understanding the therapeutic potential of PPARδ agonists in correcting metabolic dysfunction in diabetes.

Co3O4-Ni-MOF composite was successfully prepared by solvent-thermal method and then was combined with acidified multi-walled carbon nanotubes (MWCNTs); the resulting Co3O4-Ni-MOF/MWCNTs hybrid was applied in supercapacitor and characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscope (SEM). The electrochemical tests including cyclic voltammetric (CV), galvanostatic charge and discharge (GCD), electrochemical impedance spectroscopy (EIS), and cycle life were also performed to investigate the supercapacitor properties of the as-prepared materials. The experimental results show that when the molar ratio of metal oxide material and Ni-MOF material is 1:1, Co3O4-Ni-MOF material displays better electrochemical performance. As the mass ratio of Co3O4-Ni-MOF and MWCNTs is 1:1, Co3O4-Ni-MOF/MWCNTs hybrid exhibits lower Rct value, higher cyclic capacitance stability, and better supercapacitor performance. Therefore, Co3O4-Ni-MOF/MWCNTs hybrid as an electrode material has a relatively ideal application prospect in terms of supercapacitor materials.

HMGA1 protein is an architectural transcription factor that has been implicated in the progression of multiple malignant tumors. However, the role of HMGA1 in the growth and metastasis of gastric cancer (GC) has not yet been elucidated. Here, we show that HMGA1 is overexpressed in GC cells and the high expression of HMGA1 was correlated with worse survival in GC patients using a bioinformatics assay. Functionally, HMGA1 affected the EdU incorporation, colony formation, migration and invasion of GC cells by exogenously increasing or decreasing the expression of HMGA1. Mechanistically, HMGA1 directly bound to the SUZ12 and CCDC43 promoter and transactivated its expression in GC cells. Inhibition of SUZ12 and CCDC43 attenuated the proliferation, migration and invasiveness of HMGA1-overexpressing GC cells in vitro. Moreover, both HMGA1 and SUZ12/CCDC43 were highly expressed in cancer cells but not in normal gastric tissues, and their expressions were positively correlated. Finally, a tail vein metastatic assay showed that HMGA1 promoted SUZ12/CCDC43-mediated GC cell metastasis in vivo. Our findings suggest that HMGA1 promotes GC growth and metastasis by transactivating SUZ12 and CCDC43 expression, highlighting HMGA1 as a potential prognostic biomarker in the treatment of GC.

Developing effective internal wound dressing materials is important for postoperative tissue regeneration while remains a challenge due to the poor biological environment-adaptability of conventional materials. Here, we report an example of injectable self-healing hydrogel based on gastric environment-adaptive supramolecular assembly, and have explored its application for gastric perforation healing. By leveraging the gastric environment-modulated supramolecular interactions, the self-assembled hydrogel network is orchestrated with sensitive thermo-responsibility, injectability, printability and rapid self-healing capability. The hydrogel dressing can effectively inhibit the attachment of microorganisms and demonstrates outstanding antibiofouling property. In vivo rat model further demonstrates the as-prepared hydrogel dressing simplifies the surgical procedures, reduces postoperative complications as well as enhances the healing process of gastric perforation compared with the conventional treatment. This work provides useful insights into the development of biological environment-adaptive functional materials for various biomedical applications.

While the chemistry of trivalent rare-earth metal hydrido complexes has been well developed in the past 40 years, that of the divalent rare-earth metal hydrido complexes remains in its infancy because of the synthetic challenge of such complexes. In this paper, we report the synthesis and structural characterization of a divalent ytterbium hydrido complex supported by a bulky β-diketiminato-based tetradentate ligand. This hydrido complex is a dimer containing two μ-hydrogen ligands, and it easily undergoes a hydrido shift reaction to form a new divalent ytterbium hydrido complex that contains only one hydrido bridge. Furthermore, this hydrido complex reacts with pyridine and pyridine derivatives, showing versatile reactivity [Yb-H addition to pyridine, hydrido shift to ancillary ligand, and ytterbium(II)-center-induced redox reaction with bipyridine]. This hydrido complex reacts with Ph3P═O, resulting in a P-CPh cleavage of Ph3P═O and an elimination of C6H6; on the other hand, the reaction with Ph3P═S is a hydrido coupling-based redox reaction. The reactions of this hydrido complex with 1 and 2 equiv of PhSSPh clearly indicate that the hydrido coupling-based redox reaction is prior to the ytterbium(II) oxidation-based redox reaction.

Diffusion bonding was successfully applied to join 304 stainless steel (SS) and tungsten (W) using interlayers of Cu and Ni, and the effect of bonding temperature on microstructure and strength of 304SS/Cu/W and 304SS/Ni/W joints is investigated. The present study shows that a sound 304SS/Cu/W joint with sufficient mutual diffusion across 304SS/Cu and Cu/W interfaces is obtained at a bonding temperature of 1000 ℃, in which solid solutions occur at Cu/W interface. The 304SS/Cu/W joint bonded at 1000 ℃ shows the highest shear strength of 277.2 MPa and good ductility. The occurrence of cracks at 304SS/Cu interface with the increasing of bonding temperature results in the decrease in shear strength of 304SS/Cu/W joints under brittle fracture. The 304SS/Ni/W joints are free of crack in the bonding temperatures of 850 ℃–1000 ℃, which shows the highest shear strength of 237 MPa bonded at 950 ℃ due to occurrence of intermetallic compound Ni4W in the diffusion layer close to Ni/W interface. No obvious diffusion layer at 304SS/Ni/W is observed following bonding at 850 ℃ and 900 ℃. The micro-voids in the diffusion layer bonded at 1000 ℃ are responsible for the lower shear strength of joint than that of 950 ℃.

The pesticide residues have become one of the issues in the fields of environmental health and food safety. Herein, an effective method was successfully developed to rapidly determine imidacloprid in environmental water samples based on magnetic molecular imprinted polymers (MMIP) coupled with high-performance liquid chromatography. MMIP were creatively synthesized in one-pot synthesis step via the nucleation process of Fe3O4 magnetic nanoparticles and the polymerization process of molecular imprinted polymers simultaneously, using imidacloprid as template and dopamine as functional monomer. The parameters effected on the extraction efficiency, including pH value and the amount of the adsorbent, have been optimized. Under the optimal conditions, MMIP was used to extract imidacloprid in water samples with excellent recovery (88–97.3%) and precision (1.2–3.3%). Therefore, magnetic nanoparticles-based dispersion solid-phase extraction could be a good candidate for highly efficient extraction of imidacloprid without complicated operations.

Aiming at reducing the energy absorption of the hydrogen cylinder for fuel cell vehicles in collision, which may lead to fierce explosion, this paper introduces an energy-absorbing protective shell combining with negative Poisson’s ratio (NPR) structure to the hydrogen cylinder. It adopts three honeycomb structures of the same mass and three kinds of aluminum alloy to determine the optimal structure and material scheme of the protective shell. Besides, sensitivity analysis is selected to screen the design parameters of the optimal structure scheme. Based on this, the overall mass of the designed protective shell, the specific energy absorption of NPR structure, the maximum impact force of rigid wall, and the maximum stress of the liner are taken to establish the optimization mathematical model. Furthermore, adaptive mutation genetic algorithm (AMGA), non-dominated sorting genetic algorithm-ii (NSGA-II), and adaptive simulated annealing algorithm (ASA) are exerted as the optimization algorithms separately to conduct optimization design and a comparison is made between the optimization results. The results show that the optimized energy-absorbing protective shell has better crashworthiness and energy absorption effect, which can effectively improve the collision safety of the hydrogen cylinder. It provides a new idea for the protection design of hydrogen storage system in fuel cells in the future.

To obtain the excellent permeate flux, rejection performance and mechanical properties, the chlorinated polyvinyl chloride (CPVC) porous membrane was fabricated on the polyethylene terephthalate (PET) non-woven fabric by non-solvent induced phase separation (NIPS), using Tween80 (polyoxyethylene sorbitan monooleate) as a hydrophilic surfactant to regulate the microstructure of the membrane. Porous skin layer and sub-layer were achieved when 3 wt.% Tween80 was added with a small amount of deionized water as additive, and internal layer consisted of various finger-like holes. The forming mechanism of microstructures was investigated according to the effects of Tween80 molecular chain structure on the viscosity and surface tension of casting solution. Significantly, the modified membranes obviously exhibited higher pure water flux, which was increased by 257 % compared with the pristine membrane. The rejection to ink suspension was over 99 %. Furthermore, the antifouling performance of modified membrane was also greatly improved on account of the above microstructure and more hydrophilic surface. This study provides a new idea for the construction of membrane microstructure and the hydrophilic modification.

C24H16N2O4Cu, triclinic, P 1 ‾ $P‾{1}$ (no. 2), a = 11.2454(6) Å, b = 13.5960(7) Å, c = 14.0076(8) Å, V = 1958.9(2) Å3, α = 79.019(5)°, β = 71.729(5)°, γ = 76.126(5)°, Z = 4, R gt (F) = 0.0438, wR ref (F 2) = 0.1030, T = 150 K.

Catalytic oxidation of volatile organic compounds (VOCs) usually encounters complicated components in flue gas causing severe deactivation that restrict its application in specific conditions. The Cl substitution in chlorobenzene further increases poisoning risks. Ozone assistance has unique superiority that can overcome these bottleneck problems. Herein, this study performs a comparative investigation of CB oxidation by oxygen and ozone over a simple Mn/Al2O3 catalyst. CB conversion suffered from slight deactivation in oxygen atmosphere (from 90 to 70%) and more severe deactivation in the presence of SO2 (from 90 to 45%) at 480 °C. Introduction of ozone successfully attained high CB conversion at low temperature (120 °C) with excellent stability and less byproducts. Especially, CB oxidation by ozone maintained its original conversion in the presence of SO2. The deactivation process was simulated by synthesizing several sulfated catalysts. Direct sulfation on Mn/Al2O3 attained more severe deactivation in CB conversion and CO2 formation than sulfation on the Al2O3 support. Ozone with a strong oxidation property promoted the CB oxidation cycle, facilitated desorption of carbonaceous intermediates, and protected MnOx species from severe erosion, thus exhibiting high and stable performance in CB oxidation.

A simple and efficient electrochemical sensor based on a homemade reshaped micropipette tip carbon paste electrode is reported. Molecularly imprinted polymer membranes of graphene oxide and polypyrrole are synthesized and modified on the surface of micropipette tip carbon paste electrode. The merit of the method is evaluated under optimized conditions via differential pulse voltammetrics. The prepared sensor exhibits remarkable sensitivity toward dopamine with a linear range of 6.4 × 10−8–2 × 10−4 M, with a limit of detection as low as 1 × 10−8 M. The proposed method is applied for the determination of dopamine in urine samples by the standard addition route. A range of 1 × 10−7–1 × 10−4 M is obtained from these samples. The relative recoveries are in the range of 95.2%–104%. The proposed method has acceptable performance for the determination of dopamine in real samples with excellent sensitivity and selectivity.

International audience; The first isolation and structural characterization of a rare-earth metal-terminal imido complex were reported in 2010, but a rare-earth metal-terminal phosphinidene complex is still absent, to date. Herein, we report the synthesis and structure of the first example of a rare-earth-terminal phosphinidene complex, namely the scandium boronylphosphinidene complex. Single-crystal X-ray diffraction shows that the complex has a much shorter Sc-P bond length as compared to that in a related scandium boronylphosphido complex, 2.381(1) angstrom vs 2.564(1) angstrom. DFT calculations indicate the presence of a strong Sc-P pi interaction in this complex, which is in striking contrast to the weak interaction found in the phosphido complex. A preliminary reactivity study demonstrates that the scandium-terminal boronylphosphinidene complex behaves as a nucleophilic phosphinidene complex.

By structurally and practically analyzing the use of Nd: YAG laser for cutting black walnut veneer, this study considered practical and environmental concerns regarding the global warming protection measures. A numerical model of laser wood veneer cutting was based on the relation between process parameters and the material thickness. A pulsed Nd: YAG was used to cut black walnut veneer of 0.3 mm thickness under different machining conditions regarding laser power and cutting speed to study the cut kerf width. An analysis of variance was conducted to test the significance of machining parameters. The parameters studied were laser power, cutting speed, kerf width, cut surface, safety, and eco-friendliness. The results showed that the kerf width decreased significantly with increased cut speed and, inversely, by laser output power. An efficient cut with a narrow kerf, clean and smooth, with less burn, was possible at laser cutting speeds of 2.5, 5.0, and 5.5 mm/s with kerf widths of 0.544, 0.69, 0.62 mm, respectively. As multiple factors affect the micro-thin wood laser cutting process, finding the optimal process parameters is crucial for successful machining with no burn effect.

Smart materials based on photo-responsive dynamic covalent bonds have the potential for use in many applications, such as photo-modulated manipulators, actuators and self-healing materials. However, the development of high-performance multifunction visible-light-driven dynamic covalent systems has been insufficient. Herein, we report a novel linear polyurethane elastomer (HABI-PU) containing visible-light-switchable hexaarylbiimidazole (HABI) units in the polymer backbone with photo-induced scission and rapid healing capacities. When exposed to 405 nm light, the scratches on the HABI-PU film took only a few seconds to heal. More serious cut damage could be healed after exposure for 30 s and placed in the dark at room temperature for 6 h. Moreover, when a certain weight was loaded during light irradiation, the elastomers broke off as the toughness of the HABI-PU elastomers decreased. The reversible dissociation of the C–N bond of the HABI units caused the scission of long polymer chains into short chains upon light irradiation and further endowed HABI-PU with the properties of photo-induced fracture/healing. Such elastomers are promising for application in the fields of photo-controlled triggers, biomimetic systems, recycled materials, optical machining, and other engineering streams.

Water-soluble conjugated polymers (WSCPs) with the dual capability of two-photon imaging and singlet oxygen (1O2) production have become one of the most promising agents for noninvasive imaging guided photodynamic therapy (PDT). To obtain good imaging and PDT effects, two-photon excited (TPE) red-emitting WSCPs with good biocompatibility and 1O2 production capability are highly needed. Herein, a novel zwitterionic red-emitting WSCP P1′′ and its cationic analogue P1′ were synthesized and studied by comparison. The backbones of both polymers consisted of electron-rich poly[9,9′-bis(2-(2-(2-bromoethoxy)ethoxy)ethyl)fluorene-2,7-ylene vinylene] doped with a small amount of electron-deficient red-emitting unit, 4,7-bis(2-thienyl)-2,1,3-benzothiadiazole (TBT). Both P1′ and P1′′ achieved TPE red-emission through fluorescence resonance energy transfer (FRET). However, when compared with P1′, P1′′ exhibited higher water-solubility and resistance to nonspecific binding in the physiological environment, which could lead to a 5-fold increase in cellular uptake. Moreover, two-photon cell imaging experiments indicated that more of P1′′ entered into HeLa cells than P1′ and located in the cytoplasm instead of adhering near the cell membrane. Furthermore, P1′′ displayed a 1O2 quantum yield of 61%, which was much higher than that of P1′ (39%). These results could be mainly attributed to the anionic sulfonate groups within the zwitterionic side chains, which probably not only further enhanced the water solubility, but also promoted the generation of 1O2 by facilitating the transfer of the singlet-to-triplet excited state. Hence, zwitterionic P1′′ was demonstrated to show potential as an excellent TPE red-emitting photosensitizer for two-photon imaging-guided PDT.

Aluminum anodization process requires a lot of electrical energy for the migration of ions in a barrier-type oxide film, in which electrode polarization leads to massive energy consumption. The cathodes are considered to be modified with catalysts, reducing their hydrogen evolution reaction (HER) overpotential in order to improve its energy utilization efficiency. In this study, N-doped carbon nanotube (NCNT)-supported Pt nanoparticle (NCNTs/Pt) electrodes were prepared instead of the traditional stainless steel cathodes. Considering the neutral electrolyte used for the aluminum anodizing process, the NCNTs/Pt electrodes were tested in an ammonium adipate (pH = 6.8), exhibiting an overpotential of 125 mV at −10 mA cm−2 and a mass activity of 107.6 A gPt−1. The NCNTs/Pt electrodes were employed as cathodes to measure the aluminum anodization energy consumption, which enabled 9.04% reduction at a formation voltage of 150 V compared with stainless steel electrodes. This study provides a way for energy conservation in the aluminum anodization process, with the novel pathway altering the cathodic electrode using carbon-based noble metals as efficient catalysts.

This work obtained and identified pterocephanoside A (1), one new iridoid glucoside derivative with rare structure of three iridoid glycosides linked to cyclopenta[c]pyran-3(1H)-one, and 10 known iridoids (2-11) from Pterocephalus hookeri through silica gel column chromatography and semi-preparative HPLC. The structure of the new compound was confirmed by 1D and 2D NMR and HRMS data analysis. Compounds 1 and 2 were isolated from this plant for the first time. The iridoids mostly possessed seco-iridoid subtype and iridoid subtype skeletons from P. hookeri. Compounds 1, 3, 4, and 6-11 showed weak anti-inflammatory activity.

Synthesis of silacycle compounds are of fundamental and application importance. Herein we report the first example of insertion of metal-substituted silylene fragment into naphthalene's aromatic ring. More significantly, this insertion is followed by interesting rearrangements to yield silaspiro-benzocycloheptenyl and cyclobutenosilaindan derivatives. The formation of cyclobutenosilaindan derivative includes the C-C bond cleavage and 4π electrocyclization steps; the formation of silaspiro-benzocycloheptenyl derivative is more complicated, including the C-C bond cleavage, reversible 4π electrocyclization, C-H bond activation and C-Si bond cleavage. DFT investigations were carried out to shed light on the mechanistic aspects of these two rearrangements. The formed cyclobutenosilaindan potassium can readily react with PhOH, MeOTf, EtOTf, PhCH2 Cl or PhCOCl at room temperature to afford the hydrogen, alkyl, benzyl or benzoyl substituted cyclobutenosilaindans in high yields.

Silicon oxycarbide (SiOC) as a prospective electrode material for next-generation lithium ion batteries (LIBs) was restricted by the unsatisfactory discharge capacity and inflexibility used in flexible and wearable electronics. Herein, freestanding flexible SiOC/nitrogen-doped carbon fiber films are constructed through electrospinning process followed by carbonizing in NH3 atmosphere. In this way, SiOC particles are tightly embedded in N-doped carbon fibers, forming a 3D conductive network to promote electron transport and faster reaction kinetics. The nitrogen dopants create more defects in carbon fibers matrix, which improve the electronic conductivity and electrochemical active sites of the electrodes. Owing to the above synergistic effect, SiOC/nitrogen-doped carbon fiber electrodes exhibit a high initial Coulombic efficiency of 73 % and a reversible remaining capacity of 595 mA h g−1 at 200 mA g−1 even after 200 cycles. The electrodes with good flexibility can successfully drive a light-emitting diode even when the package battery is bended to 180°.

Summary Smoking is mainly sustained by nicotine dependence (ND), which varies across ethnic groups principally due to genetic as well as environmental factors. The Fagerström Test for Nicotine Dependence (FTND) and biomarkers of tobacco exposure are two important approaches to assess ND. However, the relationship between ND and FTND of Chinese smokers has not been studied. The aim of this study was to assess the relationship between FTND scores and nicotine, cotinine, 3′-hydroxycotinine (3HC) and nicotine metabolite ratio (NMR, the concentration ratio of 3HC to cotinine) in Chinese smokers. FTND was carried out and general characteristics were collected using a self-administered smoking questionnaire with 289 smokers. Nicotine, cotinine and 3HC in urine were simultaneously determined by liquid chromatography–mass spectrometry/mass spectrometry (LC-MS/MS). The concentrations of nicotine, cotinine and 3HC in the urine of smokers with a high FTND score were higher than in the urine of those with a low FTND score. There were significant correlations between urinary biomarker and FTND scores. Except for FTND item 2 (difficulty to refrain), the other items showed significant associations with the urinary biomarkers. No relationship was found between the nicotine metabolite ratio (NMR, 3′-hydroxycotinine/cotinine) and FTND scores or general characteristics of the participants. In conclusion, biomarkers of tobacco exposure levels are significantly associated with FTND scores. However, FTND Item 2 and NMR were not found to be associated with nicotine dependence in Chinese smokers.

Hierarchical porous zinc oxide (ZnO)/silver (Ag) microspheres were prepared by two-step method. The porous ZnO microspheres were prepared firstly, and then Ag nanoparticles were evenly anchored on the surface of ZnO microspheres by Sn2+ activation method. The results show that ZnO is wurtzite phase, and Ag particles are only coated on the surface of ZnO microspheres. Compared with pure ZnO, there are two obvious absorption peaks of Ag-doped ZnO, which corresponds to the ultraviolet absorption peak of ZnO and the plasma resonance absorption peak of Ag, respectively. The intensities of photoluminescence peak of ZnO/Ag microspheres are significantly lower than that of pure ZnO. Moreover, ZnO/Ag microspheres show higher photocatalytic activity than ZnO, which may be attributed to the existence of highly dispersed Ag.

Introduction Colitis-associated cancer (CAC) accounts for approximately 15% of IBD patient mortalities. However, currently available anti-CAC drugs possess many disadvantages including safety, specificity and side effects. Therefore, the development of novel anti-CAC compounds is imperative. HLJ2 was a monomeric compound synthesized by our institute and reported to have an effect on ulcer colitis. Methods In vivo the AOM/DSS-induced CAC model was used to evaluate the effects of HLJ2 on ameliorating CAC symptoms, immunohistochemical analysis was used to analyze the pathological damage to colons and epithelial-mesenchymal transition was for changes of cytokines. In vitro, flow cytometric analysis, immunofluorescence and Western blot were used to detect the inhibition effect of HLJ2 on nuclear factor-κB and epithelial-mesenchymal transition in TGF-β1-stimulated SW480 cells. Results In the AOM/DSS animal model, HLJ2 was demonstrated to inhibit the secretion of inflammatory cytokines and nuclear factor-κB, levels of tumorigenesis-related proteins including snail, and finally inhibited a key step in metastasis, epithelial-mesenchymal transition. In vitro, HLJ2 was also shown to inhibit nuclear factor-κB and epithelial-mesenchymal transition in TGF-β1-stimulated SW480 cells in accordance with in vivo results. Meanwhile, the nuclear factor-κB inhibitor could interrupt the effect of HLJ2 on epithelial-mesenchymal transition. Discussion HLJ2 may ameliorate CAC through inhibiting nuclear factor-κB and then downstream epithelial-mesenchymal transition. The combination of the obvious improvement in effects on CAC without obvious side effects suggests that HLJ2 could be developed as a potential CAC therapeutic candidate.

Starting from ZrO2 and boron (molar ratio: 1:4), four ZrB2 powders were synthesized by borothermal reduction method, three of which were designed to introduce minor modifications by combining solid solution with Ti and/or water-washing. The sinterability, microstructures, mechanical properties and thermal conductivity were investigated. In comparison with the conventional borothermal reduction, the modified methods offered significant improvement in terms of densification of ZrB2 ceramics, particularly the mixture that included water-washing. Owing to the refined particle size and boron residues, ZrB2 ceramics from the modified borothermal reduction which included water-washing demonstrated nearly full densification, Vickers hardness of 14.0 GPa and thermal conductivity of 82.5 W/m K after spark plasma sintering at 2000 °C for 10 min. It was revealed that the properties of ZrB2 ceramics could be enhanced utilizing the proposed minor modification, starting from the same raw materials and adopting the same sintering conditions.

A series of silica nanoparticles (SNP-1, SNP-2, SNP-3, SNP-4, SNP-5 and SNP-6) were synthesized in ethanol by the hydrolysis and polycondensation reaction of tetraethoxysilane with the aids of water initiator and ammonia catalyst and then investigated in a comprehensive manner in terms of morphological structure by using synchrotron transmission small-angle X-ray scattering and grazing incidence wide-angle X-ray scattering and combined together with dynamic light scattering, scanning electron microscopy, infrared spectroscopy and thermogravimetry. They were confirmed to be successfully synthesized as oblate amorphous ellipsoids (Re = 9.70∼56.30 nm, equatorial radius; e = 0.78∼0.80, ellipsoidicity) with sharp surfaces in single unimodal and narrow size distributions. The radial density profile details, including two-phases (i.e., less dense core and denser shell), were determined for the first time, in addition to a set of structural parameter details (radius of gyration, radius, core radius, shell thickness, and radius distribution). Larger particle was synthesized conveniently by higher loading of ammonia solution with respect to the silane monomer. The as-synthesized silica particles were found to undergo two-step mass loss behaviors in heat treatment up to 500 °C; the first-step loss took place below 120 °C due to removals of physically absorbed water molecules and possible solvent residues and the second-step loss above 180 °C occurred by removals of water and ethanol byproducts due to the post condensation reactions of hydroxy and ethoxy residues.

Purpose Growing evidence indicates that aberrant expression of microRNAs contributes to tumor development. However, the biological role of microRNA-4490 (miR-4490) in gastric cancer (GC) remains to be clarified. Methods To explore the function of miR-4490 in GC, we performed colony formation, EdU incorporation, qRT-PCR, Western blotting, in situ hybridization (ISH), immunohistochemistry (IHC), flow cytometry, ChIP and dual-luciferase reporter assays. In addition, the growth, migration and invasion capacities of GC cells were evaluated. Results We found that miR-4490 was significantly downregulated in primary GC samples and in GC-derived cell lines compared with normal controls, and that this expression level was negatively correlated with GC malignancy. Exogenous miR-4490 expression not only reduced cell cycle progression and proliferation, but also significantly inhibited GC cell migration, invasion and epithelial-mesenchymal transition (EMT) in vitro. Mechanistically, we found that miR-4490 directly targets USP22, which mediates inhibition of GC cell proliferation and EMT-induced metastasis in vitro and in vivo. Moreover, we found through luciferase and ChIP assays that transcription factor POU2F1 can directly bind to POU2F1 binding sites within the miR-4490 and USP22 promoters and, by doing so, modulate their transcription. Spearman’s correlation analysis revealed a positive correlation between USP22 and POU2F1 expression and negative correlations between miR-4490 and USP22 as well as miR-4490 and POU2F1 expression in primary GC tissues. Conclusion Based on our results we conclude that miR-4490 acts as a tumor suppressor, and that the POU2F1/miR-4490/USP22 axis plays an important role in the regulation of growth, invasion and EMT of GC cells.

The morphology of a polymer brush is of great importance in determining surface properties, such as lubrication. In light of this, we systematically study the morphologies of ring polyelectrolyte b...

A novel pollutant, tris(2,4-di-tert-butylphenyl)phosphate (I168O), was identified in urban fine particulate matter (PM2.5) samples in a nontargeted screening based on mass spectrometry for the first time. I168O was detected in all samples collected from two typical cities far away from each other in China. The concentrations of I168O reached up to 851 (median: 153) ng/m3, indicating that it was a widespread and abundant pollutant in the air. The antioxidant Irgafos 168 [I168, tris(2,4-di-tert-butylphenyl)phosphite] popularly added in plastics was the most suspected source for the detected I168O. Simulation studies indicated that heating, UV radiation, and water contact might significantly (p < 0.05) transform I168 to I168O. In particular, I168O might be magnificently evaporated into the air at high temperatures. The outdoor inhalation exposure of I168O may exert substantial health risks.

A series of spinel CuM2O4 (M = Mn, Fe, and Al) was used as the catalyst to investigate the effective degradation of toluene, and then CuMn2O4 with better catalytic activity was selected as the research object to study its activity at different ratios of Cu and Mn. Meanwhile, CeO2 was introduced to modify CuMn bimetallic oxide to improve its catalytic performance. The structure, morphology, and valence states of surface elements of as-prepared catalysts were characterized by XRD, TEM, SEM, N2 adsorption-desorption, XPS, and H2-TPR. Using toluene as a probe molecule, the catalytic activity of the catalyst was tested and the results showed that the conversion rate of toluene catalyzed by CeO2-CuMn2O4 catalyst can reach 90% at 200 °C (T90) and 100% at 240 °C (T100). The CO2 yield can also reach 100% at 248 °C. Moreover, the possible catalytic mechanism for toluene by the CeO2-CuMn2O4 was briefly explored. The catalytic oxidation of toluene over the oxide follows the Mars-van Krevelen mechanism.

A novel coordination polymer based on Zn(II) ions as nodes, {[Zn2TTPA(GA)2]·2H2O}n, has been successfully synthesized by employment of tris[4-(1H-1,2,4-triazol-1-yl)phenyl]amine (TTPA), a 1,2,4-triazole derivative with the presence of the flexible glutaric acid (H2GA) ligand with Zn(II) nitrate salts. Luminescent detection experiments show that the complex could be applied as a sensor for 2,4,6-trinitrophenol via the luminescence quenching. To develop new candidates for the sepsis treatment in clinic and evaluate the influence of the compound on the immune cells, the western blotting was conducted to detect the activation of the anti-bacterial response in the macrophages after compound treatment under infection. The relative expression levels of the miR-16 in the immune cells was measured for revealing the detail mechanism of the compound.

Purpose To determine the role of NLRP3 inflammasome activation in low-dose radiation-induced radiation pneumonitis (RP) and to assess whether inhibition or deletion of the NLRP3 inflammasome is critical for conferring protection against RP. Methods and Materials The human monocytic THP-1 cells were treated with increasing doses of radiation to assess the activation of NLRP3 by Western blot and enzyme-linked immunosorbent assay. Reactive oxygen species (ROS) production was measured by flow cytometry, with or without ROS inhibitor treatment. A mouse thoracic radiation model that received different doses of radiation was used, and the lung tissues of thoracic-irradiated nlrp3-/- and wild-type C57BL/6 mice were examined by hematoxylin and eosin and immunofluorescence staining. The concentrations of cytokines in the bronchoalveolar lavage fluid were measured by enzyme-linked immunosorbent assay and Luminex multiplex assays. Lipopolysaccharide (LPS) was administered intranasally 28 days after thoracic irradiation, and NLRP3 inhibitor, MCC950 was administered intraperitoneally after irradiation at 2 different doses. Results (1) The NLRP3 inflammasome was activated in 2 Gy irradiated THP-1 cells; NLRP3 and cleaved-caspase-1 levels were not associated with dose escalation of irradiation. (2) Activation of the NLRP3 inflammasome was mediated by ROS, and ROS inhibitor treatment decreased the production of IL-1β and IL-18 in vitro. (3) NLRP3 was activated in mouse lungs by irradiation at 2 Gy, 4 Gy, and 16 Gy, and NLRP3 activation was continuous for 8 weeks. (4) NLRP3 deletion protects against LPS-mediated monocyte infiltration in the mouse lung. (5) The administration of MCC950 decreased the inflammation score of the mice irradiated with 2 Gy or 16 Gy in vivo. Conclusions Our results indicate that the NLRP3 inflammasome is activated by low-dose irradiation both in vitro and in vivo. Inhibition or deletion of NLRP3 can specifically alleviate the mouse lung inflammation caused by radiation and LPS treatment. This study reveals the mechanism of low-dose radiation therapy–induced RP and offers a possible treatment strategy.

Objective To explore the effects of electroacupuncture pretreatment on mitochondrial energy metabolism in the rats with myocardial ischemia reperfusion injury (MIRI). Methods A total of 60 SPF Wistar rats were randomly divided into a sham-operation group (sham group), a myocardial ischemia reperfusion injury group (MIRI group) and an electroacupuncture pretreatment group (EA group), 20 rats in each one. The rats in the sham group and the MIRI group were binded for 7 days, once a day, 20 min each time. On the 8th day, the sample was collected after the heart exposed for 50 min in thoractomy in the sham group and the sample was collected after ischemia for 20 min and reperfusion for 30 min in thoractomy in the MIRI group. In the EA group, the pretreatment intervention with electroacupuncture was applied at "Neiguān (内关PC6)", "Guānyuan (关元CV4)" and "Zusānlĭ (足三里ST36)" in the rats for 7 days, once a day, 20 min each time. On the 8th day, after ischemia for 20 min and reperfusion for 30 min in thoractomy, the sample was collected in the EA group. The changes in STⅡ segment of electroacardiogram (ECG) were observed and measured. Using enzyme-linked immunosorbent assay (ELISA), the concentrations of cardiac troponin T (cTnT) and cardiac troponin I (cTnI)were detected. Using nitro blue tetrazolium chloride monohydrate (NBT) staining, the myocardial infarction weight percentage was measured. Using ELISA, the concentrations of mitochondrial adenosine monophosphate (AMP), adenosine diphosphate (ADP)and adenosine triphosphate (ATP)were detected. Results (1) STⅡ changes: in 20 min of ligation, compared with the sham group, the STⅡ segment of electrocardiograph (ECG) was elevated significantly in the MIRI group and EA group (both P Conclusions Electroacupuncture pretreatment reduces the elevation of ECG STⅡ segment, decreases the concentrations of myocardial injury markers, cTnT and cTnI and regulates the transfer among AMP, ATP and ADP. The protective effect of electroacupuncture pretreatment may result from the regulation of mitochondrial energy metabolism.

Silicon carbide ceramics were pressureless joined by using Ti foil and Si powder, which generated Ti3SiC2 phase as the interlayer. The phase composition, microstructure and the shear strength were investigated. It was revealed that the SiC assembly after joining at 1500oC showed the high shear strength of 76.2 ± 19.5 MPa. The secondary phase of TiC within the interlayer was expected to contribute to densification improvement of Ti3SiC2 phase and thermal stress reduction.

High-temperature calcination was used to modify garnet media. Brunauer–Emmett–Teller (BET) measurements, X-ray diffractometer (XRD), scanning electron microscopy (SEM), zeta potential analysis, and a static adsorption experiment on humic acid removal were carried out to compare unmodified garnet and traditional quartz sand. Fitting adsorption isotherm of the media before and after modification was conducted to determine the adsorption type, and a dynamic filtration experiment was performed to treat micro-polluted water. Results of the characterization analysis and the static adsorption experiment revealed that, compared with the smooth surface of unmodified garnet, the surface of modified garnet media was covered with Fe2O3, which showed a rough concave-convex structure with a specific area that was 2.44 times larger than that of unmodified garnet. The removal efficiency of organic matter after modification increased from 2.5–4.5% to 51.7–63.1%, and the adsorption capacity increased 11–24 times. The adsorption type of the modified garnet media belongs to the Langmuir and Freundlich adsorption mode, while that of the original media belongs to the Freundlich adsorption mode. Results of the dynamic filtration experiment revealed that the effect of modified garnet media on turbidity, CODMn, and UV254 removal was better than that of unmodified garnet and traditional quartz sand.

B lymphocyte hyperactivity plays a pathogenic role in systemic lupus erythematosus (SLE), and spliced X box-binding protein 1 (XBP1s) has been implicated in B cell maturation and differentiation. We hypothesized that blockade of the XBP1s pathway inhibits the B cell hyperactivity underlying SLE and lupus nephritis (LN) development. In the present study, we systematically evaluated the changes in B cell activation induced by the Xbp1 splicing inhibitor STF083010 in a pristane-induced lupus mouse model. The lupus mouse model was successfully established, as indicated by the presence of LN with markedly increased urine protein levels, renal deposition of Ig, and mesangial cell proliferation. In lupus mice, B cell hyperactivity was confirmed by increased CD40 and B cell-activating factor levels. B cell activation and plasma cell overproduction were determined by increases in CD40-positive and CD138-positive cells in the spleens of lupus mice by flow cytometry and further confirmed by CD45R and Ig light chain staining in the splenic tissues of lupus mice. mRNA and protein expression of XBP1s in B cells was assessed by real-time PCR, Western blot analysis, and immunofluorescence analysis and was increased in lupus mice. In addition, almost all changes were reversed by STF083010 treatment. However, the expression of XBP1s in the kidneys did not change when mice were exposed to pristane and STF083010. Taken together, these findings suggest that expression of XBP1s in B cells plays key roles in SLE and LN development. Blockade of the XBP1s pathway may be a potential strategy for SLE and LN treatment.