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The Ru-catalyzed carbonylation of alkenes with CO2 as a C1 surrogate and imidazole chlorides as the promotor is investigated by a combination of computational and experimental study. The conversion rate of CO2 to CO is positively correlated with the efficiency of both hydroesterification and hydroformylation, which is found facilitated in the presence of chloride additives with a decreasing order of BmimCl ∼ B3MimCl > BmmimCl ∼ LiCl. Taking the hydroesterification with MeOH as a representative example, BmimCl bearing C–H functionality at the C2 site of the cation assists the reduction of CO2 to CO as a hydrogen donor medium, with the anion and cation acting in a synergistic fashion. Subsequent insertion of CO2 into the formed Ru–H bond with the assistance of chloride anion produces the Ru–COOH species, which ultimately accelerates the activation of CO2.

Introduction Although capsaicin has long been used as food additive and medication worldwide, its actions on gastrointestinal tract as its most delivery pathway have not been well addressed. Objectives In the present study, we aimed to study GI actions of capsaicin on mesenteric arterioles in normal and colitis mice and to elucidate the underlying mechanisms. Methods Vasorelaxation of human submucosal arterioles and the mesenteric arterioles from wide-type (WT) mice, TRPV1−/− and TRPV4−/− (KO) mice were measured. The expression and function of TRPV channels in endothelial cells were examined by q-PCR, immunostaining, Ca2+ imaging and membrane potential measurements. Results Capsaicin dose-dependently induced vasorelaxation of human submucosal arterioles and mouse mesenteric arterioles in vitro and in vivo through endothelium-dependent hyperpolarization (EDH), nitric oxide (NO), and prostacyclin (PGI2). Using TRPV1 and TRPV4 KO mice, we found that capsaicin-induced vasorelaxation was predominately through TRPV4/EDH, but marginally through TRPV1/NO/PGI2. Capsaicin induced hyperpolarization through activation of endothelial TRPV4 channels and intermediate-conductance of Ca2+-activated K+ channels to finally stimulate vasorelaxation. Importantly, capsaicin exerted anti-colitis action by rescuing the impaired ACh-induced vasorelaxation in WT colitis mice but not in TRPV4 KO colitis mice. Conclusions Capsaicin increases intestinal mucosal blood perfusion to potentially prevent/treat colitis through a novel TRPV4/EDH-dependent vasorelaxation of submucosal arterioles in health and colitis. This study further supports our previous notion that TRPV4/EDH in mesenteric circulation plays a critical role in the pathogenesis of colitis.

Binding and unbinding of transcription factors to DNA are kinetically controlled to regulate the transcriptional outcome. Control of the release of the transcription factor NF-κB from DNA is achieved through accelerated dissociation by the inhibitor protein IκBα. Using single-molecule FRET, we observe a continuum of conformations of NF-κB in free and DNA-bound states interconverting on the subseconds to minutes timescale, comparable to in vivo binding on the seconds timescale, suggesting that structural dynamics directly control binding kinetics. Much of the DNA-bound NF-κB is partially bound, allowing IκBα invasion to facilitate DNA dissociation. IκBα induces a locked conformation where the DNA-binding domains of NF-κB are too far apart to bind DNA, whereas the loss-of-function IκBα mutant retains the NF-κB conformational ensemble. Overall, our results suggest a novel mechanism with a continuum of binding modes for controlling association and dissociation of transcription factors.

Summary Drought and salt stresses impose major constraints on soybean production worldwide. However, improving agronomically valuable soybean traits under drought conditions can be challenging due to trait complexity and multiple factors that influence yield. Here, we identified a nuclear factor Y C subunit (NF‐YC) family transcription factor member, GmNF‐YC14, which formed a heterotrimer with GmNF‐YA16 and GmNF‐YB2 to activate the GmPYR1‐mediated abscisic acid (ABA) signalling pathway to regulate stress tolerance in soybean. Notably, we found that CRISPR/Cas9‐generated GmNF‐YC14 knockout mutants were more sensitive to drought than wild‐type soybean plants. Furthermore, field trials showed that overexpression of GmNF‐YC14 or GmPYR1 could increase yield per plant, grain plumpness, and stem base circumference, thus indicating improved adaptation of soybean plants to drought conditions. Taken together, our findings expand the known functional scope of the NF‐Y transcription factor functions and raise important questions about the integration of ABA signalling pathways in plants. Moreover, GmNF‐YC14 and GmPYR1 have potential for application in the improvement of drought tolerance in soybean plants.

Herein, thiourea (TA) was firstly used as the structure-directing agent to simultaneously tune the morphology and surface acidity of CeO2(w/o) synthesized via one-pot hydrothermal treatment, and exhibits better enhancement on its NH3-SCR activity than urea (UA). In addition, CeO2-TA(10) obtained at the suitable TA/Ce molar ratio of 10 presents the superior NH3-SCR activity in a broad temperature window. The introduction of thiourea promotes the formation of cubic CeO2 nanocubes in catalyst, but not the nanoparticles formed in CeO2(w/o) and CeO2-UA(10). Furthermore, the cubic CeO2 nanocubes mainly expose the crystal faces of {100}, which is helpful to the formation of more oxygen vacancies on the surface of CeO2-TA(10). At the same time, the formation of the specific sulfate species (CeOSO4) is also promoted under the influence of thiourea, thus simultaneously tunes the surface acidity of CeO2(w/o) by enhancing the Bronsted acid sites, although its Lewis acid sites are significantly decreased due to the diminution of the BET surface area. Compared with urea, the using of thiourea as the structure-directing agent also adjusts the physical-chemical properties of CeO2(w/o) and promotes its chemisorbed oxygen concentration. The results presented herein give a new thought for the development of state-of-the-art cerium-based catalysts for the NH3-SCR reaction.

Infantile pneumonia is a common inflammatory disease with the infections of various pathogens in lower respiratory tracts. Here, the role and working mechanism of circular RNA (circRNA) ubiquinol-cytochrome c reductase core protein 2 (circ-UQCRC2; hsa_circ_0038467) in infantile pneumonia were investigated. Cell viability, apoptosis, and inflammatory response were assessed by 3-(4,5-dimethyl-thiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay, flow cytometry, and enzyme-linked immunosorbent assay (ELISA). Cell oxidative stress was analyzed by measuring the production of malondialdehyde (MDA) and superoxide dismutase (SOD). Reverse transcription-quantitative polymerase chain reaction (RT-qPCR) and Western blot assay were performed to determine the expression of RNAs and proteins. Dual-luciferase reporter assay and RNA immunoprecipitation (RIP) assay were performed to confirm the interaction between microRNA-495-3p (miR-495-3p) and circ-UQCRC2 or myeloid differentiation primary response protein 88 (MYD88). Lipopolysaccharide (LPS) treatment suppressed the viability while induced the apoptosis, inflammation, and oxidative stress of 16HBE cells in a dose-dependent manner. LPS exposure dose-dependently up-regulated the expression of circ-UQCRC2 in 16HBE cells. Circ-UQCRC2 absence attenuated LPS-induced injury in 16HBE cells. miR-495-3p was a target of circ-UQCRC2, and circ-UQCRC2 silencing-mediated protective effects in LPS-induced 16HBE cells were partly reversed by anti-miR-495-3p. MYD88 was a target of miR-495-3p, and MYD88 overexpression partly counteracted miR-495-3p accumulation-mediated influences in 16HBE cells upon LPS exposure. Circ-UQCRC2 interference decreased the protein expression of MYD88 partly by up-regulating miR-495-3p in LPS-induced 16HBE cells. In conclusion, circ-UQCRC2 contributed to LPS-induced injury of 16HBE cells by targeting miR-495-3p/MYD88 signalling-mediated inflammatory response and oxidative stress.

Metal halide perovskites have attracted great attention for their superior light energy conversion applications. Herein, we demonstrated a facile synthesis of zero-dimensional Sn2+ perovskite Cs4-xMxSnBr6(M = K+ and Rb+) material through the cation transformation reaction at room temperature. Cs4SnBr6 NCs was mixed with pure metal bromide salts (KBr and RbBr) via the mechanochemical process to successfully synthesize Cs4-xMxSnBr6 perovskite where transformation of Cs to mixed Cs/Rb and mixed Cs/K was achieved. By substituting different cations, the bright fluorescence of the Cs4-xMxSnBr6 was tuned from dim green to greenish-cyan while achieving the photoluminescence (PL) quantum yield of ∼39%. The crystal structure of Sn based perovskite with the substitution of K+ or Rb+ cations was determined by X-ray diffraction (XRD). Moreover, the Cs4-xMxSnBr6 demonstrated superior air stability and exhibited a better photocatalytic activity for CO2 reduction reaction (CO2RR) with high selectivity of CH4 gas with a higher yield rate compared to the pristine Cs4SnBr6 NCs.

The morphology modulation of multi-level structures and the multifunctional design of their composites are challenging research priorities in the field of electromagnetic wave absorption. In this work, the abandoned polyurethane is adopted as a sacrificial template of a three-dimensional carbon network. The morphology-controlled Fe/Fe2O3@porous carbon composites with highly cross-linked 3D structures are synthesized by simple hydrothermal and thermal treatments. Among them, the PM-700 with a coral-like structure has a minimum reflection loss of −54.7 dB at a thickness of 1.4 mm and an effective absorption bandwidth of 6.4 GHz (10.8–18 GHz) at 1.9 mm. The excellent absorption performance is attributed to the three-dimensional magnetic conductive network, which provides superior impedance matching, synergistic effects of dual-loss mechanisms, and multiple attenuation. Furthermore, benefiting from its unique three-dimensional structure, the PM-700 possesses low density (0.088 g/cm3), excellent mechanical properties (withstand more than 4000 times of its own weight), and high thermal management (thermal insulation and flame retardancy). Meanwhile, PM-700 exhibits excellent infrared stealth performance, which is conducive to the development of multi-band compatible stealth materials. This work not only contributes to the conservation of resources and reuse of wasted polyurethane, but also facilitates the multifunctional application of microwave absorbing materials with multi-level structures.

A series of dicyano-imidazole-based molecules with thermally activated delayed fluorescence (TADF) properties were synthesized to obtain pure blue-emitting organic light-emitting diodes (OLEDs). The targeted molecules used dicyano-imidazole with a short-conjugated system as the electron acceptor to strong intermolecular π-π interactions, and provide a relatively shallow energy level of the lowest unoccupied molecular orbital (LUMO). The cyano group was selected to improve imidazole as an electron acceptor due to its prominent electron-transporting characteristics. Four different electron donors, that is, 9,9-dimethyl-9,10-dihydroacridine (DMAC), 10H-spiro(acridine-9,9'-fluoren) (SPAC), and 9,9-diphenyl-9,10-dihydroacridine (DPAC), were used to alternate the highest occupied molecular orbital (HOMO) energy level to tune the emission color further. The crowded molecular structure in space makes the electron donor and acceptor almost orthogonal, reducing the energy gap (ΔEST ) between the first excited singlet (S1 ) and the triplet (T1 ) states and introducing significant TADF property. The efficiencies of the blue-emissive devices with imM-SPAC and imM-DMAC obtained in this work are the highest among the reported imidazole-based TADF-OLEDs, which are 13.8 % and 13.4 %, respectively. Both of Commission Internationale de l'Eclairage (CIE) coordinates are close to the saturated blue region at (0.17, 0.18) and (0.16, 0.19), respectively. Combining these tailor-made TADF compounds with specific device architectures, electroluminescent (EL) emission from sky-blue to deep-blue could be achieved, proving their great potential in EL applications.

Ionic liquids (ILs) are an important class of media that are usually used in combination with polar solvents to reduce costs and tune their physicochemical properties. In this regard, it is essential to understand the influence of adding solvents on the properties of ILs. In this work, the micro-heterogeneity and H-bonding interactions between a hydroxyl-functionalized IL, [HOEmim][TFSI], and acetonitrile (ACN) were investigated by attenuated total reflection Fourier transform infrared spectroscopy and molecular simulations. All studied IL-ACN mixtures were found to deviate from the ideal mixtures. The degree of deviations reaches the maximum at about x(ACN)=0.7 with the presence of both homogeneous clusters of pure IL/ACN and heterogeneous clusters of IL-ACN. With the addition of ACN to IL, the mixtures undergo the transformation from "ACN solvated in [HOEmim][TFSI]" to "[HOEmim][TFSI] solvated in ACN". It is found that the newly formed H-bonding interactions between the IL and ACN is the main factor that contributes to the red shifts of O-H, C2 -H, C4,5 -H, and Calkyl -H of [HOEmim]+ cation, and the blue shifts of C-D, C≡N of ACN, and C-F, S=O of [TFSI]- anion. These in-depth studies on the mixtures of hydroxyl-functionalized IL and acetonitrile would help to understand the micro-heterogeneity and H-bonding interactions of miscible solutions and shed light on exploring their applications.

Computational study on relationship between molecular structure and property of small molecule hole-transporting materials (HTMs) is an efficient pathway to acquire potential HTMs for perovskite solar cells (PSCs). Herein, by conjugating the acceptor groups of electron-deficient diazatriphenylene (DAT), tetraazatriphenylene (TAT) and hexaazatriphenylene (HAT), and p-methoxy-substituted triphenylamine (MeOTPA) electron-donors, six novel donor–acceptor-donor (D-A-D) typed HTMs (SM11 ~ SM16) are designed. Furthermore, three thiophene-substituted acceptors (SM17 ~ SM19) are also investigated. The influences of acceptor moiety on the performance of HTMs are studied by carrying out theoretical chemical calculations. Compared with the reported HTM with triphenylene unit (TPH-T), the new tailored HTMs (SM11 ~ SM19) exhibit more negative highest occupied molecular orbital (HOMO) energy levels and slightly red-shifted light absorption due to the increased electron-deficient property of acceptor group and linked positions with the MeOTPA-donor. Meanwhile, our results show that the small torsion angle between the acceptor and the donor is beneficial to promote the hole transport in HTMs, and the thiophene units on acceptor may also be helpful to enhance the charge mobility of HTMs. In addition, the large charge transfer amounts and small exciton binding energies are found for designed HTMs, which will be favorable to facilitate the electron-hole separation in HTMs. The stability of HTMs may be decreased based on the calculated results of electrostatic surface potential and absolute hardness. We hope this work could highlight the potential of azatriphenylene acceptor-based D-A-D typed HTMs for efficient PSCs.

To explore the synergistic mechanism of polymer and surfactant in the binary combination flooding of low-permeability reservoirs, the adaptability experiment of polymer salt-resistant partially hydrolyzed polyacrylamide and nonionic surfactant was carried out in the indoor system. Experiments at different ratios are also performed. The results show that the selected poly/surface binary flooding system increases with the concentration of polymer or surfactant, the viscosity of the poly/surface binary system also increases and, at the same time, has better temperature and salt resistance. The viscosity of the binary system will decrease when the salinity increases. When the surfactant concentration CS = 0.2% and the polymer concentration CP = 0.2%, the viscosity of the system is the highest. The viscosity of the poly/table binary system at different concentrations decreases when the temperature rises: pure polymer (CP = 0.2%), poly/table binary system displacement fluid CP = 0.1% + CS = 0.2% and CP = 0.2% + CS = 0.2%; and the injection pressure first rises and then drops. The final recovery rate is 51.8%, which meets the development of most oil reservoirs.

Unipolar barrier structures are used to suppress dark current in photodetectors by blocking majority carriers. Designing unipolar barriers with conventional materials is challenging due to the strict requirements of lattice and band matching. Two-dimensional materials have self-passivated surfaces and tunable band structures, and can thus be used to design unipolar barriers in which lattice mismatch and interface defects are avoided. Here, we show that band-engineered van der Waals heterostructures can be used to build visible and mid-wavelength infrared unipolar barrier photodetectors. Our nBn unipolar barrier photodetectors, which are based on a tungsten disulfide/hexagonal boron nitride/palladium diselenide heterostructure, exhibit a low dark current of 15 pA, a photocurrent of 20 μA and a detectivity of 2.7 × 1012 cm Hz1/2 W−1. Our pBp unipolar barrier photodetectors, which are based on a black phosphorus/molybdenum disulfide/graphene heterostructure, exhibit a room-temperature detectivity of 2.3 × 1010 cm Hz1/2 W−1 in the mid-wavelength infrared region under blackbody radiation. The pBp devices also show a dichroic ratio of 4.9 under blackbody radiation, and a response time of 23 μs under 2 μm laser illumination. Band-engineered van der Waals heterostructures that block dark current without suppressing photocurrent can be used to build detectors with high room-temperature detectivity for visible light and blackbody infrared light.

We show a top-down synthesis approach to mass-produce phosphorene-graphene nanosheet composites with superior cycle stability and rate capability. Currently, using exfoliation to achieve two-dimensional (2D) materials is primarily limited to pure crystals. We discover that high-quality nanoscale 2D composite phosphorene-graphene sheets can be directly exfoliated from extremely low-cost bulk three-dimensional (3D) black phosphorus-graphite composites synthesized by mechanical milling while maintaining the chemical bonding and intimate electronic contact between 2D composite layers. The hybrid phosphorene-graphene material delivers high reversible capacities of 2030, 2003, and 1597 mAh/g at high current densities of 2, 4, and 6 A/g, respectively. Quantifying the dimensional electrochemical performance, we show that 2D phosphorene-graphene nanosheets not only have excellent electrochemical kinetics for fast lithium-ion diffusion and storage but also maintain the overall structural robustness of the entire electrode for long-term cyclability. This scalable synthesis paves the way for the practical application of phosphorene-graphene materials in batteries.

Progesterone resistance can significantly restrict the efficacy of conservative treatment for patients with endometrial cancer who wish to preserve their fertility or those who suffer from advanced and recurrent cancer. SREBP1 is known to be involved in the occurrence and progression of endometrial cancer, although the precise mechanism involved remains unclear. In the present study, we carried out microarray analysis in progesterone-sensitive and progesterone-resistant cell lines and demonstrated that SREBP1 is related to progesterone resistance. Furthermore, we verified that SREBP1 is over-expressed in both drug-resistant tissues and cells. Functional studies further demonstrated that the inhibition of SREBP1 restored the sensitivity of endometrial cancer to progesterone both in vitro and in vivo, and that the over-expression of SREBP1 promoted resistance to progesterone. With regards to the mechanism involved, we found that SREBP1 promoted the proliferation of endometrial cancer cells and inhibited their apoptosis by activating the NF-κB pathway. To solve the problem of clinical application, we found that Fatostatin, an inhibitor of SREBP1, could increase the sensitivity of endometrial cancer to progesterone and reverse progesterone resistance by inhibiting SREBP1 both in vitro and in vivo. Our results highlight the important role of SREBP1 in progesterone resistance and suggest that the use of Fatostatin to target SREBP1 may represent a new method to solve progesterone resistance in patients with endometrial cancer.

Poly(6-cyanoindole) (P(CnId)) is blended with poly(styrenesulfonic acid) via doping periods of 1, 10, 20, and 30 s to obtain P(CnId)–1PSS, P(CnId)–10PSS, P(CnId)–20PSS, and P(CnId)–30PSS electrodes, respectively. FT-IR studies have revealed that P(CnId) is doped with PSS. Pt particles can be doped into P(CnId)–1PSS, P(CnId)–10PSS, P(CnId)–20PSS, and P(CnId)–30PSS by chronocoulometry (0.15 C) using electrodeposition to acquire P(CnId)–1PSS–Pt, P(CnId)–10PSS–Pt, P(CnId)–20PSS–Pt, and P(CnId)–30PSS–Pt films, respectively. For comparative purposes, in this study, Pt particles were deposited into P(CnId) under the same conditions. Scanning electron microscopy (SEM) characterization revealed that platinum distributes more uniformly into the as-prepared P(CnId)–10PSS films. The anodic peak currents could be clearly observed to reach the saturation point at a methanol concentration larger than 0.8 M. A large electrocatalytic current towards methanol oxidation (27 mA cm−2 mg−1) was noticed in P(CnId)–10PSS–Pt electrodes in comparison to P(CnId)–Pt without PSS (6.3 mA cm−2 mg−1) at +0.86 V (vs. RHE), indicating that the P(CnId)–10PSS–Pt electrode reveals potential applicability as an electrocatalyst support.

Introduction THP-1 cells, a human leukemia monocytic cell line, differentiated by phorbol myristate acetate (PMA) are widely used as surrogate of human macrophages. Differentiated THP-1 cells acquire macrophage-like characteristics including more adherence and altered cell function. Nitric oxide (NO), an intracellular messenger, is critical in regulating cell differentiation. Here we elucidated whether NO relates to PMA-induced monocyte-to-macrophage differentiation of THP-1 cells. The mutual regulation of calcium and NO was also investigated. Material & methods THP-1 cells were incubated with PMA for 24 h, followed by assay of adherence, morphological change, migration or IL-1β release. L-NG-Nitroarginine methyl ester ( l -NAME, a nitric oxide synthase inhibitor) or BAPTA-AM (a calcium chelator) was added before PMA stimulation, and levels of calcium and NO were measured. Furthermore, a selective inhibitor of inducible nitric oxide synthase (iNOS) activity was employed to study the role of iNOS. Results and Discussion Effects of PMA on upregulation of adherence, lipopolysaccharide-triggered IL-1β, and migration ability of THP-1 cells were consistent with NO concentrations. Both l -NAME and BAPTA-AM mitigated effects of PMA on THP-1 cells differentiation. BAPTA-AM decreased levels of NO, while l -NAME had no effect on calcium levels. Of note, inhibition of iNOS activity decreased PMA-triggered upregulation of NO. Conclusion PMA induced differentiation of THP-1 cells partially in a NO-dependent manner. The calcium signaling may mediate PMA-triggered upregulation of NO.

Ferroelectric barium titanate nanoparticles (BTO NPs) may play critical roles in miniaturized passive electronic devices such as multi-layered ceramic capacitors. While increasing experimental and theoretical understandings on the structure of BTO and doped BTO have been developed over the past decade, the majority of the investigation was carried out in thin-film materials; therefore, the doping effect on nanoparticles remains unclear. Especially, doping-induced local composition and structure fluctuation across single nanoparticles have yet to be unveiled. In this work, we use electron microscopy-based techniques including high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), integrated differential phase contrast (iDPC)-STEM, and energy dispersive X-ray spectroscopy (EDX) mapping to reveal atomically resolved chemical and crystal structure of BTO and strontium doped BTO nanoparticles. Powder X-ray diffraction (PXRD) results indicate that the increasing strontium doping causes a structural transition from tetragonal to cubic phase, but the microscopic data validate substantial compositional and microstructural inhomogeneities in strontium doped BTO nanoparticles. Our work provides new insights into the structure of doped BTO NPs and will facilitate the materials design for next-generation high-density nano-dielectric devices.

The integration of molecular design and imidazole ionic liquids produces a synergistic effect to enhance and fine-tune the molecular sieve capability of polyimide (PI) membranes. The most difficult problem was to choose the right ionic liquids and moderate polymer combination. In this work, a series of systems of CO₂ in [EMIM][Tf₂N], [EMIM][BF₄], and [EMIM][PF₆] composited with 6FDA-based PI with different IL concentrations were discussed by all-atom molecular dynamics simulations. The results indicated that the CO₂ diffusion coefficient decreases with the compatibility of the PI structure with CO₂ molecules and increases with an increased IL concentration of up to 75 wt %. Therefore, this study may provide guidance for the design of PI membranes.

With the rapid development of industrialization and urbanization in China, energy and vehicle consumption have continued to increase in recent years and air pollution has become serious. In early 2020, Corona Virus Disease 2019 broke out in Wuhan, China. From January 29, 2020, several sources of the air pollution almost all stopped working, including gasoline burning vehicles, dust producing building sites, coal-fired factories, etc. Five indicators of the atmospheric environmental quality were observed from December 19, 2019 to April 30, 2020 in nine cities and 1-h average concentrations, 24-h average concentrations and Air Quality Index were assessed. The 1-h average concentrations of the nitrogen dioxide, the ozone and the sulfur dioxide showed obvious difference though the closure did not change the sequence of the five pollutants’ concentrations in the air at diverse sampling moments. The changing of the 24-h average concentrations of the five pollutants indicated the amount of pollutants in the air were greatly affected by human activities. The nitrogen dioxide, the sulfur dioxide and the particulate matters decreased obviously in the closure. The air in the metropolis and the south-east cities were relatively clean and the pollutants’ concentrations decreased slightly during the closure period. The northern and the heavy industrial cities showed significant drop on air pollution indicators and the air quality of the two city groups could be greatly improved if some effective measures could be taken of environmental management and regional development.

Simple and fast methods for the detection of target genes with single-nucleotide specificity could open up genetic research and diagnostics beyond laboratory settings. We recently reported a biosensor for the electronic detection of unamplified target genes using liquid-gated graphene field-effect transistors employing an RNA-guided catalytically deactivated CRISPR-associated protein 9 (Cas9) anchored to a graphene monolayer. Here, using unamplified genomic samples from patients and by measuring multiple types of electrical response, we show that the biosensors can discriminate within one hour between wild-type and homozygous mutant alleles differing by a single nucleotide. We also show that biosensors using a guide RNA-Cas9 orthologue complex targeting genes within the protospacer-adjacent motif discriminated between homozygous and heterozygous DNA samples from patients with sickle cell disease, and that the biosensors can also be used to rapidly screen for guide RNA-Cas9 complexes that maximize gene-targeting efficiency.

Glutamate is the major excitatory neurotransmitter in the brain and is involved in many brain functions. In this study, we investigated whether typhaneoside, a flavonoid from Typhae angustifolia pollen, affects endogenous glutamate release from rat cortical synaptosomes. Using a one-line enzyme-coupled fluorometric assay, glutamate release stimulated by the K+ channel blocker 4-aminopyridine was monitored to explore the possible underlying mechanisms. The vesicular transporter inhibitor bafilomycin A1 and chelation of extracellular Ca2+ ions with EGTA suppressed the effect of typhaneoside on the induced glutamate release. Nevertheless, the typhaneoside activity has not been affected by the glutamate transporter inhibitor dl-threo-beta-benzyloxyaspartate. The synaptosomal plasma membrane potential was assayed using a membrane potential-sensitive dye DiSC3(5), and cytosolic Ca2+ concentrations ([Ca2+]C) was monitored by a Ca2+ indicator Fura-2. Results showed that typhaneoside did not alter the synaptosomal membrane potential but lowered 4-aminopyridine-induced increases in [Ca2+]C. Furthermore, the Cav2.2 (N-type) channel blocker ω-conotoxin GVIA blocked Ca2+ entry and inhibited the effect of typhaneoside on 4-aminopyridine-induced glutamate release. However, the inhibitor of intracellular Ca2+ release dantrolene and the mitochondrial Na+/Ca2+ exchanger blocker 7-chloro-5-(2-chloropheny)-1,5-dihydro-4,1-benzothiazepin-2(3H)-one have no effect on the suppression of glutamate release mediated by typhaneoside. Moreover, inhibition of mitogen-activated protein kinase (MAPK)/extracellular signal-regulated kinase (ERK) prevented the inhibitory effect of typhaneoside on induced glutamate release. Typhaneoside reduced 4-aminopyridine-induced phosphorylation of ERK1/2 and the major presynaptic ERK target synapsin I, which is a synaptic vesicle-associated protein. In conclusion, these findings suggest a role for typhaneoside in modulating glutamate release by suppressing voltage-dependent Ca2+ channel mediated presynaptic Ca2+ influx and the MAPK/ERK/synapsin I signaling cascade.

The Notch1-mediated inflammatory response participates in the development of abdominal aortic aneurysm (AAA). The vascular endogenous bioactive peptide intermedin (IMD) plays an important role in maintaining vascular homeostasis. However, whether IMD inhibits AAA by inhibiting Notch1-mediated inflammation is unclear. In this study, we found Notch intracellular domain (NICD) and hes1 expression were higher in AAA patients’ aortas than in healthy controls. In angiotensin II (AngII)-induced AAA mouse model, IMD treatment significantly reduced AAA incidence and maximal aortic diameter. IMD inhibited AngII-enlarged aortas and -degraded elastic lamina, reduced NICD, hes1 and inflammatory factors expression, decreased infiltration of CD68 positive macrophages and the NOD-like receptor family pyrin domain containing 3 protein level. IMD inhibited lipopolysaccharide-induced macrophage migration in vitro and regulated macrophage polarization. Moreover, IMD overexpression significantly reduced CaCl2-induced AAA incidence and down-regulated NICD and hes1 expression. However, IMD deficiency showed opposite results. Mechanically, IMD treatment significantly decreased cleavage enzyme-a disintegrin and metalloproteinase domain-containing protein 10 (ADAM10) level. Pre-incubation with IMD17-47 (IMD receptors blocking peptide) and the phosphatidylinositol 3-kinase/protein kinase b (PI3K/Akt) inhibitor LY294002 reversed ADAM10 level. In conclusion, exogenous and endogenous IMD could inhibit the development of AAA by inhibiting Notch1 signaling-mediated inflammation via reducing ADAM10 through IMD receptor and PI3K/Akt pathway.

The morphology effect of tungsten oxide on the NH3-SCR activity of the supported CeO2 catalyst was experimentally investigated by comparing the catalytic performance of WO3 in different morphologies. Nanoparticles (W-NP), nanorods (W-NR) and microspheres self-assembled by nanorods (W-MP) of WO3 were synthesized by using different carboxylic acid structure-directing agents. Based on this, the impregnation method was adopted to form the composite catalysts including the Ce/W-NP, the Ce/W-NR and the Ce/W-MP. After the impregnation of Ce species, a new redox cycle of Ce4++W5+↔Ce3++W6+ is formed due to the interaction of W and Ce ions, which significantly facilitates the redox reaction on the composite catalyst. However, compared with nanorods (W-NR) and microspheres self-assembled by nanorods (W-MP), WO3 nanoparticles (W-NP) enclosed with (0 0 1) facets of the hexagonal WO3 shows the best redox ability due to the largest molar ratio of W5+/(W5++W6+) and the highest concentration of Ce4+ on the surface of Ce/W-NP, which was proven by the results of XPS. As a consequence, the Ce/W-NP presents the strongest surface redox properties and the largest molar ratio of Oα/(Oα+Oβ), which is beneficial to promote the NH3-SCR activity of the catalyst. It is worth mentioning that the morphology of tungsten oxide that remarkably affects the activity of the catalyst is determined by tartaric acid, citric acid and oxalic acid, indicating the significance of the structure-directing agents for improving the NH3-SCR activity of the impregnated Ce/W catalyst.

The structural elucidation of chiral molecules with more than one stereocenter is usually a tricky problem. In this paper, efficient 1H NMR spectroscopic approaches for assigning the erythro and threo configurations of 1-oxygenated 1,2-diarylpropan-3-ols were developed. By analysis of the chemical shift differences of diastereotopic methylene H2-3 (Δδ3) in CDCl3 or the chemical shift differences of H-1 and H-2 (Δδ1,2) in methanol-d4, deuterated dimethyl sulfoxide, and acetone-d6, the configurations of 1-oxygenated 1,2-diarylpropan-3-ols can be rapidly and conveniently determined.

Ionic liquids (ILs) play an important role in conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) based electronics and thermoelectrics through regulating morphology and electronic properties. Herein, the hole transport and interface electronic coupling properties of three kinds of IL ([BMIM]:[BF4], [BuPhIM]:[BF4], and [BnPhIM]:[BF4]) mediated PEDOT systems have been researched via multiscale molecular mechanics simulations and quantum mechanics calculations, where the cations of the ILs feature gradually extended π-conjugation. It is indicated that [BnPhIM]:[BF4] induces PEDOT to show more ordered π–π stacking than its counterparts, where the chains are oriented with face-to-face alignment. This is attributed to the larger evenness of the net charge distribution at the [BnPhIM]:[BF4]-PEDOT interface. Consequently, the average mobility in [BnPhIM]:[BF4]-PEDOT is 4.01 cm2 V−1 s−1 and the instantaneous maximum reaches 17 cm2 V−1 s−1, far surpassing its counterparts. Although the predicted PEDOT single crystal presents a well-ordered lamellar structure, the one-dimensional orientation causes hole tunneling along the nanowire-like direction, leading to its mobility lagging behind the [BnPhIM]:[BF4] decorated system by one order of magnitude. On the other hand, the interface electronic coupling and doping efficiency in [BnPhIM]:[BF4]-PEDOT is strengthened, confirming that improving the π-conjugation of the cation of the IL can enhance the mobility of PEDOT and interface electronic coupling synergistically. To improve the mobility further, a novel series of cations containing [BnPhIM-oOMe]+, [BnPhIM-mOMe]+, and [BnPhIM-pOMe]+ has been designed based on the outstanding properties of [BnPhIM]+. Combining the novel designed cations with [BF4]− and [B(CN)4]−, it is observed that [BnPhIM-pOMe]:[B(CN)4] causes PEDOT to assemble with well-ordered π–π stacking. Assessments rationalize that it could serve as a potential candidate for application in PEDOT-based electronics, since it shows similar interface electronic coupling and has a 35–43% improvement in PEDOT mobility compared to the excellent reference [BnPhIM]:[BF4].

We developed poly(vinyl alcohol-co-itaconic acid) (PV) hydrogels grafted with laminin-derived peptides that had different joint segments and several specific designs, including dual chain motifs. PV hydrogels grafted with a peptide derived from laminin-β4 (PMQKMRGDVFSP) containing a joint segment, dual chain motif and cationic amino acid insertion could attach human pluripotent stem (hPS) cells and promoted high expansion folds in long-term culture (over 10 passages) with low differentiation rates, whereas hPS cells attached poorly on PV hydrogels grafted with laminin-α5 peptides that had joint segments with and without a cationic amino acid or on PV hydrogels grafted with laminin-β4 peptides containing the joint segment only. The inclusion of a cationic amino acid in the laminin-β4 peptide was critical for hPS cell attachment on PV hydrogels, which contributed to the zeta potential shifting to higher values (3–4 mV enhancement). The novel peptide segment-grafted PV hydrogels developed in this study supported hPS cell proliferation, which induced better hPS cell expansion than recombinant vitronectin-coated dishes (gold standard of hPS cell culture dishes) in xeno-free culture conditions. After long-term culture on peptide-grafted hydrogels, hPS cells could be induced to differentiate into specific lineages of cells, such as cardiomyocytes, with high efficiency.

Polycondensation via direct C–H arylation of thiophene derivatives gave thiophene- and bithiophene-based alternating copolymers in good yields. The optimization of the reaction conditions was investigated in terms of a catalytic system and reaction time. Under optimized conditions, the polycondensation reaction of 3,3′,4,4′-tetramethylbithiophene with 2,7-dibromo-9,9-dioctylfluorene gave poly[2,7-(9,9-dioctylfluorene)-alt-5,5′-(3,3′,4,4′-tetramethyl-2,2′-bithiophene)] with a molecular weight of 31 800 in 91% yield. The polycondensation reaction proceeded with 2 mol % of Pd(OAc)2 without the addition of a phosphine ligand in a short reaction time (3 h). Six kinds of π-conjugated polymers were synthesized by the polycondensation reaction without the use of bifunctional organometallic reagents as monomers.

Autophagy is a critical cellular process that generally protects cells and organisms from harsh environment, including limitations in adenosine triphosphate (ATP) availability or a lack of essential nutrients. Metabolic reprogramming, a hallmark of cancer, has recently gained interest in the area of cancer therapy. It is well known that cancer cells prefer to utilize glycolysis rather than oxidative phosphorylation (OXPHOS) as their major energy source to rapidly generate ATP even in aerobic environment called the Warburg effect. Both autophagy and glycolysis play essential roles in pathological processes of cancer. A mechanism of metabolic changes to drive tumor progression is its ability to regulate autophagy. This review will elucidate the role and the mechanism of glycolysis in regulating autophagy during tumor growth. Indeed, understanding how glycolysis can modulate cellular autophagy will enable more effective combinatorial therapeutic strategies.

Aims/Introduction To define the target value for the percentage coefficient of variation for glucose (%CV) as a measure of glycemic variability (GV) in Chinese diabetes patients. Materials and Methods This retrospective study included 3,007 diabetes patients who underwent continuous glucose monitoring for 3 days. Type 2 diabetes was divided into groups according to the received treatment: group 1, non‐insulinotropic agent (n = 138); group 2, insulinotropic agent (n = 761); group 3, basal insulin therapy (n = 100); group 4, premixed insulin (n = 784); and group 5, intensive insulin therapy (n = 612). Type 1 diabetes patients were included as group 6 (n = 612). %CV and percentage of time per day within, below (3.9mmol/L; TBR3.9) and above (10.0 mmol/L) the target glucose range (3.9–10.0 mmol/L) were computed. TBR3.9 ≥4% was defined as excessive hypoglycemia. Results Type 2 diabetes with a premixed or intensive insulin regimen had an increased %CV compared with those receiving oral therapy or basal insulin. The upper limit of %CV in group 1 was 33%, which was adopted as the threshold to define excessive GV. For each treatment group, the percentage of people with TBR3.9 ≥4% was significantly greater in the subgroup with %CV >33% than ≤33% (P 70% and time per day above 10.0 mmol/L

A practical and concise total synthesis of tricyclic ketone 7 (CDE ring), a valuable intermediate for the synthesis of racemic camptothecin and analogs, was described (8 chemical steps and 29% overall yield). The synthesis starts with two inexpensive, readily available materials and is operationally simple to perform. It is worth mentioning that the reported protecting group-free synthesis, with advantages of a short route, would be helpful for the future development of industry-scale syntheses of camptothecin-family alkaloids.

Methane metabolism in deep subsurface petroleum reservoirs is of paramount interest in the global biogeochemical cycle of carbon. Methanogenesis in such habitats is driven mostly by methanogens in ...

A novel tungsten-doped magnetic iron oxide catalyst was fabricated for selective catalytic reduction of NOx with NH3 (NH3-SCR), which was supported by carbon-included magnetic materials of Fe2O3–-H synthesized by the solution combustion followed by the oxidization of hydrogen peroxide. As a consequence, the thermal stability of γ-Fe2O3 crystallites located in the magnetic support is significantly enhanced. Meanwhile, the irreversible transformation of Fe2O3 crystallites from γ-phase to α-phase during the annealing process at high temperatures (i.e. 400 °C) is restrained to a large extent. In addition, the magnetic W/Fe2O3 catalyst presents a superb porous structure with higher BET surface area and pore volume due to the anti-sintering effect of tungsten doping on the magnetic Fe2O3. In this regard, the surface acidity as well as the molar ratio of the surface-adsorbed oxygen is substantially augmented, leading to a remarkable improvement of the redox ability of the active bulk species in the catalyst. It is worth mentioning that the promotions in thermal stability and redox ability is affected by the doping amount of tungsten in the catalyst, the molar ratio of glucose/urea/iron, and the ignition temperature for synthesizing the magnetic iron oxide support. The experiments revealed that with a doping amount of 7.5 wt%, a molar ratio of glucose/urea/iron of 5:20:8, and an ignition temperature of 400 °C, the NH3-SCR activity of the novel catalyst could be optimized.

Background Prospective registry studies of congenital heart disease (CHD)-associated pulmonary artery hypertension (PAH) are rare. We established a multicenter registry of CHD-PAH: the TACHYON (TAiwan Congenital Heart disease associated with pulmonarY arterial hypertension) registry. Methods The prospective TACHYON registry was initiated in January 2016. Nine pediatric cardiology centers with 99 patients were included. Using this database, we evaluated clinical characteristics and outcomes. Results Twelve patients with incomplete data were excluded. For the remaining 87 patients, mean age of enrollment was 37.4 (SD 18.2) years, and the male to female ratio was 60:27. PAH after defect closure accounted for 46 (52.9%) and Eisenmenger syndrome for 30 (34.5%) cases. Atrial septal defect was the most common (48.3%) disease, followed by ventricular septal defect. Mean pulmonary artery pressure was 56.7 (SD 19.4) mmHg. PAH-targeted therapy was used in 95.4% of patients. Sildenafil and bosentan were the most common drugs. After mean 23.9 months of follow-up, the 2-year Kaplan–Meier survival rate was 93.2%. According to univariate Cox regression analysis, significant risk factors included right heart failure signs, symptom progression, high-risk baseline N-terminal pro–brain natriuretic peptide (BNP)/BNP, high-risk baseline 6-min walking distance (6MWD), and high baseline hemoglobin/hematocrit level. Using the three noninvasive parameters (functional class, 6MWD, NT-pro BNP/BNP) proposed by the European Society of Cardiology, the total number of high-risk criteria predicted survival rate reliably. Conclusions Using the TACHYON registry is feasible, but the physicians' adherences to guidelines are unsatisfactory. Midterm outcomes of PAH-target therapy are favorable and predictable using noninvasive parameters.

Superionic conductors with ionic conductivity on the order of mS cm-1 are expected to revolutionize the development of solid-state batteries (SSBs). However, currently available superionic conductors are limited to only a few structural families such as garnet oxides and sulfide-based glass/ceramic. Interfaces in composite systems such as alumina in lithium iodide have long been identified as a viable ionic conduction channel, but practical superionic conductors employing the interfacial conduction mechanism are yet to be realized. Here we report a novel method that creates continuous interfaces in the bulk of composite thin films. Ions can conduct through the interface, and consequently, the inorganic phase can be ionically insulating in this type of bulk interface superionic conductors (BISCs). Ionic conductivities of lithium, sodium, and magnesium ion BISCs have reached 1.16 mS cm-1, 0.40 mS cm-1, and 0.23 mS cm-1 at 25 °C in 25 μm thick films, corresponding to areal conductance as high as 464 mS cm-2, 160 mS cm-2, and 92 mS cm-2, respectively. Ultralow overpotential and stable long-term cycling for up to 5000 h were obtained for solid-state Li metal symmetric batteries employing Li ion BISCs. This work opens new structural space for superionic conductors and urges for future investigations on detailed conduction mechanisms and material design principles.

Novel functionalized polysulfone with high local density of sulfonic acid groups, N,N-bis(sulfopropyl)aminyl-4-phenyl polysulfone or O,O′-bis(sulfopropyl)resorcinol-5-yl-4-phenyl polysulfone (PSF-X-C3H6SO3H, X = N or O) are synthesized. These polymers are synthesized by bromination of polysulfone followed by Suzuki cross-coupling reaction to graft the aminophenyl groups and the dimethoxyphenyl groups onto the polymeric backbone, followed by introduction of the sulfopropyl groups via sultone ring-opening reaction. In addition, the composite membrane of PSF-O-C3H6SO3H and PSF-N-C3H6SO3H is also synthesized for comparison. The maximum proton conductivity of composite PSF-O-C3H6SO3H and PSF-N-C3H6SO3H reaches 46.66 mS cm−1 at 95 °C and 90% RH, higher than PSF-O-C3H6SO3H (42.06 mS cm−1) and PSF-N-C3H6SO3H (38.76 mS cm−1). Meanwhile, the composite exhibits compromised water uptake and swelling ratio, and low methanol permeability. The excellent overall performance of the composite is attributed to phase-separation between the hydrophilic and the hydrophobic subphases, and the hydrogen-bonding network developed in the hydrophilic subphases.

Polycrystalline materials are widely utilized in engineering fields. In this study, peridynamic (PD) models are developed for the first time in the literature to investigate thermally-induced fracture phenomenon for cubic polycrystals and ceramic made of different materials. After validating the current model, the influences of the grain size, grain boundary strength and composition of the materials on the fracture behavior are analyzed. Two different types of pre-existing cracks, i.e. vertical and horizontal, are considered. The effect of grain size is much more obvious for ceramic materials and crack branching is observed for both vertical and horizontal crack cases. Grain boundary strength has a significant influence on crack behaviour. For weaker grain boundaries intergranular fracture pattern is observed whereas for stronger grain boundaries transgranular crack pattern is more dominant. Crack branching is much more significant when the silicon carbide ratio is higher due to the difference in coefficients of thermal expansion of two different materials. By comparing with the reference results available in the literature similar fracture features are obtained.

A spherical carbon coated nano-structured LiFePO4 composite is synthesized by a polymer-assisted method from inexpensive iron(III) raw material. The synthesis process includes two steps: (1) nano-FePO4/polyaniline composites with core–shell structure are synthesized through the in-situ polymerization of aniline; (2) LiFePO4/C composites are prepared through carbothermal reduction with the nano-FePO4/polyaniline and sucrose as raw materials. The structure, surface morphology of the materials and the properties of the coated carbon are investigated by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, and high-resolution transmission electron microscopy. The obtained nano-structured LiFePO4/carbon composite has a spherical morphology compose of ordered olivine structure, which is coated with 2 nm thick amorphous layer of carbon. At the same time, the materials are linked together by amorphous carbon from sucrose decomposition. The aniline plays an important role during the synthesis process. The electrochemical properties of the materials are tested by charge–discharge measurements. The obtained nano-structured LiFePO4/carbon composite shows excellent electrochemical properties, especially its high rate performance. It exhibits initial discharge capacities of 138, 136, 118, 103, and 92 mA h g–1 at 0.2, 1, 10, 20, and 30 C rate between 3.65 and 2.0 V, respectively. That makes it a promising cathode material for advanced power Li-ion batteries. The excellent electrochemical properties of the materials can be ascribed to the two different amorphous carbons. The carbon coated on the surface of LiFePO4 effectively reduces inter-particle agglomeration of the LiFePO4 particles. The carbon interlinked between the composite improve the electronic conductivity. Those shorten the lithium ions diffusion length and improve the electric contact between LiFePO4 particles.

Efficient seed germination and establishment are important traits for field and glasshouse crops. Large-scale germination experiments are laborious and prone to observer errors, leading to the necessity for automated methods. We experimented with five crop species, including tomato, pepper, Brassica, barley, and maize, and concluded an approach for large-scale germination scoring. Here, we present the SeedGerm system, which combines cost-effective hardware and open-source software for seed germination experiments, automated seed imaging, and machine-learning based phenotypic analysis. The software can process multiple image series simultaneously and produce reliable analysis of germination- and establishment-related traits, in both comma-separated values (CSV) and processed images (PNG) formats. In this article, we describe the hardware and software design in detail. We also demonstrate that SeedGerm could match specialists' scoring of radicle emergence. Germination curves were produced based on seed-level germination timing and rates rather than a fitted curve. In particular, by scoring germination across a diverse panel of Brassica napus varieties, SeedGerm implicates a gene important in abscisic acid (ABA) signalling in seeds. We compared SeedGerm with existing methods and concluded that it could have wide utilities in large-scale seed phenotyping and testing, for both research and routine seed technology applications.

The immunomodulatory effects of maca polysaccharides (MCPs) on macrophages have been demonstrated in many studies. However, the effects of MCPs on CD4+ T cells have not been studied. Four water-soluble MCPs, labeled MCP1 (weight-average molecular weights [Mws] of 896.1 and 276.6 kDa), MCP2 (Mws of 337.8 and 219.0 kDa), MCP3 (Mws of 110.6, 58.1, and 38.9 kDa), and MCP4 (Mws of 15.7, 12.6, and 12.1 kDa), were obtained from maca by graded ethanol precipitation. The immunoregulatory effects of MCPs on CD4+ T cells were evaluated for the first time. The experimental results indicated that all MCPs had immunoregulatory effects on CD4+ T cells. However, the effects of MCP2 were stronger compared to the other three components, not only in promoting the proliferation of CD4+ T cells but also in terms of secretion of interferon-γ (IFN-γ). The molecular weight and monosaccharide compositions of MCPs were analyzed to explore the structure–activity relationship. The results suggested that the molecular weight and the galactosamine (GalN) of MCPs might be determining factors for its bioactivity. These findings suggest that the MCP2 isolated in our study have immune potentiation effects on CD4+ T cells.

Lessons LearnedTreatment with the Aurora kinase A inhibitor yields often durable disease control, but limited tumor regression, in heavily pretreated patients with unresectable malignant pleural or peritoneal mesothelioma. In a limited sample size, MYC copy-number gain or gene amplification, a candidate predictive biomarker for alisertib, did not correlate with improved response numbers or patient outcomes.BackgroundMalignant mesothelioma is an aggressive disease for which few effective therapies are available. The Aurora family kinases are critical for mitotic fidelity and highly expressed in mesothelioma, wherein their inhibition leads to growth arrest in vitro. We evaluated the efficacy of alisertib, an Aurora A kinase inhibitor, in relapsed malignant mesothelioma.MethodsTwenty-six patients with previously treated, unresectable pleural or peritoneal mesothelioma were enrolled on a single-arm, single-institution phase II trial of alisertib at a dosage of 50 mg twice daily for 7 of every 21 days. The primary endpoint was 4-month disease control rate. Secondary endpoints included overall response rate, progression free survival, overall survival, safety/toxicity, and correlation of endpoints with MYC copy number.ResultsOf the 25 evaluable patients treated on study, 8 (32%) experienced 4-month disease control, surpassing the futility endpoint. There were no confirmed partial or complete responses. Median progression-free and overall survival were 2.8 months and 6.3 months, respectively. No associations between MYC copy number and outcomes were observed.ConclusionAlisertib has modest activity in this unselected malignant mesothelioma population. Several patients achieved durable disease control. Although the study did meet its prespecified futility endpoint, the sponsor elected to close the trial at the interim analysis.

In view of the polyvinyl chloride (PVC) in the processing and molding easy degradation, the stability effect of different components is not good when used alone, and PVC in thermal degradation with the release of hydrogen chloride will lead to the formation of toxic gas dioxins to the environment and human problems. For this purpose, the nanosized titanium dioxide (NT), calcium–zinc (Ca-Zn)*, dipentaerythritol (Dip) and organotin (OT) were modified with butyl titanate (BT), coupling agent to synthesize the composite material and used as the strengthening agent for PVC. The composites and PVC were characterized, and their properties were determined using Raman, XRD, TG, TG-IR, Congo red and DMA. The results showed that the BT/NT/Dip/OT/(Ca-Zn)* complex not only kept the basic configuration of NT particles, but also had strong interaction between components due to BT coupling, which had synergistic effect on PVC. Similarly, BT was involved in the coupling between PVC and Dip/OT, resulting in prolonged initial discoloration time. When 3.8mass%BT/NT, 0.32mass%OT, 0.32mass%(Ca-Zn)* and 0.63mass% Dip were added to the PVC film, compared with blank sample and only 1phr of OT stabilizer, the new composite material was formed. The longest initial discoloration time was observed by Congo red, and the temperature was improved when TG was used to analyze the maximum mass loss rate, and the maximum mass loss rate was reduced by 115%. As the conversion rate reached 1%, the decomposition temperatures of PVC composite film and blank sample were 234.7 °C and 175.2 °C, respectively, indicating that the formed PVC film had excellent thermal stability. TG-FTIR analysis showed that after adding OT at 0.5 phr, (Ca-Zn)* at 0.5 phr and Dip at 1.0 phr, the composite film was around 331.1 °C and 476.6 °C, and the peak strength of CH4 gas released by thermal degradation was 114.0 and 262.0% higher than that of blank sample, respectively. It can be seen that pentaerythritol has a promoting effect on CH4 release of PVC, and the peak strength of CO2 is shifted to the high temperature zone, contrary to the blank sample, there is no formation of hydroxyl or water, which means that the thermal degradation pathway of PVC has changed, and it is possible to inhibit the generation of aromatic hydrocarbons and dioxins. By introducing 3.8 mass% BT/NT composite reinforcement, compared with the blank sample, the observed storage modulus increased by 22.4%, and the mechanical properties of PVC composite material were improved.

A proof-of-principle prototype of a volumetric 3D-displaying system is demonstrated by utilizing the photo-activated phosphorescence of two long-lived phosphorescent metal-porphyrins in dimethyl sulfoxide (DMSO), a photochemically deoxygenating solvent. The first phosphorescent sensitizer, Pt(TPBP), absorbs a light beam with a wavelength of 635 nm, and the sensitized singlet oxygen is scavenged by DMSO. The second phosphorescent emitter, Pt(OEP), absorbs a light beam with a wavelength of 532 nm and visibly phosphoresces only in the deoxygenated zone generated by the first sensitizer. The phosphorescent voxels, 3D images, and animations are well-defined by the intersections of the 635-nm and 532-nm light beams that are programmable by tuning of the excitation-power densities, the beam shapes, and the kinetics. As a pivotal selection rule for the phosphorescent molecular couple used in this 3D-displaying system, their absorptions and emissions must be orthogonal to each other, so that they can be excited and addressed independently.

The Nod-like receptor protein 3 (NLRP3) inflammasome is a multi-protein complex composed of NLRP3, pro-caspase-1, and apoptosis-associated speck-like protein that contains a caspase recruitment domain (ASC). After NLRP3 priming by lipopolysaccharide (LPS), the ligand of toll-like receptor 4 (TLR4), activation of the NLRP3 inflammasome triggers caspase-1 maturation, leading to pyroptosis and release of interleukin-1beta (IL-1beta). Expression of TLR4 modulates LPS-triggered inflammatory cascades as well as the NLRP3 signaling. L-type calcium channel antagonists are widely used as anti-hypertensive drugs and also exert anti-inflammatory effects through inhibiting release of cytokines including IL-1beta. However, few studies reveal effects of L-type calcium channel antagonists on the NLRP3 inflammasome. In this study, we investigated the effects of nicardipine and verapamil, both L-type calcium channel antagonists, on the NLRP3 inflammasome using differentiated THP-1 cells. Pyroptosis or levels of IL-1beta and caspase-1 were assayed by flow cytometry or enzyme-linked immunosorbent assay, respectively. ASC oligomerization was assayed by immunofluorescence microscopy. Expression of NLRP3 or TLR4 was assayed by polymerase chain reaction and immunoblotting. Nuclear factor-kappaB (NF-kappaB) pathway was also studied. Our results showed that pyroptosis and IL-1beta release were attenuated by nicardipine, but not verapamil. Nicardipine also mitigated caspase-1 activation, inhibited ASC oligomerization, and reduced NLRP3 expression. Furthermore, nicardipine downregulated phosphorylation or nuclear translocation of NF-kappaB p65, consistent with the inhibitory effect of nicardipine on LPS-induced TLR4 expression. In conclusion, nicardipine exerted anti-inflammatory effects through inhibiting NLRP3 inflammasome pathway. Nicardipine may mitigate NLRP3 priming via inhibiting NF-kappaB activation, mediated by suppressing LPS-induced TLR4 expression.

The cycloaddition of CO2 with epoxides catalyzed by ionic liquids (ILs) has been a widely ongoing studied hot topic over the years. Recent experimental research has shown that the protic ionic liquids (PILs) behave stronger hydrogen proton donating ability than aprotic ionic liquids (APILs), and can effectively catalyze the cycloaddition of CO2. Unfortunately, the mechanistic explanation remains primarily unraveled. Herein, a detailed simulation study on the cycloaddition reaction catalyzed by PIL ([HDBU][Mim]) in comparison with APIL ([MeDBU][Mim]) reaction catalysts was conducted, including the three-step route (ring-opening of PO (propylene oxide), insertion of CO2 and ring-closure of propylene carbonate (PC)) and two-step route (simultaneously ring-opening of PO and addition of CO2, and then ring-closure of PC). Based on the activation energy barrier of the rate-determining step, PIL preferentially activates PO as the optimal route for the reaction with the energy barrier of 23.2 kcal mol-1, while that of APIL is 31.2 kcal mol-1. The role of [HDBU]+ in the reaction was also explored and found that the direct formation of intermolecular hydrogen bond (H-bond) between [HDBU]+ and the reactants (PO + CO2) was unfavorable for the reaction, while the cooperation with the anion [Mim]- to assist indirectly was more conducive. To fully consider the reaction microenvironment of ILs, ONIOM calculation was used to study the solvent effect. At last, the above conclusions were further verified by the analysis of intermediates with charge, non-covalent interaction (NCI), and atoms in molecules (AIM) methods. The computational findings show that ILs studied in this work have dual functions of catalyst and solvent, enabling a microscopic understanding of the ILs catalyst for CO2 utilization as well as providing guidance for the rational design of more efficient ILs-based catalysts.

Context Unlike other commonly used invasive blood glucose–monitoring methods, saliva detection prevents patients from suffering physical uneasiness. However, there are few studies on saliva 1,5-anhydroglucitol (1,5-AG) in patients with diabetes mellitus (DM). Objective This study aimed to evaluate the effectiveness of saliva 1,5-AG in diabetes screening in a Chinese population. Design and Participants This was a population-based cross-sectional study. A total of 641 subjects without a valid diabetic history were recruited from September 2018 to June 2019. Saliva 1,5-AG was measured with liquid chromatography–mass spectrometry. Main outcome measures DM was defined per American Diabetes Association criteria. The efficiency of saliva 1,5-AG for diabetes screening was analyzed by receiver operating characteristic curves, and the optimal cutoff point was determined according to the Youden index. Results Saliva 1,5-AG levels in subjects with DM were lower than those in subjects who did not have DM (both P < .05). Saliva 1,5-AG was positively correlated with serum 1,5-AG and negatively correlated with blood glucose and glycated hemoglobin (HbA1c) (all P < .05). The optimal cutoff points of saliva 1,5-AG0 and 1,5-AG120 for diabetes screening were 0.436 μg/mL (sensitivity: 63.58%, specificity: 60.61%) and 0.438 μg/mL (sensitivity: 62.25%, specificity: 60.41%), respectively. Fasting plasma glucose (FPG) combined with fasting saliva 1,5-AG reduced the proportion of people who required an oral glucose tolerance test by 47.22% compared with FPG alone. Conclusion Saliva 1,5-AG combined with FPG or HbA1c improved the efficiency of diabetes screening. Saliva 1,5-AG is robust in nonfasting measurements and a noninvasive and convenient tool for diabetes screening.