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Reservoir quality is one of the important geological factors controlling the development of tight oil in the Honghe oilfield, Ordos Basin, northwestern China. Analyses of core, well logging, mud logging and geophysical data as well as thin sections (casting and fluorescence) were combined with testing methods (such as grain size analysis, constant-rate mercury injection, and scanning electron microscopy) to characterize the micropore–throat development in reservoirs of the eighth member of Yanchang Formation in the oilfield. From the perspective of sedimentation and diagenesis, the mechanisms causing reservoir quality difference were explored and a method for characterizing reservoir quality difference and distribution was proposed. The results show that complex and diverse pore–throat configurations and multi-scale throat development are the microscale manifestations of reservoir quality differences in the member. Three types of pore–throat combinations are recognized, including intergranular pore-wide lamellar throat, intergranular and intragranular pore-wide lamellar throat, and intergranular/clustered micropore-wide lamellar throat. Different diagenesis processes and intensities under the control of sedimentary conditions determine the differential development of the reservoirs. Diagenetic facies are the indicators of reservoir quality. Diagenetic facies with chlorite cementation-moderate dissolution indicates reservoirs with the most ideal physical properties for hydrocarbon accumulation, while that with moderate calcite and kaolinite cementations are usually observed in reservoirs with less ideal physical properties. Reservoirs with the worst physical properties often correlate with diagenetic facies with strong calcite cementation and compaction facies. A multi-level constrained method under the control of sedimentation and diagenetic facies is proposed for characterizing tight reservoir quality difference in the member. The spatial distribution of sedimentary elements is analyzed through sedimentary configurations, the diagenetic facies distribution is constrained by sedimentary elements and the reservoir quality distribution is predicted with constraint of diagenetic facies. It suggests that the high-quality reservoirs in the member occur vertically in the middle of thick channel sandstone, while poor reservoirs occur in the upper or lower parts of the channel sandstone due to intensive compaction and cementation. Laterally, the quality of reservoirs enhances along the channels with a change in shape to lens or strips along the middle and downstream sections.

Paraquat is one of the most widely used nonselective herbicides in agriculture. Due to its wide use, paraquat resistant weeds have emerged and is becoming a potential threat to agriculture. The molecular mechanisms of paraquat resistance in weeds remain largely unknown. Physiological studies indicated that the impaired translocation of paraquat and enhanced antioxidation could improve paraquat resistance in plants. However, the detoxification of paraquat via active metabolism by plants has not been reported to date. Here we report that an activated expression of At1g01600 encoding the P450 protein CYP86A4 confers paraquat resistance as revealed by the gain-of-function mutant paraquat tolerance 11D (pqt11D), in which a T-DNA with four 35S enhancers was inserted at 1646 bp upstream the ATG of At1g01600. The paraquat resistance can be recapitulated in Arabidopsis wild type by overexpressing AtPQT11 (At1g01600), while its knockout mutant is hypersensitive to paraquat. Moreover, AtPQT11 also confers paraquat resistance in E. coli when overexpressed. We further demonstrate that AtPQT11 has P450 enzyme activity that converts paraquat to N-demethyl paraquat nontoxic to Arabidopsis, therefore detoxifying paraquat in plants. Taken together, our results unequivocally demonstrate that AtPQT11/ CYP86A4 detoxifies paraquat via active metabolism, thus revealing a novel molecular mechanism of paraquat resistance in plants and providing a means potentially enabling crops to resist paraquat.

To monitor the reaction between Ce4+ ion and Cl– ion at the electron level, an electrochemical experiment was designed in this work. Herein, the intermediate and final products that may be produced during the redox reaction are directly tracked by using cyclic voltammetry, and the influences of Ce4+ ion concentration, temperature and F– ion on the reduction peak potential of Ce4+ ion were investigated. The results show that Ce4+ ion reacts with Cl– ion through an irreversible reaction without any intermediate products, and the rate-determining step of the reaction is diffusion during the electrode reaction. The effects of temperature (20–40 °C) and Ce4+ ion concentration (0.04–0.12 mol/L) on the reduction peak potential of Ce4+ ion can be ignored, but the higher the molar ratio of F– to Ce4+ (0–3 mol/mol), the more easily the reduction of Ce4+ ion to Ce3+ ion occurs. Additionally, the Ce4+ ions are preferentially reduced by thiourea when thiourea is added in the HCl solution, and thiourea inhibits the oxidation of Cl– ions to Cl2 by forming a complex with Cl– ions. This work provides a theoretical basis for the role of thiourea in inhibiting Cl2 production and offers a new way to find new reductants.

Autosomal dominant polycystic kidney disease (ADPKD) is a debilitating renal neoplastic disorder with limited treatment options. It is characterized by the formation of large fluid-filled cysts that develop from kidney tubules through abnormal cell proliferation and cyst-filling fluid secretion driven by cAMP-dependent Cl−secretion. We have examined the effectiveness of the indazole carboxylic acid, H2-gamendazole (H2-GMZ), a derivative of lonidamine, to inhibit these processes and cyst formation usingin vitroandin vivomodels of ADPKD. H2-GMZ was effective in rapidly blocking forskolin-induced, Cl−-mediated short-circuit currents in human ADPKD cells at 1 μM and it significantly inhibited both cAMP- and EGF-induced proliferation of ADPKD cells with an IC50of 5-10 μM. Western blot analysis of H2-GMZ-treated ADPKD cells showed decreased phosphorylated ERK and hyperphosphorylated Rb levels. H2-GMZ treatment also decreased ErbB2, Akt, and Cdk4, consistent with inhibition of the chaperone Hsp90, and reduced the levels of the CFTR Cl−channel. H2-GMZ-treated ADPKD cultures contained a higher proportion of smaller cells with fewer and smaller lamellipodia and decreased cytoplasmic actin staining, and they were unable to accomplish wound closure even at low H2-GMZ concentrations, consistent with an alteration in the actin cytoskeleton and decreased cell motility. Studies using mouse metanephric organ cultures showed that H2-GMZ inhibited cAMP-stimulated cyst growth and enlargement.In vivo, H2-GMZ (20mg/kg) was effective in slowing postnatal cyst formation and kidney enlargement in thePkd1flox/flox:Pkhd1-Cremouse model. Thus, H2-GMZ treatment decreases Cl−secretion, cell proliferation, cell motility, and cyst growth. These properties, along with its reported low toxicity, suggest that H2-GMZ might be an attractive candidate for treatment of ADPKD.

Idiopathic pulmonary fibrosis (IPF) is a progressive and irreversible interstitial pulmonary disease due to chronic inflammatory responses. The prognosis of IPF is very poor, however, the therapeutic options are very limited. Previously we developed a polymeric micellar drug delivery system of carbon monoxide (CO) that is a pivotal anti-inflammatory gaseous molecule, i.e., SMA/CORM2, which exhibited therapeutic potentials against dextran sulfate sodium (DSS)-induced mouse colitis and acetaminophen (APAP) induced liver injury. Along this line, here we investigate the applicability of SMA/CORM2 on IPF using a bleomycin (BLM)-induced pulmonary fibrosis model. Severe inflammation and the consequent pulmonary fibrosis were triggered by BLM, whereas SMA/CORM2 treatment remarkably suppressed the inflammation progression and ameliorated the formation of fibrosis. CO is the effector molecule of SMA/CORM2, which exerted the therapeutic/protective effect mostly through suppressing the reprogramming of anti-inflammatory macrophages as revealed by the decreased expressions of CD206 and arginase-1 that were remarkably upregulated by BLM exposure. The suppression of macrophage polarization accompanied the downregulated hypoxia-inducible factor-1α (HIF-1α) and its target molecule heme oxygenase-1 (HO-1), suggesting a HIF-1α/HO-1 pathway for modulating macrophage reprogramming. As the downstream event of anti-inflammatory macrophage polarization, the alveolar epithelial to mesenchymal transition that is the major source of myofibroblast, the hallmark of IPF, was significantly suppressed by SMA/CORM2 via a TGF-β/Smad2/3 pathway. Compared to native CORM2 of equivalent dose, SMA/CROM2 exhibited a much better protective effect indicating its superior bioavailability as an enhanced permeability and retention (EPR) effect-based nanomedicine. We thus anticipate the application of SMA/CORM2 as a therapeutic candidate for IPF as well as other inflammatory diseases and disorders.

Epoxy resin powder coating has been successfully applied on the corrosion protection of magnesium lithium alloys. However, poor wear resistance and microcracks formed during the solidification have limited it extensive application. There are limited approaches to exploit such anti-corrosion and mechanical properties of magnesium lithium alloys. Herein, the epoxy resin powder coating with polydopamine modified molybdenum disulfide (MoS2@PDA-EP powder coating with 0, 0.1, 0.2, 0.5, 1.0 wt.% loading) was well prepared by melt extrusion to investigate its anticorrosion performance and wear resistance. The results revealed that the addition of MoS2@PDA enhanced the adhesion strength between coatings and alloys, wear resistance and corrosion protection of the powder coatings. Among them, the optimum was obtained by 0.2 wt.% MoS2@PDA-EP powder coating which could be attributed to well dispersion and efficient adhesion with coating matrix. To conclude, MoS2@PDA-EP powder coating is meaningfully beneficial for the anticorrosive and wear performance improvement of magnesium lithium alloys.

To explore the antitumor and potential off-target effects of systemically delivered cholesterol-conjugatedThe antitumor effects of two intravenous dosing regimens ofContinuous treatment with

It is of great importance to directionally construct advanced carbon host to achieve high-performance carbon/sulfur cathodes for lithium sulfur batteries (LSBs). Herein, we report a unique hollow pumpkin-like carbon with notable rich-wrinkle microstructure and intrinsically dual doping with N&P elements via a facile annealing process of Aspergillus niger spore. Furthermore, highly conductive polar absorbents, TiC nanoparticles, are in situ implanted into the above Aspergillus niger spore carbon (ANSC) by carbothermal reaction, accordingly forming high-performance ANSC/TiC composite host for sulfur. Impressively, TiC nanoparticles play dual roles of not only pore formation in ANSC matrix but also enhancement of chemical absorption with polysulfides. With the positive synergistic effect between N&P co-doped ANSC matrix and TiC polar absorbent, the designed ANSC/TiC-S cathodes show unique advantages including larger accommodation space for sulfur, higher surface area, enhanced conductivity and better chemical absorption with soluble polysulfide intermediates. Consequently, the ANSC/TiC-S cathodes are endowed with good rate performance (496 mAh/g at 0.5 C) and enhanced long-term cycling stability (736 mAh/g with a capacity retention of 78.8% at 0.1 C after 100 cycles). Our research opens a new door to controllably design advanced composite cathodes from microorganisms for application in lithium sulfur batteries.

Designing visible light photocatalysts with a metal oxide semiconductor as the starting material could expand a new horizon for the conversion and storage of solar energy. Here, the benchmark photocatalyst TiO2 was used to pursue this goal by anchoring aromatic acids. With benzoic acid (BA) as the initial molecule, horizontally extending one or two benzene rings furnishes 2-naphthoic acid (2-NA) and 2-anthracene acid (2-AA). Extending the aromatic acid was strategically deployed to design TiO2 complexes with violet light-induced selective aerobic oxidation of sulfide as the probe reaction. Moreover, triethylamine (TEA), an electron transfer mediator, was introduced to maintain the integrity of the anchored aromatic acids. Notably, there was a direct correlation between the π-conjugation of aromatic acid ligand and the selective aerobic oxidation of sulfides. Among the three aromatic acids, 2-AA delivered the best result over TiO2 due to the most extensive π-conjugated system. Ultimately, violet light-induced selective aerobic oxidation of sulfides into corresponding sulfoxides was conveniently realized by cooperative photocatalysis of 2-AA-TiO2 with 10 mol% of TEA. This work affords an extending strategy for designing the next-generation ligands for semiconductors to expand visible light-induced selective reactions.

Ketones serve as one of the most critical building blocks in organic synthesis, involving numerous functional group transformations. Herein, we report an unprecedented photoredox–nickel metallaphot...

The structural diversity and designability of metal–organic frameworks (MOFs) make these porous materials a strong candidate for NH3 uptake. However, to achieve a high NH3 capture capacity and good...

Acute lung injury (ALI) is associated with a high mortality due to inflammatory cell infiltration and lung edema. The development of ALI commonly involves the activation of NF-κB. Since bergamottin is a natural furanocoumarin showing the ability to inhibit the activation of NF-κB, in this study we aimed to determine the effect of bergamottin on ALI. RAW264.7 mouse macrophages were pre-treated with bergamottin and then stimulated with LPS. Macrophage inflammatory responses were examined. Bergamottin (50 mg/kg body mass) was intraperitoneally administrated to mice 12 h before injection of LPS, and the effect of bergamottin on LPS-induced ALI was evaluated. Our results showed that LPS exposure led to increased production of TNF-α, IL-6, and monocyte chemoattractant protein-1 (MCP-1), which was impaired by bergamottin pre-treatment. In vivo studies confirmed that bergamottin pre-treatment suppressed LPS-induced lung inflammation and edema and reduced the levels of pro-inflammatory cytokines in lung tissues and bronchoalveolar lavage fluids. Mechanistically, bergamottin blocked LPS-induced activation of NF-κB signaling in lung tissues. Additionally, bergamottin treatment reduced NF-κB p65 protein acetylation, which was coupled with induction of SIRT1 expression. In conclusion, our results reveal the anti-inflammatory property of bergamottin in preventing ALI. Induction of SIRT1 and inhibition of NF-κB underlies the anti-inflammatory activity of bergamottin.

An investigation of the fruiting bodies of edible mushroom Ganoderma lucidum produced 13 steroids, containing one new lanostane-type triterpene compound, named ganoderterpene A (1). Nuclear magnetic resonance and high-resolution electrospray ionization mass spectrometry data were used to deduce these structures. All the isolates were evaluated for their ability to suppress NO generation in BV-2 microglial cells treated with lipopolysaccharide (LPS) and exhibited moderate to strong inhibition effects, with IC50 values in the range 7.15-36.88 μM. Among the tested compounds, compound 1 exhibited the most marked activity with an IC50 value of 7.15 μM, and the structure-activity relationships were studied. This study showed that compound 1 significantly suppressed the activation of MAPK and TLR-4/NF-κB signaling pathways, as evidenced by an immunofluorescence assay and a molecular docking experiment. Furthermore, compound 1 effectively improved the LPS-induced mitochondrial membrane potential and apoptosis. These findings suggest that ganoderterpene A could exert protective effects in microglial cells from apoptosis by restraining the inflammatory response. Hence, G. lucidum could be used as a novel preventative agent for neurodegenerative disorders.

Butenyl-spinosyn is a highly effective and broad-spectrum biopesticide produced by Saccharopolyspora pogona. However, the yield of this compound is difficult to increase because the regulatory mechanism of secondary metabolism is still unknown. Here, the transcriptional regulator Sp13016 was discovered to be highly associated with butenyl-spinosyn synthesis and bacterial growth. Overexpression of sp13016 improved butenyl-spinosyn production to a level that was 2.84-fold that of the original strain, while deletion of sp13016 resulted in a significant decrease in yield and growth inhibition. Comparative proteomics revealed that these phenotypic changes were attributed to the influence of Sp13016 on the central carbon metabolism pathway to regulate the supply of precursors. Our research helps to reveal the regulatory mechanism of butenyl-spinosyn biosynthesis and provides a reference for increasing the yield of natural products of Actinomycetes.

Basic leucine zipper (bZIP) is a diverse transcription factor in plants that is involved in many stress responses, especially salt stress. However, the roles of bZIP genes in the common bean have not been elucidated. 84 proteins in common bean were identified here. Through phylogenetic analysis, the PvbZIPs were classified into five subfamilies, and these clusters were supported by several group-specific features, including gene structure, motifs, and cis-regulatory elements. Collinearity analysis revealed the connection between PvbZIPs and bZIPs from two other dicotyledonous species, namely Arabidopsis and Soybean (Glycine max). Expression patterns of the PvbZIPs genes indicated that they exhibit a tissue-specific manner at the sprouting stage. RNA-seq and qRT-PCR analyses indicated that PvbZIPs exhibit different expression patterns under salt stress in salt tolerance and salt-sensitive varieties. According to KEGG analysis of PvbZIPs-enriched pathways, PvbZIPs appear to target the abscisic acid (ABA) signaling pathway which might result in enhanced salt tolerance. Our findings elucidate on functional characterization of PvbZIP in Phaseolus vulgaris and its role in salt stress regulation through ABA.

Metal organophosphonates have been explored in energy-related fields due to their high chemical and thermal stability as a type of uniformly precursor, but only few of pristine metal organophosphonate are directly used for oxygen evolution reaction (OER) catalysts. Here, a mixed-valence iron phosphonate (Fe3-ppat) has been constructed and applied to OER catalysis considered the potential active sites in pillars FeII(H2O)4(COO)2 and inorganic layers FeIII(μ2–OH)PO3. Specifically, isostructural trimetallic framework Fe1.7Co0.3Ni1.0-ppat possesses a minimum overpotential (291 mV), small Tafel slope (91.65 mV dec−1), and high stability up to 83 h. The enhanced catalytic performance could be mainly ascribed to the synergistic effect of NiII equivalent occupancy in pillars and Co/FeIII in layers.

Based on the new process named “Combination Method” for metallurgy and separation of Baotou mixed rare earth concentrate (BMREC), the aim of this paper is to clearly elucidate the phase change behavior of BMREC without additives during oxidative roasting at 450–800 °C. The results indicate that the bastnaesite in BMREC is decomposed at 450–550 °C, the weight loss is about 10.3 wt%, and the activation energy (E) is 144 kJ/mol. The bastnaesite in BMREC is decomposed into rare earth fluoride, rare earth oxides (La2O3, Ce7O12, Pr6O11 and Nd2O3), and CO2, particularly, with the increase of roasting temperature, bastnaesite in BMREC is more completely decomposed into LaF3, which causes a decrease in leaching rate of La during the HCl leaching process. Additionally, the maximum cerium oxidation efficiency reaches about 60 wt% when the roasting temperature is equal to or above 500 °C, and the oxidation reaction rate of cerium increases with the increasing roasting temperature.

In this work, six energetic complexes were prepared and used as promoters for the hypergolic reaction of 1-ethyl-3-methylimidazolium cyanoborohydride [EMIM][BH3CN] and 90% H2O2. The structures of these compounds were studied by FT-IR spectroscopy, powder XRD, and single crystal X-ray diffraction. The results revealed that all the compounds were iso-structural and each metal centre was coordinated with four organic ligands and two counter ions. The decomposition temperatures of these compounds ranged from 169.6-255.9 °C. After adding 10 wt.% of prepared complexes to an ionic liquid, [EMIM][BH3CN], the shortest ignition delay time achieved was 94 ms. Moreover, the formed homogenous catalytic fuels had similar densities, thermal stabilities, as well as specific impulses similar to that of pure [EMIM][BH3CN]. The simple preparation method, excellent yield, as well as high performance of these compounds make them promising promoters for use in green hypergolic bipropellants.

Tumor-targeted delivery of nanomedicine is of great importance to improve therapeutic efficacy of cancer and minimize systemic side effects. Unfortunately, nowadays the targeting efficiency of nanomedicine toward tumor is still quite limited and far from clinical requirements. In this work, we develop an innovative peptide-based nanoparticle to realize light-triggered nitric oxide (NO) release and structural transformation for enhanced intratumoral retention and simultaneously sensitizing photodynamic therapy (PDT). The designed nanoparticle is self-assembled from a chimeric peptide monomer, TPP-RRRKLVFFK-Ce6, which contains a photosensitive moiety (chlorin e6, Ce6), a β-sheet-forming peptide domain (Lys-Leu-Val-Phe-Phe, KLVFF), an oligoarginine domain (RRR) as NO donor and a triphenylphosphonium (TPP) moiety for targeting mitochondria. When irradiated by light, the constructed nanoparticles undergo rapid structural transformation from nanosphere to nanorod, enabling to achieve a significantly higher intratumoral accumulation by 3.26 times compared to that without light irradiation. More importantly, the conversion of generated NO and reactive oxygen species (ROS) in a light-responsive way to peroxynitrite anions (ONOO−) with higher cytotoxicity enables NO to sensitize PDT in cancer treatment. Both in vitro and in vivo studies demonstrate that NO sensitized PDT based on the well-designed transformable nanoparticles enables to eradicate tumors efficiently. The light-triggered transformable nanoplatform developed in this work provides a new strategy for enhanced intratumoral retention and improved therapeutic outcome., Graphical abstract Image 1, Highlights • An innovative mitochondria-targeting chimeric peptide composed of four discrete functional domains is designed and prepared. • The peptide can self-assemble into nanospheres and transform into nanorods via light-triggered ROS generation and NO release. • The sphere−to−rod structural transformation remarkably enhances the intratumoral retention and accumulation of nanomedicine. • The conversion of generated ROS and NO to RNS with higher cytotoxicity enables NO to sensitize PDT in cancer treatment.

Retinal pigment epithelial (RPE) is primarily impaired in age-related macular degeneration (AMD), leading to progressive loss of photoreceptors and sometimes choroidal neovascularization (CNV). mTOR has been proposed as a promising therapeutic target, while the usage of its specific inhibitor, rapamycin, was greatly limited. To mediate the mTOR pathway in the retina by a noninvasive approach, we developed novel biomimetic nanocomplexes where rapamycin-loaded nanoparticles were coated with cell membrane derived from macrophages (termed as MRaNPs). Taking advantage of the macrophage-inherited property, intravenous injection of MRaNPs exhibited significantly enhanced accumulation in the CNV lesions, thereby increasing the local concentration of rapamycin. Consequently, MRaNPs effectively downregulated the mTOR pathway and attenuate angiogenesis in the eye. Particularly, MRaNPs also efficiently activated autophagy in the RPE, which was acknowledged to rescue RPE in response to deleterious stimuli. Overall, we design and prepare macrophage-disguised rapamycin nanocarriers and demonstrate the therapeutic advantages of employing biomimetic cell membrane materials for treatment of AMD.

In this work, a novel in situ auto-reduction strategy was developed to encapsulate uniformly dispersed Pd clusters/nanoparticles in MIL-125-NH2. It is demonstrated that the amino groups in MIL-125-NH2 can react with formaldehyde to form novel reducing groups (-NH CH2OH), which can in situ auto-reduce the encapsulated Pd2+ ions to metallic Pd clusters/nanoparticles. As no additional reductants are required, the strategy limits the aggregation and migration of Pd clusters and the formation of large Pd nanoparticles via controlling the amount of Pd2+ precursor. When applied as catalysts in the hydrogenation of phenol in the aqueous phase, the obtained Pd(1.5)/MIL-125-NH-CH2OH catalyst with highly dispersed Pd clusters/nanoparticles with the size of around 2 nm exhibited 100% of phenol conversion and 100% of cyclohexanone selectivity at 70 °C after 5 h, as well as remarkable reusability for at least five cycles due to the large MOF surface area, the highly dispersed Pd clusters/nanoparticles and their excellent stability within the MIL-125-NH-CH2OH framework.

Introduction Fusarium graminearum is a most destructive fungal pathogen that causes Fusarium head blight (FHB) disease in cereal crops, resulting in severe yield loss and mycotoxin contamination in food and feed. Silver nanoparticles (AgNPs) are extensively applied in multiple fields due to their strong antimicrobial activity and are considered alternatives to fungicides. However, the antifungal mechanisms and the effects of AgNPs on mycotoxin production have not been well characterized. Objectives This study aimed to investigate the antifungal activity and mechanisms of AgNPs against both fungicide-resistant and fungicide-sensitive F. graminearum strains, determine their effects on mycotoxin deoxynivalenol (DON) production, and evaluate the potential of AgNPs for FHB management in the field. Methods Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and fluorescence microscopy were used to examine the fungal morphological changes caused by AgNPs. In addition, RNA-Seq, qRT-PCR, and western blotting were conducted to detect gene transcription and DON levels. Results AgNPs with a diameter of 2 nm exhibited effective antifungal activity against both fungicide-sensitive and fungicide-resistant strains of F. graminearum. Further studies showed that AgNP application could impair the development, cell structure, cellular energy utilization, and metabolism pathways of this fungus. RNA-Seq analysis and sensitivity determination revealed that AgNP treatment significantly induced the expression of azole-related ATP-binding cassette (ABC) transporters without compromising the control efficacy of azoles in F. graminearum. AgNP treatment stimulated the generation of reactive oxygen species (ROS), subsequently induced transcription of DON biosynthesis genes, toxisome formation, and mycotoxin production. Conclusion This study revealed the underlying mechanisms of AgNPs against F. graminearum, determined their effects on DON production, and evaluated the potential of AgNPs for controlling fungicide-resistant F. graminearum strains. Together, our findings suggest that combinations of AgNPs with DON-reducing fungicides could be used for the management of FHB in the future.

Oxygen ligation is envisioned to provide a stable and distinctive coordination environment to the strongly oxophilic rare-earth metals. However, the well-defined dialkyl complexes bearing oxyanion ancillary ligand had been rarely addressed for the instability of the complexes and the shortage of easily available ligands. Herein, we report the synthesis of phosphate ligated dialkyl yttrium complexes (PYR2) featuring a high stability and a tunable ligand. Treated with the borate reagent, the phosphate yttrium complex displays high activity and selectivity in the catalytic cis-1,4-polymerization of isoprene (up to 96.5%). Furthermore, using AlMe3 as an additive, the stereoselectivity switches to trans-1,4-polymerization (up to 92.0%).

Pb-free Sn-based perovskite solar cells (PSCs) have recently made inspiring progress, and power conversion efficiency (PCE) of 14.8% has been achieved. However, due to the energy-level mismatch and poor interfacial contact between commonly used hole transport layer (i.e., poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate), PEDOT:PSS) and FASnI3 film, it is still challenging to effectively extract holes at the interface. Owing to the p-type nature of Sn-based perovskites, the efficient hole extraction is of particular significance to improve the PCE of their solar cells. In this work, for the first time, the role of chiral cations, α-methylbenzylamine (S-/R-/rac-MBA), in promoting hole transportation of FASnI3-based PSCs is demonstrated. The introduction of MBAs is found to form 2D/3D film with low-dimensional structures locating at PEDOT:PSS/FASnI3 interface, which facilitates the energy level alignment and efficient charge transfer at the interface. Importantly, chiral-induced spin selectivity (CISS) effect of R-MBA2SnI4 induced by chiral R-MBA cation is found to further assist the specific interfacial transport of accumulated holes. As a result, R-MBA-based PSCs achieve decent PCE of 10.73% with much suppressed hysteresis and enhanced device stability. This work opens up a new strategy to efficiently promote the interfacial extraction of accumulated charges in working PSCs.

Off-stoichiometry of perovskite structural Bi0.5Na0.5TiO3 (BNT) ferroelectrics can give rise to considerable oxide-ion conductivity. The inherent structural characteristics are urgent to be resolved due to its particular sensitivity of the conduction mechanism to the nominal composition and synthesis process. Herein, a thorough study of the temperature-dependent neutron, X-ray diffraction and Raman spectrum is carried out on a series of equivalently substituted A-site deficient non-stoichiometric and pristine BNT. Phase transition and defect association are systemically investigated in these dominated rhombohedral phases at room temperature, associated with well saturated ferroelectric states. Significant structural evolution identified by Rietveld refinements and the origin of the electrical performance are clarified at elevated temperatures, focusing on the subtle distortions of ionic displacements, oxygen octahedral tilts and local chemical environments for oxygen vacancies. The ion migration ability mediated by oxygen vacancies that are not energetically favorable in BNT mainly depends on the external substitutional disorder, and is strongly affected by the dopant concentration. Together with the lone pair substitution concept, superior oxide ionic conductivity is achieved, and an alternative strategy is provided in designing BNT based oxide ion conductors.

Background and objectives Both artesunate and fractional CO2 laser have been proved effective in the treatment of hypertrophic scars, yet little data are available for the efficacy of artesunate combined with fractional CO2 laser. In order to assess the pre-clinical significance and the underlying mechanism of this combined treatment profile, we attempted to observe the effectiveness of this therapy in rabbit models through determining the expression of BMP-7 and Fas. Materials and methods Twenty-Four New Zealand white rabbits with established hypertrophic scar samples were randomly divided into control group and three treatment groups. Artesunate (20 μl/cm2) was injected into the rat’s scar of artesunate and combination groups, while fractional CO2 laser (Combo mode, deep energy:10 mJ, super energy: 50 mJ) was applied to rats in fractional CO2 laser and combination groups at week 4 after model establishment. All rabbits underwent a total of 3 sessions of treatment once every 2 weeks. Histological and immunohistochemistry study, Western blot assay, cell viability, ELISA and RT-QPCR were performed at week 10 to observe the aspects of hypertrophic scar sample changes and expression of BMP-7 and Fas in the scar tissues. Results Compared with control group, hypertrophic scars and the collagen fibers were significantly inhibited after treatment, and higher inhibition was seen in the samples in combination group compared to that in artesunate and fractional CO2 laser groups (P Conclusions Artesunate combined with fractional CO2 laser is effective in hypertrophic scarring in this rabbit model. Our findings can serve as a potential alternative strategy to treatment of hypertrophic scar in clinical practice.

Background: Developing the high-efficiency and low-risk small-molecule greennematocide is the key of effective control of the nematodes. Paeonol, is a naturally occurring phenolic compound, isolated from the root bark of Paeonia suffruticosa and the whole plant of Cynanchum paniculatum. Due to its crucial phenolic ketone skeleton, modern biological science research has indicated that paeonol has a wide range of biological activities. The structural modification of paeonol into paeonol carbonyl hydrazone derivatives is a potential approach for the development of novel nematodes, which showed more toxicity than paeonol. However, there are no reports on the nematicidal activity of paeonol carbonyl hydrazone derivatives to control Heterodera glycines. Results: We always endeavor to discover and develop biorational natural products-based pesticidal agents, 4 significant intermediates and 21 novel 3/5(3,5)-(di)nitro/chloropaeonol carbonyl hydrazone derivatives were prepared, and their structures well characterized by 1H NMR, HRMS, MS, and mp. Due to the steric hindrance, the substituents on the C=N double bond of all hydrazine compounds adopted E configuration. Results of nematicidal activity revealed that, among all compounds, especially 5-nitropaeonol (5) and 3,5-dinitropaeonol (7) displayed the most potent nematicidal activity H. glycines in vivo with LC50 values of 0.0323 and 0.0367 mg/mL, respectively. Conclusion: It suggested that for the 3/5(3,5)-(di)nitro/chloropaeonol carbonyl hydrazone derivatives, a nitro group introduced at C5 position of 1 was necessary for obtaining the potent compound as nematicidal agents. These preliminary results will pave the way for further modification of paeonol in the development of potential new nematicides.

Brassica rapa (AA, 2n = 20) and Raphanus sativus (RR, 2n = 18) are popular vegetables containing multiple secondary metabolites, such as flavonoids and anthocyanins. Nevertheless, few studies on miRNA expression profiles and potential regulatory network of flavonoid metabolism have been reported in the intergeneric hybrid of B. rapa and R. sativus (Brassicacoraphanus, AARR, 2n = 38). Here, the miRNAs of Brassicacoraphanus and its parents were first identified by small RNA sequencing. It was revealed that 315 conserved miRNAs and 193 novel miRNAs were found in Brassicacoraphanus and its parents. Moreover, the miRNA expression profiles were characterized and 204 miRNAs with differential expression were obtained. Further analysis showed that 184 miRNAs were non-additively expressed in Brassicacoraphanus. At last, the potential regulatory network of flavonoid metabolism in Brassicacoraphanus was analyzed by multi-omics data, suggesting possible roles of miR858a and miR157a in regulating flavonoid synthesis pathway in Brassicacoraphanus. Taken together, this study provides useful resources for probing global miRNA expression patterns in Brassicacoraphanus, which facilitates regulatory mechanism research on the biosynthesis pathway of secondary metabolites in Brassicacoraphanus.

Upconversion nanosensitizers have been widely considered to have important applications in the treatment of major diseases such as tumors and the utilization of solar energy. Majority of the efforts so far have been focused on improving the efficiency of energy transfer (ET) between upconversion nanoparticles (UCNPs) and the anchored sensitizers with premise that high ET efficiency will lead to high acceptor efficacy. This premise is, however, proved by our current work to be invalid for commonly used load. Interaction between adjacent sensitizing molecules was found to be critical which undermines the amount of excited monomer sensitizers and thus fades the efficacy. Here NaYF4:Yb3+,Er3+ UCNPs and rose bengal (RB) photosensitizer molecules were used as the model energy donors and acceptors, respectively. Contrary to monotonous increase of the ET efficiency from UCNPs to RB species with increasing RB loading, acceptor efficacy characterized by the reactive oxygen species, as well as the RB fluorescence, exhibits bizarre dependence on the RB loading. The underlying mechanism was well studied by the steady-state and time-resolved spectroscopy of a series of samples. RB aggregates are believed to be responsible for the severe deviation between the ET efficiency and acceptor efficacy. The conclusion was validated by in vitro test where the photodynamic therapy with the most monomer RB in UCNPs-RB nanosensitizers kills 35.8% more cells than that with the highest RB loading. This understanding sheds light on construction of new ET based nanosystems for broad applications, such as medicine, solar energy utilization and optical storage.

With rapid development of marine infrastructures, materials with better biocorrosion resistance and antibiofouling performance will be highly demanded. Ti6Al4V alloy is susceptible to the above. The inhibition to the microbiologically influenced corrosion of Ti6Al4V-5Cu alloy against Pseudomonas aeruginosa was investigated using antibacterial test, electrochemical techniques, surface analysis, and weight loss test conducted for 2.5 months. At a sputtering depth of 0 nm, the passive film of Ti6Al4V-5Cu alloy was mainly composed of ideal oxide TiO2. With increasing sputtering thickness to 6 nm, Ti2O3 and TiO were detected with a relative fraction of 14.6% and 14.8%, respectively, in the oxide layer of Ti6Al4V-5Cu alloy. In contrast, the outermost layer of Ti6Al4V alloy was predominantly composed of TiO2 but Ti2O3 (22.8%), Al2O3 and V2O5 were also detected. With increasing sputtering depth to 6 nm, fitting revealed the presence of Ti2O3 and TiO with relative fractions of 25.3% and 35.8%, respectively. Yet, a spot of TiO (8%) was also observed at 12 nm in the oxide layer of Ti6Al4V alloy. Although the addition of Cu into Ti6Al4V alloy generated the self-healing property of passive film in the presence of P. aeruginosa, it also reduced resistance to corrosion in general condition.

Background: Natural products (NPs) are important sources for the design of new drugs and agrochemicals. Neopeltolide, a marine NP, has been identified as a potent Qo-site inhibitor of cytochrome bc1 complex. Methods: In this study, a series of neopeltolide derivatives was designed and synthesized by the simplification of its 14-membered macrolactone ring with a diphenyl ether fragment. The enzymatic inhibition bioassays and mycelium growth inhibition experiments against a range of fungi were performed to determine their fungicidal activities. Results: The derivatives have potent activity against the porcine bc1 complex. Compound 8q showed the best activity with an IC50 value of 24.41 nM, which was 8-fold more effective than that of positive control azoxystrobin. Compound 8a exhibited a 100% inhibitory rate against Zymoseptoria tritici and Alternaria solani at a 20 mg/L dose. Conclusion: Computational results indicated that compounds with suitable physicochemical properties, as well as those forming a hydrogen bond with His161, would have good fungicidal activity. These data could be useful for the design of bc1 complex inhibitors in the future.

Although peroxidase-like nanozymes have made great progress in bioanalysis, few current nanozyme-based biosensors are constructed for discriminating isomers of organic compounds. Herein, fluorescent metal-organic framework (MOF)-based nanozyme is utilized for phenylenediamine isomers discrimination and detection. NH2-MIL-101(Fe), as a member of Fe-based MOFs, functions as not only fluorescent indicator but also peroxidase mimics. In the presence of H2O2, NH2-MIL-101(Fe) can catalyze the oxidation of o-phenylenediamine (OPD) and p-phenylenediamine (PPD) into their corresponding oxidation products (OPDox and PPDox), which in turn quench its intrinsic fluorescence at 445 nm via inner filter effect (IFE). Differently, a new fluorescence peak at 574 nm is observed for OPDox. Thus, a ratiometric fluorescence method for the detection of OPD can be designed with the fluorescence intensity ratio F574/F445 as readout. This proposed strategy displays excellent discrimination ability for three phenylenediamines and may open new applications of MOFs in environmental science.

Conductive hydrogels have attracted considerable attention owing to their potential for use as electronic skin and sensors. However, the loss of the inherent elasticity or conductivity in cold environments severely limits their working conditions. Generally, organic solvents or inorganic salts can be incorporated into hydrogels as cryoprotectants. However, their toxicity and/or corrosive nature as well as the significant water loss during the solvent exchange present serious difficulties. Herein, a liquid-like yet non-toxic polymer-polyethylene glycol (PEG) was attempted as one of the components of solvent for hydrogels. In the premixed PEG-water hybrid solvent, polyacrylamide (PAAm) was in situ polymerized, overcoming the inevitable water loss induced by the high osmotic pressure of the PEG solution and achieving tailored water capacity. Interestingly, the mechanical strength (“soft-to-rigid” transition) and anti-freezing properties of organohydrogels can be simultaneously tuned over a very wide range through adjusting PEG content. This was due to that with increasing PEG in solvent, the PAAm chains transformed from stretching to curling conformation, while PEG bonded with water molecules via hydrogen bonds, weakening the crystallization of water at subzero temperature. Additionally, a highly conductive Ti3C2Tx-MXene was further introduced into the organohydrogels, achieving a uniform distribution triggered by the attractive interaction between the rich functional groups of the nanofillers and the polymer chains. The nanocomposite hydrogels demonstrate high electrical conductivity and strain sensitivity, along with a wide working temperature window. Such a material can be used for monitoring human joint movement even at low temperature and has potential applications in wearable strain sensors.

Volatile organic compounds (VOCs) which exist widely in indoor air, are confirmed to be harmful to human health. In this study, gaseous toluene, the representative VOCs, was degraded by photo-catalytic oxidation (PCO) under visible light. The Ag3PO4-g-C3N4 composites with different weight ratios of Ag3PO4/g-C3N4 were synthesized and used as the photo-catalysts. The results indicated that the Ag3PO4-g-C3N4 composites with the weight ratio of 2.6 % exhibited the most superior photo-catalytic activity, and the removal efficiency of toluene was 87.52 % within 100 min irradiation, which was higher than that of bare g-C3N4 and Ag3PO4. The pseudo-one-order model was applied to analyzing the reaction process, and the apparent reaction rate constant of 2.6 %-APO-g-C3N4 was 0.005 min−1. After 3 cycles, the removal efficiency was still higher than 80.72 %. According to the results of PLS and ESR, the combination of Ag3PO4 and g-C3N4 could improve photo-induced carrier separation as well as OH and O2− radicals were both detected. Furthermore, the Z-scheme mechanism of Ag3PO4-g-C3N4 photo-catalysts was proposed. Therefore, the superior photo-catalytic activity of composites was significantly increased by the Z-scheme. In addition, the small proportion of Ag3PO4 in composites may be beneficial for a wide range of applications, given the cost of noble metal Ag.

Solvothermal synthesis technique is an effective method to create composite materials. In this paper, a series of TiO2@MIL-101(Cr) were prepared by the solvothermal method for photocatalytic denitrification of pyridine in fuel under visible light irradiation. The products were characterized by XRD, FT-IR, SEM, TEM, BET, DRS, and ESR. The result shows that 20%TiO2@MIL-101(Cr) has high catalytic activity, the pyridine removal efficiency reaches values as high as 70% after irradiation for 240 min. Finally, we obtained the possible mechanism of photocatalytic denitrification according to the HPLC-MS spectrometry results analysis.

Electrocatalytic oxygen reduction reaction (ORR) via two-electron pathway is a promising approach to decentralized and on-site hydrogen peroxide (H2O2) production beyond the traditional anthraquinone process. In recent years, electrochemical H2O2 production in acidic media has attracted increasing attention owing to its stronger oxidizing capacity, superior stability, and higher compatibility with various applications. Here, recent advances of H2O2 electrosynthesis in acidic media are summarized. Specifically, fundamental aspects of two-electron ORR mechanism are firstly presented with an emphasis on the pH effect on catalytic performance. Major categories of promising electrocatalysts are then reviewed, including noble-metal-based materials, non-noble-metal single-atom catalysts, non-noble-metal compounds, and metal-free carbon-based materials. The innovative development of electrochemical devices and in situ/on-site application of electrogenerated H2O2 are also highlighted to bridge the gap between laboratory-scale fundamental research and practically relevant H2O2 electrosynthesis. Finally, critical perspectives on present challenges and promising opportunities for future research are provided.

Cobalt oxide (Co3O4) is currently suitable in energy storage applications because of its high capacity based on the conversion reaction mechanism. However, unmodified Co3O4 suffers from distinctly inferior rate capability and poor cycling stability. On the basis of the aforementioned considerations and density functional theory (DFT) simulations, the three-dimensional hierarchical porous structure (HPS) ultrasmall Co3O4 anchored into ionic liquid (IL) modified graphene oxide (GO) has been successfully prepared (ultrasmall/Co3O4-GA-IL). The ultrasmall/Co3O4-GA-IL consists of Co3O4 co-assembled with IL modified GO to generate the HPS which can facilitate ion transfer channels through reduction of the electron and ion transportation path and transmission impedance. In addition, N-doping graphene can enhance the inherent electrical conductivity of Co3O4, which is proved by the DFT calculations. By virtue of the novel superstructure, the ultrasmall/Co3O4-GA-IL electrode demonstrates a high reversible capacity of 1,304 mAh·g−1, an enhanced high-rate capability (715 mAh·g−1 at 5 C), and a capacity retention of 98.4% even after 500 cycles at 5 C rate, which corresponds to 0.0003% capacity loss per cycle. Pouch cells based on the cathode are further fabricated and demonstrate excellent mechanical and electrochemical properties under bent and folded state, highlighting the practical application of our deliberately designed electrode in wearable electronics.

The progression of esophagus cancer (EC) is associated with the alterative expressions of multiple microRNAs (miRs). MiR-1-3p is reported to inhibit the development of EC by targeting TAGLN2. Quercetin (Que) is a natural compound capable of antagonizing esophagus carcinoma (EC). In the current study, the role of miR-1-3p/TAGLN2 axis in the anti-EC function of Que was explored. Human EC cell lines KYSE-510 and TE-7 were treated with Que. Then the effects of Que on the growth and metastasis of EC cells, and on the activity of miR-1-3p/TAGLN2 axis were detected. The interaction between Que and miR-1-3p axis was further assessed by inhibiting miR-1-3p level in EC cells. The results showed that the treatment of Que impaired the growth and induced cell apoptosis in EC cells. The invasive ability of EC cells was also suppressed by Que. At molecular level, the expression of miR-1-3p was induced, while the expression of TAGLN2 was suppressed by Que. Moreover, the anti-EC effects of Que were blocked by miR-1-3p inhibition, which was represented by the restored growth and invasion of EC cells. Collectively, the current study demonstrated that Que exerted inhibitory effects on EC cells by inducing miR-1-3p.Supplemental data for this article is available online at https://doi.org/10.1080/01635581.2021.1972125.

Reversible thermochromic inorganic materials show stable and perceptible color change with changing environmental temperatures. This property makes them excellent materials for fabricating temperature indicators, military camouflage materials, and thermal warning devices. However, the mechanism of thermochromism has not been fully understood. Here, we prepared novel bismuth molybdate materials by calcination of Bi2O3 and MoO3 mixtures. The materials exhibit reversible thermochromism, gradually changing color from milky white at 25 °C to bright yellow at 500 °C. The phase composition of the product is tunable by adjusting the ratio of Bi2O3 and MoO3 in the starting materials, producing either single phase of α-Bi2Mo3O12 or mixed phases of α-Bi2Mo3O12, β-Bi2Mo2O9 and γ-Bi2MoO6. The mechanism of reversible thermochromism was studied by in situ UV/Vis diffuse reflectance spectroscopy (UV/Vis DRS), in situ synchrotron radiation powder X-ray diffraction (SRPXRD), and differential scanning calorimetry (DSC). In situ SRPXRD revealed no phase transition during heating and cooling, which agrees with DSC analysis with no thermal event detected until the melting temperature of α-Bi2Mo3O12 at 661.6 °C. With increasing temperature, in situ SRPXRD also revealed anisotropic expansion of the α-Bi2Mo3O12 lattice parameters, while in situ UV/Vis DRS showed a continuous red shift in the absorption edge and gradual decrease of band gap, suggesting that lattice expansion and shrinking upon heating and cooling is the main reason for the thermochromic behavior in bismuth molybdate materials.

Follicular helper T (TFH) cells are a specialized subset of CD4+ T cells that essentially support germinal center responses where high-affinity and long-lived humoral immunity is generated. The regulation of TFH cell survival remains unclear. Here we report that TFH cells show intensified lipid peroxidation and altered mitochondrial morphology, resembling the features of ferroptosis, a form of programmed cell death that is driven by iron-dependent accumulation of lipid peroxidation. Glutathione peroxidase 4 (GPX4) is the major lipid peroxidation scavenger and is necessary for TFH cell survival. The deletion of GPX4 in T cells selectively abrogated TFH cells and germinal center responses in immunized mice. Selenium supplementation enhanced GPX4 expression in T cells, increased TFH cell numbers and promoted antibody responses in immunized mice and young adults after influenza vaccination. Our findings reveal the central role of the selenium–GPX4–ferroptosis axis in regulating TFH homeostasis, which can be targeted to enhance TFH cell function in infection and following vaccination. T follicular helper (TFH) cells are important for the generation of effective antibody responses. Yu and colleagues find that TFH cells are exceptionally sensitive to death by ferroptosis and that this process is regulated by the activity of the selenoenzyme GPX4.

Background Several individual studies have shown that circulating levels of odd-chain SFAs and very-long-chain SFAs (VLSFAs) may have beneficial effects, but the results are mixed. While the dietary and metabolic factors that may influence VLSFAs are not well-known, a previous study observed associations of VLSFA concentrations with variants in serine palmitoyl-transferase long-chain base subunit 3 (SPTLC3) gene. Objectives We investigated the associations of individual plasma SFAs and SPTLC3 gene rs680379 polymorphism with metabolic risk factors and type 2 diabetes (T2D). Methods We measured plasma SFAs using gas chromatography among 898 T2D cases and 1618 matched controls, and genotyped the SPTLC3 gene rs680379 polymorphism using the MassArray System among 1178 T2D cases and 1907 matched controls. Conditional logistic regression was used to estimate ORs and 95% CIs. Results We found that plasma odd-chain SFAs and VLSFAs were correlated with favorable blood lipids and insulin resistance marker profiles. After multivariable adjustment, pentadecanoic acid (15:0) was inversely associated with the odds of T2D (OR per 1 SD difference: 0.63; 95% CI: 0.57, 0.70), as were measurements of 3 individual VLSFAs [arachidic acid (20:0), behenic acid (22:0), and lignoceric acid (24:0)], with ORs ranging from 0.60 to 0.72 (95% CIs ranging between 0.52 and 0.79). The associations between 3 individual VLSFAs and T2D were attenuated after further adjustment for triglycerides. Meanwhile, compared with the rs680379 GG genotype carriers, the ORs of T2D for the GA and AA genotype carriers were 0.81 (95% CI: 0.68-0.97) and 0.76 (95% CI: 0.61-0.96), respectively. Conclusions Plasma 15:0 and VLSFAs were inversely associated with T2D. Meanwhile, compared with the rs680379 GG genotype carriers, subjects with GA and AA genotypes were associated with decreased odds of T2D. More investigations are warranted to confirm our findings.

N6-methyladenosine (m6A) is the most prevalent RNA epigenetic regulator in cancer. However, the understanding of m6A modification on lipid metabolism regulation in colorectal cancer (CRC) is very limited. Here, we observed that human CRCs exhibited increased m6A mRNA methylation mediated by dysregulation of m6A erasers and readers. By performing methylated RNA-immunoprecipitation sequencing (MeRIP-seq) and transcriptomic sequencing (RNA-seq), we identified DEGS2 as a downstream target of m6A dysregulation. Overexpression or knockdown of DEGS2 confirmed the role of DEGS2 in proliferation, invasion and metastasis of CRC both in vitro and in vivo. Mechanistic studies identified the specific m6A modification site within DEGS2 mRNA, and mutation of this target site was found to drastically enhance the proliferative and invasive ability of CRC cells in vitro and promote tumorigenicity in vivo. Lipidome analysis showed that lipid metabolism was dysregulated in CRC. Moreover, ceramide synthesis was suppressed due to DEGS2 upregulation mediated by m6A modification in CRC tissues. Our findings highlight that the function of DEGS2 m6A methylation in CRC and extend the understanding of the importance of RNA epigenetics in cancer biology.

We report an amino-functionalized indium-organic framework for efficient CO2 reduction to formate. The immobilized amino groups strengthen the absorption and activation of CO2 and stabilize the active intermediates, which endow an enhanced catalytic conversion to formate despite the inevitable reduction and reconstruction of the functionalized indium-based catalyst during electrocatalysis. The reconstructed amino-functionalized indium-based catalyst demonstrates a high Faradaic efficiency of 94.4 % and a partial current density of 108 mA cm-2 at -1.1 V vs. RHE in a liquid-phase flow cell, and also delivers an enhanced current density of ca. 800 mA cm-2 at 3.4 V for the formate production in a gas-phase flow cell configuration. This work not only provides a molecular functionalization and assembling concept of hybrid electrocatalysts but also offers valuable understandings in electrocatalyst evolution and reactor optimization for CO2 electrocatalysis and beyond.

The self-assembled phospholipid- or cytosol-associated multienzyme complexes constitute necessary components of the foundation of life. As a proof of concept, metal-coordinated supramolecular nanogels (MCSGs) have been designed, with the self-assembly of di-lysine coordinated iron (Fe(Lys)2)-functionalized peptide gelators on the interface by an in situ amidation-induced protonation process. The monoatomic and highly dispersed active centers of Fe(Lys)2 offered the nanogel mimics with excellent reaction rates due to the high density and nano compartmental structure similar to the natural matrix-associated multienzyme complex. SiO2@MCSGs show both superoxide dismutase (SOD) activity and peroxidase (POD) activity, and the higher activities compared with the activity of free Fe(Lys)2 molecules can be detected. After loading the substrate 2,2′-azinobis-(3-ethylbenzthiazoline-6-sulphonate) (ABTS), SiO2@MCSGsABTS can responsively convert O2− · in the tumor microenvironment into H2O2 intermediates and then tandem catalyzed the oxidization of ABTS for contrast photoacoustic (PA) imaging of tumor by the SOD-POD mimic activity, showing their great potential as the efficient enzymatic agents for pathological theranostics.

Carbon dioxide reforming of methane can reduce emissions of greenhouse gases, and has been extensively studied. The conventional Ni-based catalysts easily coke, sinter, and deactivate in the CRM reaction. The studies suggested that the cold plasma treatment can improve the structure of Ni-based catalysts, and so enhance coke resistance of the catalysts. The review summarized the effect of cold plasma treatment on the coke resistance of Ni-based catalysts for the CRM reaction. The main goal of the paper was to illuminate: the structure change of catalysts treated by cold plasma, such as crystal planes of Ni particles, the particles size of Ni, the Ni dispersion, the metal-support interaction, and CO2 absorption capacity; the correlation between plasma treatment conditions (treatment way and parameters) and coke resistance of the catalyst treated by cold plasma; and the mechanism of plasma treatment to improve the coke resistance of the catalysts.

Urotensin II (UII) is involved in the formation of atherosclerosis, but its role in the stability of atherosclerotic plaques is unknown. The purpose of this study was to observe the dynamic changes in plasma UII and analyze its relationship to the stability of atherosclerotic plaques. One hundred thirty-five consecutive patients with acute coronary syndrome (ACS) were enrolled. The plasma UII levels were measured immediately after admission and during three-month follow-up. A vulnerable plaque model was established using local transfection of a recombinant P53 adenovirus into plaques in rabbits fed with a high-cholesterol diet and subjected to balloon arterial injury. The levels of plasma UII were measured weekly. The changes in plasma UII during the formation of atherosclerotic plaques and before and after plaque transfection were observed. The morphology of the plaques and the expression, distribution, and quantitative expression of UII in the plaques also were observed. Our results showed that the levels of plasma UII in patients with ACS at admission were lower than levels observed at the three-month follow-up. UII dynamic changes and its correlation with plaque stabilities were further verified in rabbits with atherosclerotic vulnerable plaques. The UII levels in rabbits were significantly decreased immediately after the P53 gene transfection, which led to plaque instability and rupture. These results suggested that UII expression was down-regulated in ACS, which may be related to its ability to modulate mechanisms involved in plaque stability and instability.

In recent years, graphitic carbon nitride (g-C3N4) has been developed greatly in the domain of water treatment. We adopted one-step calcination to enhance the light absorption of g-C3N4 with melamine-sponge (MS). A novel form of photocatalysts (gCNMx, x = 0.1, 0.2 and 0.3) were successfully prepared. The color of gCNMx changed with addition of MS. Experimental analysis demonstrated that C-doping and N vacancies increased the capacity of light absorption of gCNM0.2, and further increased efficiency of photothermal conversion and photogenerated holes. The sterilization efficiency of gCNM0.2 could rival a variety of metal photocatalysts. Moreover, the preparation of gCNM0.2 was cost-effective and environmental-friendly. Interestingly, the inactivation efficacy of gCNM0.2 for S. aureus depended heavily on the photogenerated holes, however, the decisive force toward S. typhimurium was photothermal conversion.

The toxic metal ions leaching and metal nanoparticles agglomeration were the critical issues for metal-based carbon materials during the peroxymonosulfate (PMS) activation processes. Herein, a facile strategy was first proposed that zero-dimensional Fe/Fe3C nanoparticles were embedded in one-dimensional N-doped carbon nanofiber (Fe/Fe3C@NCNF) to solve the above challenges. The as-obtained Fe/Fe3C@NCNF-800 possessed a low Ea value (11.7 kJ/mol) and exhibited high activity for activating PMS to degrade tetracycline (TC) in a wide range of pH 3-11. As expected, the iron ions leaching concentration of Fe/Fe3C@NCNF-800 was very low (0.082 mg/L). Meanwhile, the Fe/Fe3C@NCNF-800 was easily recovered from the reaction solution due to its magnetic properties. Both superoxide radicals (O2∙−) and non-radical of singlet oxygen (1O2) were the primary reactive oxygen species (ROS) in the Fe/Fe3C@NCNF-800/PMS system via quenching tests and electron spin resonance spectroscopy (ESR). The catalytic mechanism suggested that the Fe/Fe3C and graphitic N were the main active sites in the Fe/Fe3C@NCNF-800 for PMS activation. This work provided a facile method for the preparation of Fe-based carbon materials with high catalytic ability, low metal leaching and easy recycling, showing a broad prospect for environmental applications.

There are numerous evaluations of natural products, of which majority are food bioactives, performed up to date for their various health beneficial activities via targeting specific proteins. However, the direct identification of a targeted protein remains unexplored for natural occurring compounds. Proteolysis targeting chimera (PROTAC) is a type of bifunctional chimeric molecules that can directly degrade the binding proteins targeted by bioactive molecules in an ubiquitin-proteasome pathway. As the agents in protein degradation dependent on ubiquitin ligase, the bifunctional molecule connects the target protein ligand and E3 ligase ligand together via an appropriate linker. It is highly selective and efficient to induce the ubiquitin-mediated degradation of targeted binding proteins. Therefore, it has been demonstrated that the PROTAC technology has broad application in the modulation of the target protein level. In this review, we outlined the advances in PROTAC combined molecule compounds, summarized its quantitative structure-activity relationship, and finally reviewed the methods applied in identifying the target proteins of natural products. We hope it will provide an insightful application of PROTAC techniques in the target protein identification of natural products including food bioactive molecules.

Problem: Does sildenafil have an effect on pregnancy outcomes in patients with poor endometrial development?Methods: This study included 472 infertility patients who underwent in vitro fertilization/intracytoplasmatic sperm injection and frozen-thawed embryo transfer (IVF/ICSI-FET) and suffered from poor endometrial development in the hormone replacement cycle (HRC) from April 2017 to July 2019. The patients were divided into two groups: the sildenafil group(n=88) and the control group(n=384). Endometrial thicknesses and types on endometrial transformation day, as well as pregnancy outcomes after FET (biochemical pregnancy, clinical pregnancy, early abortion, late abortion, and live birth rates) between two groups were analyzed. Results: No significant differences were observed in endometrial thicknesses and types on endometrial transformation day between the sildenafil group and the control group. There were also no statistically significant differences in pregnancy outcomes between the two groups. After adjusting for confounding factors, the application of sildenafil could not improve endometrial thickness and type of the day of endometrial transformation and the growth of endometrial thickness. Moreover, the sildenafil was not closely related to clinical pregnancy outcomes.Conclusions: Sildenafil could not better endometrial development and pregnancy outcomes in patients with poor endometrial development.