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Adsorption and separation of C4 hydrocarbons are crucial steps in petrochemical processes. Employment of porous materials for enhancing the separation efficiency have paid much attention. Covalent-organic frameworks of diamond-topology, dia-COFs, often exhibit unique structural properties such as interpenetration isomerism and pedal motion. Herein, in order to get a deep insight into the structure-performance correlation of such dia-COFs, a series of dia-COF materials have been proposed and theoretically investigated on the C4 separation. It is found that these dia-COFs display an excellent adsorption and separation property towards isobutene with respect to other C4 hydrocarbons (i.e., 1,3-butadiene, 1-butene, 2-cis-butene, 2-trans-butene, isobutane and n-butane). What’s more, the correlation between the topology parameters and experimental synthesis feasibility has been established for COF-300 (dia-cN), and the unreported COF-300 (dia-c3) is predicted to be experimentally feasible synthesized. Our findings not only provide a deep insight into the mechanism of topology characteristics of dia-COFs on C4 adsorption and separation properties but also guide the design and synthesis of novel highly-effective porous materials.

Diffuse large B-cell lymphoma (DLBCL) exhibits frequent inactivating mutations of the histone acetyltransferase CREBBP, highlighting the attractiveness of targeting CREBBP deficiency as a therapeutic strategy. In this study, we demonstrate that chidamide, a novel histone deacetylase (HDAC) inhibitor, is effective in treating a subgroup of relapsed/refractory DLBCL patients, achieving an overall response rate (ORR) of 25.0% and a complete response (CR) rate of 15.0%. However, the clinical response to chidamide remains poor, as most patients exhibit resistance, hampering the clinical utility of the drug. Functional in vitro and in vivo studies have shown that CREBBP loss of function is correlated with chidamide sensitivity, which is associated with modulation of the cell cycle machinery. A combinatorial drug screening of 130 kinase inhibitors targeting cell cycle regulators identified AURKA inhibitors, which inhibit the G2/M transition during the cell cycle, as top candidates that synergistically enhanced the antitumor effects of chidamide in CREBBP-proficient DLBCL cells. Our study demonstrates that CREBBP inactivation can serve as a potential biomarker to predict chidamide sensitivity, while combination of an AURKA inhibitor and chidamide is a novel therapeutic strategy for the treatment of relapsed/refractory DLBCL.

A solid electrolyte interphase (SEI) layer on Si-based anodes should have high mechanical properties to adapt the volume changes of Si with low thickness and good ionic conductivity. To better understand the influence of carbonate solvents on the SEI composition and mechanism of formation, systematic studies were performed using dimethyl carbonate (DMC) or propylene carbonate (PC) solvent and LiPF6 as a salt. A 1 M LiPF6/EC-DMC was used for comparison. The surface chemical composition of the Si electrode was analyzed at different potentials of lithiation/delithiation and after a few cycles. Ex situ X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry results demonstrate that a thinner and more stable SEI layer is formed in LiPF6/DMC. The in situ Fourier transform infrared spectroscopy proves that the coordination between Li+ and DMC is weaker, and fewer DMC molecules take part in the formation of the SEI layer. The higher capacity retention during 60 cycles and less significant morphological modifications of the Si electrode in 1 M LiPF6/DMC compared to other electrolytes were demonstrated, confirming a good and stable interfacial layer. The possible surface reactions are discussed, and the difference in the mechanisms of formation of SEI in these three various electrolytes is proposed.

Background Despite multiple available fixed-dose combinations (FDCs) of inhaled long-acting β2-agonists (LABAs) plus long-acting muscarinic antagonists (LAMAs) and LABAs plus inhaled corticosteroids (ICS) for COPD, uncertainty remains regarding their comparative effects. Research Question Can comparative effectiveness and safety of LABA plus LAMA (LABA/LAMA) and LABA plus ICS (LABA/ICS) FDCs vary by different individual components of the dual combinations in COPD? Study Design and Methods We conducted a new user, propensity score-inverse probability of treatment weighting cohort study to compare the effectiveness and safety of two frequently used LABA/LAMA FDCs (indacaterol plus glycopyrronium [IND/GLY] and vilanterol plus umeclidinium [VI/UMEC]) vs three commonly prescribed LABA/ICS FDCs (salmeterol plus fluticasone propionate [SAL/FP], formoterol fumarate plus budesonide [FF/BUD], and formoterol fumarate plus beclomethasone dipropionate [FF/BDP]) using the Taiwanese nationwide health care claims from 2014 through 2017. The primary effectiveness outcome was the annual moderate to severe exacerbation rate, and safety outcomes included risks of severe pneumonia and cardiovascular disease requiring hospitalization. Weighted generalized linear mixed models and Cox proportional hazard models were used to assess the effectiveness and safety outcomes, respectively. Results Patients with COPD initiating IND/GLY and VI/UMEC showed an 11% (incidence rate ratio [IRR], 0.89; 95% CI, 0.80-0.98) and 20% (IRR, 0.80; 95% CI, 0.71-0.90) reduced annual rate of moderate to severe exacerbations, respectively, than those initiating SAL/FP, but showed a similar rate as those initiating FF/BUD or FF/BDP. Both LABA/LAMA FDCs, compared with SAL/FP and VI/UMEC vs FF/BDP, were associated with a 27% (hazard ratio [HR], 0.73; 95% CI, 0.59-0.90) to 42% (HR, 0.58; 95% CI, 0.48-0.70) reduced pneumonia risk. Cardiovascular risk was comparable in five groups. An intraclass difference existed in rates of moderate to severe COPD exacerbation and risks of pneumonia among LABA/ICS FDCs, but not between LABA/LAMA FDCs. Interpretation Both LABA/LAMAs vs SAL/FP are associated with a lower exacerbation rate and pneumonia risk, but exhibit similar effectiveness and safety outcomes compared with FF/BDP or FF/BUD, suggesting that comparative effects may differ by individual components of the dual therapies in COPD.

A new tyramine derivative, glycosamide A (1), together with two known amide alkaloids, N-benzoyltyramine methyl ether (2) and aurantiamide acetate (3), was isolated from the branches and leaves of Glycosmis craibii Tanaka. Their structures were elucidated through extensive 1D and 2D NMR and HR-ESI-MS spectroscopic analyses. All known compounds were isolated from the genus Glycosmis for the first time. Furthermore, the antiproliferative activities of all isolated alkaloids in vitro were evaluated. Compound 2 displayed weak antiproliferative activities against five human cancer cell lines, HL-60, SMMC-7721, A-549, MCF-7, and SW480.

In this study, alkali/acid treatment and ion exchange post-synthesis modification methods to modify the pore diameter and structure of molecular sieve 13X (MS13X) were applied to obtain products, which could then be implemented to improve the enrichment recovery of hopanoids in petroleum. The modification products were analyzed by SEM with EDS, XRD and nitrogen physisorption. The results indicated that the product which had been prepared in the oxalic acid ethanol solution formed some mesopores, and also retained the initial framework of crystal. It was revealed that this product was able to remarkably increase the recovery rate of hopanoids in petroleum without leading to a significant isotope fractionation phenomenon. It is thus shown that this modification method of non-aqueous oxalic acid solution for MS13X can be used as an effective pretreatment tool in the application of compound-specific isotope analysis of hopanes with low concentration.

CRISPR–Cas systems are bacterial adaptive immune systems, and phages counteract these systems using many approaches such as producing anti-CRISPR (Acr) proteins. Here, we report the structures of both AcrIF14 and its complex with the crRNA-guided surveillance (Csy) complex. Our study demonstrates that apart from interacting with the Csy complex to block the hybridization of target DNA to the crRNA, AcrIF14 also endows the Csy complex with the ability to interact with non-sequence-specific dsDNA as AcrIF9 does. Further structural studies of the Csy–AcrIF14–dsDNA complex and biochemical studies uncover that the PAM recognition loop of the Cas8f subunit of the Csy complex and electropositive patches within the N-terminal domain of AcrIF14 are essential for the non-sequence-specific dsDNA binding to the Csy–AcrIF14 complex, which is different from the mechanism of AcrIF9. Our findings highlight the prevalence of Acr-induced non-specific DNA binding and shed light on future studies into the mechanisms of such Acr proteins.

Two new aldoximes A–B (1−2), and two known analogues (3−4), were identified from ethanolic extracts of Glycosmis craibii. The structures of new compounds 1−2 were unambiguously elucidated based on spectroscopic methods. All isolated aldoximes were evaluated for their anti-inflammatory activity in vivo. Compounds 1−4 displayed remarkable inhibitory effects against nitric oxide (NO) production stimulated by lipopolysaccharide in mouse macrophage RAW 264.7 cells with the IC50 values ranging from 2.38 ± 0.08–8.43 ± 0.21 μM.

In the current study, by using the mixed ligand approach, a novel 2D metal–organic framework (MOF), [Zn(Hssa)(1,4-dtb)·H2O]n (H3ssa = 5-sulfosalicylic acid, dtb = 1,4-di(4H-1,2,4-triazol-4-yl)benzene) was synthesized with a high yield under solvothermal reaction conditions and through the elemental analysis and the single-crystal X-ray diffraction. Luminescence studies demonstrate that 1 is able to be utilized as a strongly sensitive luminescent sensor for Cr2O72− and CrO42− in H2O. Furthermore, the neuroprotective effect of the compound on CO poisoning patients was evaluated in biological research. The real-time RT-PCR was conducted to study the expression level of the ROS-related genes in the neurons. In addition to this, the activation of the superoxide dismutase (SOD) in the neurons was measured after treatment of the compound.

Li2O2, as the discharge product of Li-O2 batteries on cathode, is difficult to be electrochemically decomposed, which will lead to short cycling lifespan of the batteries. In this study, the cycling lifespan of Li-O2 battery was prolonged significantly by an efficient bifunctional catalyst. The Ni and N co-doped carbon nanotubes (NiNCs) were synthesized firstly, and then RuO2 nanoparticles were deposited on NiNCs by a hydrothermal route to synthesize RuO2/NiNC catalysts. Transmission electron microscopy and X-ray diffraction characterizations demonstrated that part of metallic Ni was converted into NiO and Ni(OH)2 after loading RuO2, and the existence of NiO layer can prevent further oxidation of metallic Ni. The Li-O2 battery with RuO2/NiNC as the cathode catalyst exhibits an overpotential of 0.43 V, which is much lower than the value of 1.03 V measured with the Li-O2 battery using NiNC as the cathode catalyst. At a rate of 200 mA g−1, the Li-O2 battery with the RuO2/NiNC cathode can maintain a reversible capacity of 500 mA h g−1 for 260 cycles, and 117 cycles with a higher reversible capacity of 1000 mA h g−1. The superior property of the RuO2/NiNC bifunctional catalyst could be ascribed to the high activity of RuO2 and the rich carbon nanotube structure of NiNC for deposition and decomposition of Li2O2.

The geminal difluorocyclobutane core is a valuable structural element in medicinal chemistry. Strategies for gem-difluorocyclobutanes, especially the 2-substituted cases, are limiting and often suffer from harsh reaction conditions. Reported herein is a migratory gem-difluorination of aryl-substituted methylenecycloproanes (MCPs) for the synthesis of 2-arylsubstituted gem-difluorocyclobutanes. Commercially available Selectfluor (F-TEDA-BF4) and Py·HF were used as the fluorine sources. The protocol proceeds via a Wagner-Meerwein rearrangement with mild reaction conditions, good functional group tolerance, and moderate to good yields. The product could be readily transformed to gem-difluorocyclobutane-containing carboxylic acid, amine, and alcohol, all of which are useful building blocks for biologically active molecule synthesis.

Biogenic volatile organic compounds (BVOCs) play an important role in atmospheric chemistry due to their large quantities and high reactivity. In this study, the impacts of BVOC emissions on ozone formation were investigated based on MEGANv3.1 in the Yangtze River Delta (YRD) region, which has increasingly suffered from ozone pollution in recent years. The sensitivities of BVOC emissions to different drought stress configurations and the quality of emission factors were evaluated. Furthermore, BVOC contribution to ozone formation was simulated by integrated meteorology and air quality model system and the impacts of different BVOC emission scenarios on ozone concentration were discussed. Annual BVOC emissions estimated with the default drought stress configuration (i.e., base case) was 6.8 × 105 tons. The drought stress algorithm implemented in MEGANv3.1 could suppress BVOC emissions by 58% and this algorithm was sensitive to the choice of wilting point values. The BVOC contribution to the average of daily maximum 8 h ozone concentration without drought stress effect in July 2016 was 104% higher than that in the base scenario when the drought stress effect is activated. Using an alternative set of wilting point led to BVOC contribution being 48% higher than that in the base scenario. High contributions of BVOCs to simulated ozone concentration were found in northern Zhejiang, especially in Hangzhou and its surrounding areas.

Background Poor control of diabetes mellitus (DM) increases active tuberculosis (TB) risk. Understanding risk factors for latent TB infection (LTBI) in this population and intervention completion rates is crucial for policy making. Methods Under a collaborative multidisciplinary team consisting of public health professionals, endocrinologists, and pulmonologists, patients aged >45 years with poorly controlled DM (pDM), defined as having a glycated hemoglobin level of ≥9% within the preceding year, were enrolled by endocrinologists from 2 hospitals; these patients underwent LTBI screening by using QuantiFERON (QFT). Once-weekly isoniazid and rifapentine for 12 weeks (3HP) or daily isoniazid for 9 months (9H) was administered by pulmonologists. QFT-positivity predictors were evaluated using logistic regression. Completion rates and safety were also investigated. Results Among 980 patients with pDM (age: 64.2 ± 9.7 years), 261 (26.6%) were QFT-positive. Age, DM duration, chronic kidney disease stage ≥3, and dipeptidyl peptidase-4 inhibitor use, not using metformin, were associated with QFT-positivity. Preventive therapy (3HP: 138; 9H: 62) was administered in 200 (76.6%) QFT-positive patients. The completion rates of 3HP and 9H were 84.1% and 79.0%, respectively (P = .494). Nine (6.5%) and zero patients in the 3HP and 9H groups, respectively, developed systemic drug reactions (P = .059); 78.3% and 45.2% had ≥1 adverse drug reactions (P, The latent tuberculosis infection prevalence exceeds 25% in elderly patients with poorly controlled diabetes mellitus (DM), particularly those with a long DM duration. The completion rate of preventive therapy, regardless of the regimen, approaches 80% in this population under a collaborative framework.

The interfacial electronic and geometric effects behind the size effect are crucial in determining the catalytic performance of supported metal catalysts, whereas they remain still unknown for most of important heterogeneous catalytic reactions such as water-gas shift reaction (WGSR). In this work, we report a profound size effect in five Pt/CeO2 catalysts among Pt single atoms, sub-nanoclusters (ca. 0.8 nm) and nanoparticles (3.8–9.3 nm) for the WGSR. The catalyst with about 3.8 nm Pt nanoparticles had the highest activity, superior to the other four Pt/CeO2 catalysts. Ptδ+-OV-Ce3+ species served as the interfacial active sites, wherein the carboxyl pathway seemed more preferred than the formate route, and favored high activity. Such high activity and pathway preference are due to both of the electronic and geometric effects. On the one hand, the electronic metal-support interaction (EMSI) modulated by the metal deposit size tunes the activation of the CO adsorbed on Pt sites. On the other hand, the abundant interfacial oxygen vacancies for the geometric effect of providing the active sites to activate and dissociate H2O.

Objective. The aim of the study was to investigate the potential effects of waste anesthetic gas (WAG) on oxidative stress, DNA damage, and vital organs. Methods. A total of 150 members of the staff at a hospital were assigned to an exposure group or control group. The 68 operating room (OR) staff in the exposure group were exposed to WAG, and the 82 non-OR staff in the control group were not exposed to WAG. Air samples were collected in the OR, and the sevoflurane concentrations in the samples were determined. Superoxide dismutase (SOD), glutathione peroxidase (GSH-px), and malondialdehyde (MDA) in plasma from the participants were determined to assess oxidative stress. Western blot analysis was used to detect γH2AX in peripheral blood to assess DNA damage. Hematopoietic parameters, liver function, kidney function, and changes in electrophysiology were assessed to identify the effects on the vital organs. Results. The mean (±standard deviation) sevoflurane concentration in 172 air samples from 22 operating rooms was 1.11 ± 0.65 ppm . The superoxide dismutase activity and vital organ parameters (lymphocyte, hemoglobin, and total protein concentrations and heart rate) were significantly lower ( P < 0.05 ) in the exposed group than the control group. The malondialdehyde, total bilirubin, and creatinine concentrations and QT and QTc intervals were significantly higher ( P < 0.05 ) in the exposed group than the control group. There were no significant differences between the glutathione peroxidase activities and γH2AX concentrations for the exposed and control groups. Conclusions. Long-term occupational exposure to waste anesthetic gas may affect the antioxidant defense system and probably affects vital organ functions to some extent. No correlation between DNA damage and chronic exposure to WAG was observed.

The shuttle effect and sluggish conversion kinetics of lithium polysulfides (LiPSs) restrict the practical application of lithium–sulfur (Li–S) batteries. Herein, we introduce nickel cobaltite/carbon nanofiber (NiCo₂O₄/CNF) composites as a chemical trapper and conversion accelerator for LiPSs. The experiment and density functional theory indicate that polar NiCo₂O₄ can strongly trap polysulfides through Ni–S and Co–S bonds. The CNF network provides structural stability and serves as a second barrier for polysulfides. Systematic studies on the solid₍ₛᵤₗfᵤᵣ₎–liquid₍ₚₒₗyₛᵤₗfᵢdₑₛ₎–solid₍ₛᵤₗfᵢdₑ₎ conversion reactions qualitatively and quantitatively demonstrate that the well-designed NiCo₂O₄/CNF interface with strong polysulfides affinity, affluent polar nucleation sites, and fast Li⁺/e– transport can noteworthily catalyze the liquid-phase conversion of LiPSs and the solid-phase deposition of lithium sulfide (Li₂S) and protect the lithium anode as well. Thus, the NiCo₂O₄/CNF-based batteries can exhibit a high rate capability of 870 mAh g–¹ at 5 C and excellent cycling performance evidenced by a capacity retention of 95% after 200 cycles at 0.1 C with a sulfur loading of 6.3 mg cm–². Further increasing the sulfur loading to 7.9 mg cm–² and with a lean electrolyte/sulfur (E/S) ratio of 7.2 μL mgₛ–¹, the Li–S battery can deliver a high areal capacity of 8.1 mAh cm–².

Construction of alternating donor–acceptor (D–A) units in g-C3N4 is an effective strategy to achieve more effective charge carrier separation towards improved photocatalytic performance. However, the charge carrier kinetics, especially the vague intramolecular charge transfer (ICT) details and structure–performance relationship remain unknown. Herein, a series of D–A structured g-C3N4 photocatalysts with improved performance were synthesized by introducing 2-aminobenzothiazole (ABT) into the g-C3N4 framework. Remarkably, up to 3.83-fold improvement in photocatalytic hydrogen evolution was realized at 0.8 wt% ABT incorporation. It shall be due to the broadened visible light absorption range (λ ≤ 700 nm) and accelerated charge carrier separation which originated from the ultrafast ICT (τ1 = 112.20 fs) between the benzothiazole group and heptazine ring. The boosted performance is highly associated with the purposely introduced D–A structure, which may shed light on designing of analogues with better photocatalytic hydrogen evolution performance.

Li metal is a promising anode material for next-generation energy storage systems owing to its high theoretical capacity and low potential. However, uncontrollable Li dendrite growth during Li plating and stripping results in low coulombic efficiencies and severe safety hazards. Herein, succinic anhydride (SA), an inexpensive and simple molecule, is investigated as a deposition-regulating additive. The relationship between the Li electrodeposition overpotential and the solvation structure of Li ions was systematically analyzed. Electrochemical tests and theoretical calculations indicate that strong complexation between Li+ and SA changes the solvation structure of Li+ and increases the energy barrier for Li deposition, resulting in a higher overpotential for Li electrodeposition. This increase in overpotential is conducive to generating more nucleation sites, reducing the Li nucleus size, and forming smooth Li deposits. XPS results also show that the addition of SA facilitates the formation of an improved SEI structure. Therefore, symmetric Li/Li cells with 3.0 wt% SA in the electrolyte exhibit excellent electrochemical performance over 300 cycles at 1.0 mA cm−2 with a capacity of 0.5 mA h cm−2. Enhanced cycling performance is also observed in Li/LiNi0.8Co0.1Mn0.1O2 full cells. Thus, SA can significantly alter the Li plating behavior, affording a promising strategy for suppressing Li dendrite growth in Li-metal-based batteries.

TMSCFX2 (X = Cl, Br; TMS = trimethylsilyl) have been developed as halofluorocarbene (CFX, X = Cl, Br) precursors for [2+1] cyclopropanation with alkenes. Structurally diverse halofluorocyclopropanes were obtained in good to excellent yields. It was found that the reactivity order of the three halofluorocarbene reagents (TMSCF2Br, TMSCFCl2, and TMSCFBr2) in halofluorocyclopropanation with 1,1-diphenylethylene can be very different under different reaction conditions.

Two new metal phosphate–oxalates (denoted SCU-26 and SCU-27) were prepared under solvent-free conditions using isonicotinic acid as a structure-directing agent. SCU-26 has a neutral layered structure showing intense blue-green luminescence with a high quantum yield of 28.35%. SCU-27 has an anionic layered structure with a high proton conductivity of 9.0 × 10−4 S cm−1 at 85 °C under 95% relative humidity.

Hypochlorous acid (HClO) is a significant signaling species which plays a decisive role in the immune system as an excellent defense against invasive bacteria. Therefore, it is significant to monitor HClO accurately and quickly in organisms. Herein, a new turn-on fluorescent probe (BM-HA) with a simple structure for rapid sensing of HClO is presented. BM-HA has favorable properties, including high selectivity, a large turn-on fluorescence signal (140-fold), and fast response (about 15 s). Additionally, quantum chemical calculations with DFT and TDDFT proved that reduced fluorescence of the BM-HA probe was possible due to the a-PET effect and the non-coplanarity of the coumarin and the benzothiazole. Furthermore, imaging in living cells and zebrafish indicates that the probe can potentially be used to detect HClO in complex biosystems.

Understanding the limitations of electrocatalytic activity and developing advanced catalysts with enhanced activity are of exceptional importance for future hydrogen energy applications. Due to the complexity of electrolytic hydrogen evolution in alkaline media, there are limited non-noble metal catalysts to afford large scale applications. Tungsten-based catalysts exhibit favorable stability but relatively low activity owing to their strong H* adsorption characteristics. In this work, cobalt hydroxides/cubic phase WN nanoparticles with strengthened interfaces and adjustable nitrogen vacancies anchored on multi-walled carbon nanotubes (Co(OH)2/c-WN1−x/CNTs) are exploited as highly efficient alkaline hydrogen evolution electrocatalysts, which exhibit remarkable activity with an overpotential of 78 mV at 10 mA cm−2 and a low Tafel slope of 43 mV dec−1 in 1 M KOH media. Density-functional theory calculations revealed that the interfacial combinations of Co(OH)2/c-WN1−x were tuned to facilitate the kinetics of hydrogen evolution, where Co(OH)2 promoted the adsorption of water molecules and the H–OH dissociation, and cubic phase WN with nitrogen vacancies (c-WN1−x) accelerated hydrogen generation by optimizing the hydrogen adsorption free energy.

A novel TiO2 thin film was prepared on the ceramic hollow fiber by the sol-gel method using poly(vinylpyrrolidone) (PVP) and polyvinyl alcohol (PVA) as additives. SEM images verified the formation of TiO2 layer with various thickness using different composition of titania sols. The effect of the PVP and PVA contents on the TiO2 sol properties, the separation and the antifouling performance of the ultrafiltration membranes were investigated thoroughly. When the contents of PVP and PVA were 1.0 wt% and 0.8 wt%, respectively, the resultant membrane showed a thickness of 0.55 μm with a pure water flux of 248 L m−2 h−1. In addition, the adherent foulant bovine serum albumin was applied to evaluate the antifouling performance. During the three fouling-recovery cycles, the flux recovery ratio and the flux decay ratio maintained about 99% and 30%. The BSA flux and rejection were still 169 L m−2 h−1 and 96.9% after the cycles, indicating a superior antifouling property.

Ibrutinib‐based combination therapy with high‐dose methotrexate (HD‐MTX) has recently shown clinical activity against relapse/refractory (R/R) primary central nervous system lymphoma (PCNSL). Herein, we report our real‐world experience of treating 11 newly diagnosed PCNSL patients with the ibrutinib/MTX combination. HD‐MTX was given at 3.5 g/m2 every 2‐week for eight doses. Ibrutinib was held upon HD‐MTX infusion until clearance and was administered daily post‐induction until disease progression, intolerable toxicity, or death. Nine out of 11 patients completed the induction phase and received ibrutinib as maintenance therapy. An objective response rate (ORR) of 82% (9/11) was observed including complete response (64%) and partial response (18%). The median progression‐free survival (PFS) was 7.4 months while the median overall survival (OS) was not reached. The ibrutinib/MTX combination was well tolerated in these treatment‐naïve PCNSL patients with an acceptable safety profile. Moreover, the longitudinal analysis of cerebrospinal fluid (CSF) circulating tumor DNA (ctDNA) revealed that CSF ctDNA detection was closely associated with tumor response, and sustained tumor responses correlated with the clearance of ctDNA from the CSF. In sum, our data not only demonstrated the clinical benefit of the ibrutinib and HD‐MTX combination regimen in treating newly diagnosed PCNSL patients in a real‐world setting, but also highlighted the significance of liquid biopsy including CSF ctDNA in tracing tumor burden and assessing treatment response., Our real‐world experience demonstrated the clinical benefit of the ibrutinib‐based combination therapy in treating newly diagnosed PCNSL patients, in complement to the activity of the drug combination reported for relapse/refractory PCNSL. Our data also underscored the clinical significance of liquid biopsy including cerebrospinal fluid ctDNA in tracing tumor burden and evaluating treatment response.

Identification of various emission sources and quantification of their contributions comprise an essential step in formulating scientifically sound pollution control strategies. Most previous studies have been based on traditional offline filter analysis of aerosol major components (usually inorganic ions, elemental carbon – EC, organic carbon – OC, and elements). In this study, source apportionment of PM2.5 using a positive matrix factorization (PMF) model was conducted for urban Shanghai in the Yangtze River Delta region, China, utilizing a large suite of molecular and elemental tracers, together with water-soluble inorganic ions, OC, and EC from measurements conducted at two sites from 9 November to 3 December 2018. The PMF analysis with inclusion of molecular makers (i.e., MM-PMF) identified 11 pollution sources, including 3 secondary-source factors (i.e., secondary sulfate; secondary nitrate; and secondary organic aerosol, SOA, factors) and 8 primary sources (i.e., vehicle exhaust, industrial emission and tire wear, industrial emission II, residual oil combustion, dust, coal combustion, biomass burning, and cooking). The secondary sources contributed 62.5 % of the campaign-average PM2.5 mass, with the secondary nitrate factor being the leading contributor. Cooking was a minor contributor (2.8 %) to PM2.5 mass while a significant contributor (11.4 %) to the OC mass. Traditional PMF analysis relying on major components alone (PMFt) was unable to resolve three organics-dominated sources (i.e., biomass burning, cooking, and SOA source factors). Utilizing organic tracers, the MM-PMF analysis determined that these three sources combined accounted for 24.4 % of the total PM2.5 mass. In PMFt, this significant portion of PM mass was apportioned to other sources and thereby was notably biasing the source apportionment outcome. Backward trajectory and episodic analysis were performed on the MM-PMF-resolved source factors to examine the variations in source origins and composition. It was shown that under all episodes, secondary nitrate and the SOA factor were two major source contributors to the PM2.5 pollution. Our work has demonstrated that comprehensive hourly data of molecular markers and other source tracers, coupled with MM-PMF, enables examination of detailed pollution source characteristics, especially organics-dominated sources, at a timescale suitable for monitoring episodic evolution and with finer source breakdown.

Background. Colitis-associated colorectal cancer (CAC) develops from active colonic inflammation, which is characterized by the production of proinflammatory cytokines that can induce mutations. IL-6 is produced by multiple cell types located within the tumor microenvironment including tumor-infiltrating immune cells, stromal cells, and the tumor cells themselves. The aim of our study was to explore the mechanism of Feng-Liao-Chang-Wei-Kang (FLCWK) and 5-fluorouracil (5-FU) in treating CAC. Method. HCT116 cells were treated with 5-FU in the absence or presence of FLCWK. Cell proliferation was assayed by MTT assays. Apoptosis and the cell cycle phases were detected by flow cytometry. Western blotting and Q-PCR assays were used to detect the expression levels of proteins and genes related to the IL-6/STAT3 signalling pathway. A mouse model for CAC was established by treating animals with 12.5 mg/kg azoxymethane (AOM) followed by 3 cycles of 2.5% dextran sodium sulphate (DSS). The associated pathological changes were determined after haematoxylin and eosin (H&E) staining. The expression of related proteins and genes in various tissues was examined using immunofluorescence techniques. Results. FLCWK enhanced the ability of 5-FU to promote apoptosis by inhibiting the proliferation of HCT116 cells and blocking the IL-6/STAT3 pathway. FLCWK combined with 5-FU reduced the number and size of colon tumors in mice with CAC and significantly increased their survival rate. In the CAC model, FLCWK synergized with 5-FU to inhibit the phosphorylation of STAT3, preventing IL-6/STAT3 signal transduction and thus further inducing apoptosis and inhibition of colon cancer cell proliferation. Conclusion. FLCWK can inhibit the activation of STAT3 by reducing the production of IL-6, thereby increasing the occurrence of colitis-related colorectal cancer with 5-FU.

Squid pen sample was treated by high hydrostatic pressure (HHP) prior to the extraction of chitosan. The physicochemical and antioxidant activities of the chitosan obtained with HHP (HHP-CS) were compared with chitosan of untreated squid pen sample (UT-CS). The chitosan extraction yield was optimized using response surface methodology, and the optimum condition was achieved at pressure of 500 MPa, extraction time of 10 min, and 1% (w/w) acetate concentration. The maximum yield of chitosan sample from the chitin of squid pens treated by HHP reached 81.9%. Among the process variables, the combined effects of pressure and acetate concentration significantly enhanced the extraction of chitosan from squid pens. The HHP-CS was found to be significantly effective in enhancing the fat binding capacity, water binding capacity, and water solubility index. SEM image analysis suggested that the HHP-CS had a rough surface with high porosity, while UT-CS exhibited a smooth surface. In vitro antioxidant assay suggested that HHP-CS had significantly higher DPPH radical scavenging activity, greater reducing power, and a stronger ferrous ion chelating effect than did UT-CS. Therefore, HHP can be an excellent alternative method for improving the physicochemical properties and antioxidant activities of chitosan from squid pens.

Discovering new functional genes, designing perfect crystal structures, and developing high-performance materials are the goals being pursued by scientists. Herein, the first antimony pyrophosphate, K2 Sb(P2 O7 )F, possessing an optimal layered structure, is reported, where the perfect structural arrangement induces excellent optical properties. K2 Sb(P2 O7 )F not only displays a sharply enhanced birefringence (0.157@546 nm) compared to the existing phosphate optical materials, but also exhibits a strong second-harmonic generation response (4.0×KDP). Remarkably, a new bifunctional gene, the square-pyramidal SbO4 F group, was discovered, and a unique two-dimensional arrangement of Cairo pentagonal tiling units was observed in inorganic compounds for the first time.

Discovering new functional genes, designing perfect crystal structures, and developing high performance materials are the goal being pursued by scientists. Herein, the first antimony pyrophosphate, K2Sb(P2O7)F, possessing an optimal layered structure is reported, where the perfect structure arrangement induces excellent optical properties. K2Sb(P2O7)F not only displays a sharply enhanced birefringence (0.157@546 nm) compared to the existing phosphate optical materials, but also exhibits a strong second-harmonic generation response (4.0 × KDP). Remarkably, a new bifunctional gene, the square pyramidal SbO4F group, was discovered and a unique 2D arrangement of Cairo pentagonal tiling units was observed in inorganic compounds for the first time.

Developing effective strategies to design novel, excellent birefringent materials has become an emerging challenge. Herein, we report a new UV nitrate birefringent material, CsHgNO3Cl2, which is an analogue of the known UV carbonate nonlinear optical crystal KCaCO3F. In CsHgNO3Cl2, a perfect layered structure was produced owing to the alliance of a planar π-conjugated anion NO3- and highly electropolarized Hg2+ cation. The optimized layered structure that is beneficial in enlarging the optical anisotropy induced a large birefringence (Δn = 0.145@546 nm) for CsHgNO3Cl2, even superior to that of the well-known commercial birefringent material α-BBO in the UV region. The strategy that the optimization of planar functional group arrangement is able to boost birefringence is expected to guide the development of high-performance birefringent materials in the future, especially in the field of UV.

Background. Pyroptosis, a novel form of inflammatory programmed cell death, was recently found to be a cause of mucosal barrier defect. In our pervious study, CD147 expression was documented to increase in intestinal tissue of inflammatory bowel disease (IBD). Objective. The aim of this study was to determine the function of serum CD147 in pyroptosis. Methods. The study group consisted of 96 cases. The centration of CD147, IL-1β, and IL-18 levels in serum was assessed by ELISA. Real-time PCR and WB were performed to analyze the effect of CD147 on pyroptosis. Results. In this study, our results showed that CD147 induced cell pyroptosis in intestinal epithelial cells (IECs) by enhancement of IL-1β and IL-18 expression and secretion in IECs, which is attributed to activation of inflammasomes, including caspase-1 and GSDMD as well as GSDME, leading to aggregate inflammatory reaction. Mechanically, CD147 promoted phosphorylation of NF-κB p65 in IECs, while inhibition of NF-κB activity by the NF-κB inhibitor BAY11-7082 reversed the effect of CD147 on IL-1β and IL-18 secretion. Most importantly, serum CD147 level is slightly clinically correlated with IL-1β, but not IL-18 level. Conclusion. These findings revealed a critical role of CD147 in the patients with IBD, suggesting that blockade of CD147 may be a novel therapeutic strategy for the patients with IBD.

Two new antimony fluoride sulfates named A6Sb4F12(SO4)3 (A = Rb, Cs) with unique crown-like clusters have been successfully synthesized by introducing Sb3+ with a stereochemically active lone pair in the sulfate system through a facile hydrothermal method. The structure regulation induced by the cation sizes results in the symmetry difference in these two title compounds, i.e., Rb6Sb4F12(SO4)3 crystallizing in the polar noncentrosymmetric (NCS) space group of P3 and Cs6Sb4F12(SO4)3 in the centrosymmetric (CS) space group of P1. Detailed characterizations, including XRD, thermal behaviors, optical properties, and the theoretical calculations, for these two compounds have been performed. The discovery of the unique crown-like clusters observed in A6Sb4F12(SO4)3 (A = Rb, Cs) enriches the diversity of structures for antimony sulfates systems. Simultaneously, a summary and comparison for all reported antimony halide sulfates has been made to illustrate the synergistic effect of the stoichiometric ratio and cation sizes on the macroscopic centricity and the framework structure, which will guide the systematical discovery of antimony(III)-based functional materials in future.

Alexithymia is a vulnerability factor for physical and mental illness that can significantly influence the daily function of alcohol-dependent patients. The aim of this study was to examine the indirect effect of obsessive thoughts and compulsive behaviors involving alcohol craving on the relationship between alexithymia, quality of life (QoL) of psychological well-being and health status. Three hundred and eighty-one outpatients (263 males and 118 females) in treatment for alcohol dependence completed self-report measures of alexithymia, alcohol craving, GHQ-28 (QoL-psychological well-being) and SF-36 (QoL-health status). Males scored significantly higher than females on aspects of alexithymia, and females reported significantly higher levels of alcohol craving. Path analysis showed an indirect effect of alcohol craving on the relationship between alexithymia, QoL-psychological well-being and self-reported QoL-health status for males only. The current study provides important new information about impaired self-reported health status and well-being among male alcohol-dependent treatment seekers with alexithymia.

A composite chloroaluminate ionic liquid (IL) modified with copper(I) chloride has attracted considerable attention due to its high catalytic activity and selectivity for isobutane alkylation, where the bimetallic anions of Cu(I)-Al(III) have been proposed to play important roles. Characterization of chloroaluminate and composite ionic liquids (CIL) is crucial for a better understanding of alkylation mechanism and catalysts design. In this work, a plasma-based ion source, direct analysis in real time (DART), was introduced to achieve soft but effective ionization of chloroaluminate IL and CIL with minimized hydrolysis, fragmentation and salt effects. Combined with the isotope patterns strategy and high-energy collision dissociation (HCD) technology, this developed high resolution mass spectrometry (HRMS) method, DART-Orbitrap-HRMS, was not only able to identify the accurate chemical composition of chloroaluminate IL and CIL, but also capable of structure analysis. Based on the comparison of chloroaluminate IL and CIL, it showed that similar acidic anions in both ILs were [AlCl4]−, [Al2Cl7]− and [Al3Cl10]−. The remarkable difference was the verification of Cu(I)-Al(III) bimetallic anions as [CuAlCl5]− and [CuAl2Cl8]− merely in CIL, which were proposed to count for the high catalytic activity. Moreover, Cu(I) cation ion that might be related to the alkylation selectivity was characterized as [(Et3NH)2CuCl2]+ in CIL. Structure analysis of the two bimetallic anions were then achieved by HCD technology. All the results have provided substantial support for the structure-activity study of CIL, setting the stage for in-depth research on IL-catalyzed isobutane alkylation.

Purpose The purpose of this study is to perform a retrospective analysis of disease outcomes and mutational profiles in patients with adult T-cell lymphoblastic lymphoma (T-LBL). Patients and methods A total of 43 patients were treated over a 9-year period at a single institution. The study examined treatment outcomes, clinical characteristics, and the use of circulating tumor DNA (ctDNA) and mutational profiling for patient diagnosis. Results The estimated overall survival (OS) and progression-free survival (PFS) time for all patients was 37.0 (95% CI: 17.7-56.2) and 28.1 (95% CI: 0.9-55.4) months, respectively. Chidamide maintenance was used in five patients exhibiting unfavorable genetic alterations, with no evidence of relapse. Next-generation sequencing of pretreatment tumor tissue was undertaken for 15 patients. NOTCH1 mutations were the most frequent genetic alterations, followed by mutations in PHF6, TP53, JAK1, JAK3, PTEN, and DNM2. The genetic profile of the blood was similar to that of the tumor. Kappa coefficient analysis (14 patients, 56 time points, kappa = 1.0, p = 0.00) indicated a 92.6% agreement between ctDNA response and tumor volume measurements at post treatment when compared with baseline. Detection of ctDNA predicted disease relapse in two patients. Conclusion The prognosis of patients with adult T-LBL remains very poor. Detection of tumor-associated sequences in ctDNA may be an effective method for diagnosing T-LBL and measuring treatment efficacy. Incorporation of new drugs such as histone deacetylase inhibitors (HDACi)has the potential to improve outcomes in these patients.

DNA-modified lanthanide-doped upconversion nanoparticles (DNA-UCNPs) that combine the functions of DNA and the optical features of UCNPs have shown great promise in a wide range of fields. However, challenges remain in precisely tethering and orienting the DNA strands on the UCNP surface. Herein, we systematically investigate the sequence dependence of DNAs in their interactions with UCNPs, and reveal that poly-cytosine (poly-C) has high affinity for the UCNP surface. A general approach to synthesize monodispersed DNA-UCNP conjugates is developed using poly-C-containing diblock DNA strands. The poly-C segment of the DNA strand binds to the surfaces of UCNPs and the second segment is oriented perpendicularly on the UCNP surface, making the DNA-UCNPs highly stable and monodispersed in aqueous solution. The dense layer of DNA on the UCNP surface enables the programmable assembly of UCNPs with other DNA-functionalized nanoparticles or DNA origamis through hybridization, resulting in the formation of well-organized complex structures.

Variations in the taste quality of no-added-nitrite Chinese bacon (unsmoked) during processing were investigated using 1 H-NMR and multivariate data analysis. The results showed that 21 metabolites were dominant during processing, which involved marinating, air-drying, fermentation, and baking, including amino acids, sugars, organic acids, nucleic acids and their derivatives, and alkaloids. The contents of isoleucine, leucine, valine, alanine, acetate, glutamate, succinate, glycine, sucrose, tyrosine, and phenylalanine increased continuously throughout the process. The lactate, creatine, carnosine, betaine, taurine, hypoxanthine, and AMP contents all significantly increased after baking; the inosine content significantly increased after fermentation and then decreased; the histamine content significantly increased after air-drying and then decreased; and the histidine content decreased. Each processing treatment promoted taste formation in no-added-nitrite Chinese bacon (unsmoked), especially baking. The baking point owned relatively higher levels of metabolites and sensory evaluation compared to other treatments. Sensory evaluation revealed that the ultimate taste of Chinese bacon (unsmoked) at the end of baking tended toward umami (glutamate), sweetness (AMP), and sourness (lactate). The first and second principal components explained 74.0% and 13.4% of the variables, respectively. These findings indicated the potential of NMR-based metabolomics for assessing the taste quality of no-added-nitrite Chinese bacon (unsmoked), which could contribute to a better understanding of taste compound changes in meat products. PRACTICAL APPLICATION: Nitrite is commonly used in Chinese bacon (unsmoked), but excessive intake is not good for human health. Nitrite has been replaced with nitrite substitutes to prepare no-added-nitrite Chinese bacon (unsmoked). The metabolites of no-added-nitrite Chinese bacon (unsmoked) were detected to determine the key treatment that contributes to the formation of taste during processing. This study determined the main taste components of no-added-nitrite Chinese bacon (unsmoked) and its formation process, which provides new insight into the production and characteristics of flavor in Chinese bacon (unsmoked).

Developing efficient carbon-based metal-free electrocatalysts can bridge the gap between laboratory studies and practical applications of CO2 reduction. However, along with the ambiguous understanding of the active sites in carbon-based electrocatalysts, carbon-based electrocatalysts with high selectivity and satisfactory stability for electroreduction of CO2 remain rare. Here, using the nitrogen rich silk cocoon as a precursor, carbon-based electrocatalysts with intrinsic defects can be prepared for efficient and long-term electroreduction of CO2 by a simple two-step carbonization. The obtained electrocatalyst can catalyze CO2 reduction to CO with a Faradaic efficiency of ~ 89% and maintain good selectivity for about 10 days. Particularly, our experimental studies suggest that in-plane defects are the main active sites on which the rate-determining step for CO2 reduction should be the direct electron transfer to CO2 but not the proton-coupled electron transfer. Further theoretical calculations consistently demonstrate that the intrinsic defects in carbon matrix, particularly the pentagon-containing defects, act as main active sites to accelerate the direct electron transfer for CO2 reduction. In addition, our synthetic approach can convert egg white into efficient catalysts for CO2 electroreduction. These findings, providing new insights into the biomass-derived catalysts, should pave the way for fabricating efficient and stable carbon-based electrocatalysts with catalytically active defects by using naturally abundant precursors.

Novel red Zn(ii) complex-based fluorescent probes featuring cryptolepine-curcumin derivatives, namely, [Zn(BQ)Cl2] (BQ-Zn) and [Zn(BQ)(Cur)]Cl (BQCur-Zn), were developed for the simple and fluorescent label-free detection of apoptosis, an important biological process. The probes could synergistically promote mitochondrion-mediated apoptosis and enhance tumor therapeutic effects in vitro and vivo.

Sepsis is an infection-induced systemic inflammatory syndrome. The immune response in sepsis is characterized by the activation of both proinflammatory and anti-inflammatory pathways. When sepsis occurs, the expression and activity of many inflammatory cytokines are markedly affected. Xenobiotic receptors are chemical-sensing transcription factors that play essential roles in the transcriptional regulation of drug-metabolizing enzymes (DMEs). Xenobiotic receptors mediate the functional crosstalk between sepsis and drug metabolism because the inflammatory cytokines released during sepsis can affect the expression and activity of xenobiotic receptors and thus impact the expression and activity of DMEs. Xenobiotic receptors in turn may affect the clinical outcomes of sepsis. This review focuses on the sepsis-induced inflammatory response and xenobiotic receptors such as pregnane X receptor (PXR), aryl hydrocarbon receptor (AHR), glucocorticoid receptor (GR), and constitutive androstane receptor (CAR), DMEs such as CYP1A, CYP2B6, CYP2C9, and CYP3A4, and drug transporters such as p-glycoprotein (P-gp), and multidrug resistance-associated protein (MRPs) that are affected by sepsis. Understanding the xenobiotic receptor-mediated effect of sepsis on drug metabolism will help to improve the safe use of drugs in sepsis patients and the development of new xenobiotic receptor-based therapeutic strategies for sepsis., Graphical abstract The functional crosstalk between sepsis and drug metabolism is mediated by xenobiotic receptors. The inflammatory cytokines released during sepsis can affect the expression and activity of xenobiotic receptors and thus impact the expression and activity of DMEs.Image 1

Rapid sulfate formation is recognized as a key characteristic of severe winter haze in China. However, air quality models tend to underestimate sulfate formation during heavy haze periods, and heterogeneous formation pathways have been proposed as promising mechanisms to reduce gaps between observation and model simulation. In this study, we implemented a reactive SO2 uptake mechanism through the SO2+NO2 heterogeneous reactions in the Comprehensive Air Quality Model with Extensions (CAMx) to improve simulation of sulfate formation in the Yangtze River Delta (YRD) region. Parameterization of the SO2+NO2 heterogeneous reactions is based on observations in Beijing and considered both the impact of relative humidity and aerosol pH on sulfate formation. Ammonia is reported to be critical for the formation of secondary inorganic aerosols. Estimation of ammonia emissions is usually associated with large uncertainties and models tend to underestimate ammonia concentrations substantially. Sensitivity tests were conducted to evaluate the influence of the SO2+NO2 heterogeneous reactions as well as ammonia emissions on modeled sulfate concentrations during a period with several heavy haze episodes in the YRD region. Base case model results show large underestimation of sulfate concentrations by 36 % under polluted conditions in the YRD region. Adding the SO2+NO2 heterogeneous reactions or doubling ammonia emissions alone leads to slight model improvement ( ∼6 %) on simulated sulfate concentrations in the YRD region. However, model performance significantly improved when both the SO2+NO2 heterogeneous reactions and doubled ammonia emissions were included in the simulation: predicted sulfate concentrations during polluted periods increased from 23.1 µ g m −3 in the base scenario to 29.1 µ g m −3 (representing an increase of 26 %). Aerosol pH is crucial for the SO2+NO2 heterogeneous reactions, and our calculated aerosol pH is always acidic and increased by 0.7 with doubled ammonia emissions. Modeling results also show that this reactive SO2 uptake mechanism enhanced sulfate simulations by 1 to 5 µ g m −3 for the majority of the eastern and central parts of China, with more than 20 µ g m −3 increase in sulfate concentrations over the northeastern plain. These findings suggest that the SO2+NO2 heterogeneous reactions could be potentially important for sulfate formation in the YRD region as well as other parts of China. Further studies are needed to constrain the uncertainties associated with the parameterization of the SO2+NO2 heterogeneous reactions based on local data as well as to evaluate this mechanism in other regions. In addition, ammonia emissions were found to be a key driving variable of the spatial patterns of sulfate enhancement due to the new pathway. Substantial efforts are needed to improve the accuracy of the ammonia emission inventory.

The effect of polyethylene packaging (PEP) in air cushion and vacuum packaging (VP) on histamine related to the quality of Japanese Spanish mackerel (JS mackerel) was studied with samples stored at -20, 4, 15, and 25°C. The aerobic plate count (APC), total volatile basic nitrogen (TVBN), and histamine concentrations of the PEP and VP samples stored at 25°C increased as the storage time continued. The PEP and VP samples stored at temperatures below 15°C showed lower levels of APC, TVBN, and histamine, with VP samples having considerably lower levels of APC, TVBN, and histamine than PEP samples. For the frozen JS mackerel stored at -20°C for 2 months and then thawed and stored at 25°C, the VP treatment delayed the increases of TVBN and histamine longer than did the PEP treatment. Thus, the storage of VP JS mackerel at temperatures below 4°C could prevent quality deterioration and extend shelf life.

Summary: The direct functionalization of C(sp3)-H bonds has led to the development of methods to access molecules or intermediates from basic chemicals in an atom- and step-economic fashion. Nevertheless, achieving high levels of chemo-, regio-, and enantioselectivity in these reactions remains challenging due to the ubiquity and low reactivity of C(sp3)-H bonds. Herein, we report an unprecedented protocol for enantioselective cyanation of remote C(sp3)-H bonds. With chiral Box-Cu complex as the catalyst, the reaction of N-fluorosulfonamide furnishes the corresponding products in excellent yields and high enantiomeric excess (ee) under mild reaction conditions. A radical relay pathway involving 1,5-hydrogen atom transfer (1,5-HAT) of N-center radicals followed by enantioselective cyanation of the in situ-formed benzyl radicals is proposed. This enantioselective copper-catalyzed cyanation thus offers insights into an efficient way for the synthesis of bioactive molecules for drug discovery. : Catalysis; Organic Synthesis; Stereochemistry Subject Areas: Catalysis, Organic Synthesis, Stereochemistry

Copper-containing ZSM-5 zeolite can facilitate the direct oxidation of methane to form methanol under mild condition with high selectivity. However, due to the limitation of the experimental characterization, the identification of the catalytic sites in Cu-exchanged zeolites still remains unclear. Herein, the reactivity of different [CuxOy] (x = 1, 2, 3; y = 1, 2, 3)- and [CuOH]+-ZSM-5 active sites towards methane partial oxidation process has been elucidated by using density functional theory (DFT) calculations. It is indicated that: i) C–H activation over five different active sites obeys the radical mechanism, and the reactivity follows the sequence: copper-oxyl [CuO]+ (S = 1) > tricopper [Cu3O3]2+ (S = 3/2) > bis-(μ-oxo)-dicopper [Cu2O2]2+ (S = 1) > mono-(μ-oxo)-dicopper [CuOCu]2+ (S = 1) > mono-copper [CuOH]+ (S = 1/2); ii) The rate constants for C–H bond cleavage of methane at the reaction temperature are faster at the higher temperature; iii) The descriptors for C–H activation of methane on [CuxOy] (x = 1˜3, y = 1˜3)- and [CuOH]+-ZSM-5 have been established, for which the active site with more spin density and less negative charge will induce the lower activation barriers for C–H activation of methane. Meanwhile, the stronger hydrogen affinity of the active site is, the lower the activation barriers of methane C–H activation will be. Taken the stability and activation barrier together, the catalytic performance of copper-oxyl site has been enhanced by the presence of water.

The chemical profile and the phytotoxicity of Artemisia absinthium essential oil (EO) were investigated to evaluate its potential value as a biopesticide for food safety purposes. A total of 54 compounds were identified in A. absinthium EO, with the most abundant constituents being eucalyptol (25.59%), linalool (11.99%), and β-myrcene (10.05%). The EO, linalool, and a mixture of three major components exhibited potent suppressive activity against four receiver species; however, eucalyptol and β-myrcene showed a much weaker effect. Bioassay-guided fractionation led to the isolation of linalool as the major active compound responsible for the EO's phytotoxicity. Subsequent scanning electron microscopy (SEM) analysis revealed that linalool significantly inhibited root-hair formation and metaxylem development. This is the first report on the determination of linalool as the major active phytotoxic compound in A. absinthium EO, as well as the elucidation of its mechanism of phytotoxicity from the perspective of root structure changes in the receiver species. Our results suggest that both the EO and its major constituents have potential value as environmentally friendly herbicides.

A trend in large yellow croaker (Larimichthys crocea) aquaculture is to establish new production sites that are suitable for extreme weather conditions. However, continuous and strong currents can harm fish welfare. To determine the location of the net cage, it is necessary to assess the swimming ability of large yellow croaker. Currently, our research on large yellow croakers is focusing on behavior analysis. This article investigates the effect of swimming large yellow croakers on metabolites in the body by examining the preferred speed of the group and the endurance swimming ability of single-tailed fish. We evaluated the factors that influence the large yellow croaker’s swimming fatigue by quantifying the content of metabolites and constructed the endurance swimming model using those results. Various results showed large yellow croaker populations tend to grow in low-velocity environments, and this matches their traditional habitat. The samples were taken at different swimming times at a flow rate of 0.35 m/s. According to the results of the metabolite content determination, blood glucose levels is closely related to swimming ability in large yellow croakers. The content of liver glycogen, which regulates blood glucose concentration, decreases in a certain linear relationship. The endurance swimming model of large yellow croaker was constructed according to the changes of liver glycogen content. The goals of this article are to provide a deeper understanding of the physiological characteristics of large yellow croaker swimming, and to provide a reference for choosing fishing and cage sites for large yellow croaker.

Herbaspirillum camelliae WT00C is a gram-negative endophyte isolated from the tea plant. It has an intact selenate metabolism pathway but poor selenate tolerability. In this study, microbiological properties of the strain WT00C were examined and compared with other three strains CT00C, NCT00C and NT00C, which were obtained respectively from four, six and eight rounds of 24-h exposures to 200 mM selenate. The selenate tolerability and the ability to generate red elemental selenium (Se0) and selenoproteins in H. camelliae WT00C has significantly improved by the forced evolution via 4–6 rounds of multiple exposures a high concentration of selenate. The original strain WT00C grew in 200 mM selenate with the lag phase of 12 h and 400 mM selenate with the lag phase of 60 h, whereas the strains CT00C and NCT00C grew in 800 mM selenate and showed a relatively short lag phase when they grew in 50–400 mM selenate. Besides selenate tolerance, the strains CT00C and NCT00C significantly improved the biosynthesis of red elemental selenium (Se0) and selenoproteins. Two strains exhibited more than 30% selenium conversion efficiency and 40% selenoprotein biosynthesis, compared to the original strain WT00C. These characteristics of the strains CT00C and NCT00C make them applicable in pharmaceuticals and feed industries. The strain NT00C obtained from eight rounds of 24-h exposures to 200 mM selenate was unable to grow in ≥ 400 mM selenate. Its selenium conversion efficiency and selenoprotein biosynthesis were similar to the strain WT00C, indicating that too many exposures may cause gene inactivation of some critical enzymes involving selenate metabolism and antioxidative stress. In addition, bacterial cells underwent obviously physiological and morphological changes, including gene activity, cell enlargement and surface-roughness alterations during the process of multiple exposures to high concentrations of selenate.

The chemical profile and allelopathic action of the volatiles produced by Artemisia selengensis were studied. Artemisia selengensis was found to release volatile chemicals to the environment to influence other plants' growth, which suppressed the root length of Amaranthus retroflexus and Poa annua by 50.46 % and 87.83 % under 80 g/1.5 L treatment, respectively. GC/MS analysis led to the identification of 41 compounds (by hydrodistillation, HD) and 48 compounds (by headspace solid-phase microextraction, HS-SPME), with eucalyptol (15.45 % by HD and 28.09 % by HS-SPME) being detected as the most abundant constituent. The essential oil (EO) of A. selengensis completely inhibited the seed germination of A. retroflexus and P. annua at 1 mg/mL and 0.5 mg/mL, respectively. However, eucalyptol displayed much weaker activity compared with the EO, indicating that other less abundant constituents might contribute significantly to the EO's activity. Our study is the first report on the phytotoxicity of A. selengensis EO, suggesting that A. selengensis might release allelopathic volatile agents into the environment that negatively affect other plants' development so as to facilitate its own dominance; the potential value of utilizing A. selengensis EO as an environmentally friendly herbicide is also discussed.