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Catalytic methane decomposition (CMD) is a promising route for H2 production. In this paper, MOF-derived hierarchical carbon catalysts were prepared by the carbonization of ZIF-8 with additional carbon source and used for CMD. The effects of carbonization temperature, reaction temperature, and the kinds of additional carbon sources on the structure of derived carbon materials and their catalytic performances were studied. The results showed that the morphology and textural properties can be improved by varying the carbonization temperature and additional carbon source. The specific surface area of the ZIF-derived carbon can be significantly increased, and the hierarchical pore structure with improved pore size distribution can be obtained, which leads to good performances for CMD. Catalytic performance can be obviously enhanced by increasing the reaction temperature. The C950-FA prepared by carbonization of ZIF-8 with furfuryl alcohol as additional carbon source exhibits the highest initial conversion of methane (64%) and good stability at 890 °C. About 11% methane conversion was kept after 2750 min. This study provides a new route for the preparation of carbon material catalysts to achieve high-efficient conversion of methane.

Co-pyrolysis of coke bottle (CB) with sawdust/cellulose/lignin was conducted at 700 °C in this study, aiming to understand the potential influence of interactions of the volatiles of the varied origins on properties of the char. The results indicated that the interaction of volatiles from CB with that from biomass enhanced cross-polymerization of the volatiles, decreasing the formation of gases while enhanced the formation of both char and oil. The cross-interactions of the intermediates also diminished the formation of π-conjugated organics. In addition, the varied volatiles from the pyrolysis of cellulose, lignin, or sawdust interacted with that from CB and affected the properties of char in different ways. The char from the co-pyrolysis of sawdust/CB was more aliphatic, and had a higher oxygen content (7.3%) and higher polarity but lower thermal stability. Additionally, the thermal stability, crystallinity as well as the evolution of functionalities of char versus increasing temperature were also significantly affected by the cross-interactions of the volatiles.

Little is known about the benefit-risk profile of second-generation androgen receptor inhibitors in older men with non-metastatic castration-resistant prostate cancer. We aimed to examine the efficacy and safety of second-generation androgen receptor inhibitors in men aged 80 years or older with non-metastatic castration-resistant prostate cancer.We searched for all randomised controlled clinical trials evaluating second-generation androgen receptor inhibitors in patients with non-metastatic castration-resistant prostate cancer submitted to the US Food and Drug Administration before Aug 15, 2020, and pooled data from three trials that met the selection criteria. All three trials enrolled patients who were aged 18 years or older with an Eastern Cooperative Oncology Group performance status of 0-1, castration-resistant prostate cancer, prostate-specific antigen (PSA) 2·0 μg/L or greater, PSA doubling time of 10 months or less, and no evidence of distant metastatic disease on conventional imaging per the investigator's assessment at the time of screening. All patients had histologically or cytologically confirmed adenocarcinoma of the prostate without neuroendocrine differentiation or small-cell features. All patients who were randomly assigned to androgen receptor inhibitor or placebo groups in these trials were considered assessable and were included in this pooled analysis. We evaluated the effect of age on metastasis-free survival and overall survival across age groups (80 years vs ≥80 years) in the intention-to-treat population. Safety analyses were done in patients who received at least one dose of study treatment.Between Oct 14, 2013, and March 9, 2018, 4117 patients were assigned to androgen receptor inhibitor (apalutamide, enzalutamide, or daralutamide; n=2694) or placebo (n=1423) across three randomised trials. The median follow-up duration for metastasis-free survival was 18 months (IQR 11-26) and for overall survival was 44 months (32-55). In patients aged 80 years or older (n=1023), the estimated median metastasis-free survival was 40 months (95% CI 36-41) in the androgen receptor inhibitor groups and 22 months (18-29) in the placebo groups (adjusted hazard ratio [HR] 0·37 [95% CI 0·28-0·47]), and the median overall survival was 54 months (50-61) versus 49 months (43-58), respectively (adjusted HR 0·79 [0·64-0·98]). In patients younger than 80 years of age (n=3094), the estimated median metastasis-free survival was 41 months (95% CI 36-not estimable [NE]) in the androgen receptor inhibitor groups and 16 months (15-18) in the placebo groups (adjusted HR 0·31 [95% CI 0·27-0·35]), and the median overall survival was 74 months (74-NE) versus 61 months (56-NE), respectively (adjusted HR 0·69 [0·60-0·80]). In patients aged 80 years or older, grade 3 or worse adverse events were reported in 371 (55%) of 672 patients in the androgen receptor inhibitor groups and 140 (41%) of 344 patients in the placebo groups, compared with 878 (44%) of 2015 patients in the androgen receptor inhibitor groups and 321 (30%) of 1073 patients in the placebo groups among patients younger than 80 years. The most common grade 3-4 adverse events were hypertension (168 [8%] of 2015 patients aged80 years and 51 [8%] of 672 patients aged ≥80 years in the androgen receptor inhibitor groups vs 53 [5%] of 1073 patients aged80 years and 22 [6%] of 344 patients aged ≥80 years in the placebo groups) and fracture (61 [3%] and 36 [5%] in the androgen receptor inhibitor groups vs 15 [1%] and 11 [3%] in the placebo groups).The findings of this pooled analysis support the use of androgen receptor inhibitors in older men with non-metastatic castration-resistant prostate cancer. Incorporating geriatric assessment tools in the care of older adults with non-metastatic castration-resistant prostate cancer might help clinicians to offer individualised treatment to each patient.None.

Oxides with different crystal phases can have important effects on the configuration of surface atoms, which can further affect the distribution of hydrogenation sites and acidic sites as well as the competitions of these varied types of catalytic sites. This could be potentially used to tailor the distribution of the products. In this study, zirconium oxides with different crystal phases supported copper catalysts were prepared for the hydrogenation of the biomass-derived furfural, vanillin, etc. The results showed that both calcination temperature and Cu species affected the shift of zirconia from tetragonal phase to the monoclinic phase. Monoclinic zirconia supported copper catalyst can effectively catalyze the hydrogenation of furfural to furfuryl alcohol via hydrogenation route due to its low amount of Bronsted acidic sites, although the surface area and the exposed metallic Cu surface area were much lower than the tetragonal zirconia supported copper catalyst. Zirconia with tetragonal or tetragonal/monoclinic phases supported copper catalysts contain abundant acidic sites and especially the Bronsted acidic sites, which catalyzed mainly the conversion of furfural via the acid-catalyzed routes such as the acetalization, rather than the hydrogenation. The acidic sites over the Cu/ZrO2 catalyst played more predominant roles than the hydrogenation sites in determining the conversion of the organics like furfural and vanillin.

Xia Han,1,&ast; Xiaotang Liang,2,&ast; Menghai Wu,1 Lijun Zhang,1 Honglei Jiang2 1Department of Cardiology, Jinan People’s Hospital Affiliated to Shandong First Medical University, Laiwu, 271199, People’s Republic of China; 2Shandong Second Provincial General Hospital, Jinan, Shandong Province, 250000, People’s Republic of China&ast;These authors contributed equally to this workCorrespondence: Honglei JiangShandong Second Provincial General Hospital, No. 4, Xingxi Street, Jinan, Shandong Province, 250000, People’s Republic of ChinaEmail jianghl_sd@21cn.comObjective: To evaluate the associations of genetic variants of the miR-217 gene with coronary artery disease (CAD) risk, as well as plasma level of vascular endothelial growth factor (VEGF).Methods: A case–control study with 498 CAD patients and 499 frequency-matched healthy controls was conducted to evaluate the associations of four tagSNPs of the miR-217 gene, including rs6724872, rs4999828, rs10206823, and rs41291177, with CAD risk and plasma level of VEGF.Results: SNP rs6724872 and rs4999828 were significantly associated with increased risk of CAD (P value was smaller than 0.05 even after Bonferroni multiple adjustment). Compared with the G allele, C allele of rs6724872 was significantly associated with 1.73-fold increased risk of CAD (95% CI: 1.25– 2.39; P = 0.001). While C allele of rs4999828 was significantly associated with 1.75-fold increased risk of CAD, compared with T allele (95% CI: 1.34– 2.29; P = 4 × 10− 5). Meanwhile, rs6724872 and rs4999828 were also significantly associated with higher level of VEGF (P < 0.001).Conclusion: These findings highlighted the important role of genetic variants of the miR-217 gene in the pathogenesis of CAD and potential targets for intervention.Keywords: coronary artery disease, miR-217, VEGF, genetic

Pentanediols (1,2-pentanediol and 1,5-pentanediol) are important feedstock for synthesis of fine chemicals, production of which from the biomass-derived furfural or furfuryl alcohol (FA) has been considered as a sustainable route and attracted much interest. In this study, the catalysts with Ni–Fe as the metal sites and Mg–Al layered double hydroxides (LDH) as precursor of support were synthesized. The results showed that the presence of Fe in catalyst affected both the development of the pores of the catalyst and the catalytic behaviors of nickel species. A low Fe content facilitated formation of mesoporous structure, but the higher content destroyed the LDH structure, resulting in a decreased surface area. Fe could also react with metallic Ni to form NiFe alloy. This decreased the catalytic activity for the further hydrogenation of the furan ring in FA, and FA would thus have the chance to produce pentanediols via hydrogenolysis. The In-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy characterization of hydrogenation of FA indicated that the alloying between Fe and Ni resulted in a weak adsorption of C C group in furan ring and moderate adsorption of C–O–C group, which suppressed the complete hydrogenation of FA while facilitated the ring-opening of FA to form the pentanediols.

For heterojunction composite photocatalyst, intimate contact interface is the key to the carrier transfer separation conditions. Due to the interface contact, the electron transfer rate between catalysts can be increased during photocatalytic hydrogen production, therefore, we design the close contact of 0D/2D heterojunction, which greatly enhanced the photocatalytic hydrogen production activity of the composite catalyst. The composite catalyst WO3/CoP was obtained by simple high temperature in situ synthesis. Moreover, it was proved by photoelectric chemistry and fluorescence tests that appropriate conduction band and valence band locations of WO3 and CoP provided a favorable way for thermodynamic electron transfer. In addition, fluorescence results showed that WO3 load effectively promoted photoelectron-hole transfer and increased electron lifetime. The formation of S-scheme heterojunctions can make more efficient use of useful photogenerated electrons and prevent the photogenerated electron-hole recombination of CoP itself, further promote the liveness of photocatalytic H2 evolution. Meanwhile, the study of Metal-organic frameworks (MOFs) materials further promoted the application of MOFs derivatives in the field of photocatalytic hydrogen evolution, and provided a reference for the rational design of composite catalysts for transition metal phosphide photocatalysts.

Semi-volatile organic compounds (SVOCs) include polycyclic aromatic hydrocarbons (PAHs), phthalic acid esters (PAEs), organochlorine pesticides (OCPs) and nitrobenzenes (NBs). Most of them have carcinogenic, teratogenic, mutagenic and endocrine disrupting effects. Therefore, rapid and accurate determination of SVOCs in water is very important. As the most traditional pretreatment method, liquid-liquid extraction (LLE) has the advantages of wide extraction range, high extraction efficiency, simple operation and lower cost, which is very suitable for the simultaneous extraction of multiclass SVOCs. Dichloromethane has good solubility for most SVOCs, and is slightly soluble in water with low boiling point. It is a good broad-spectrum extractive solvent of organic compounds. But at present, there is no detection standard of SVOCs in water in China. In this study, three factors including nitrogen blowing temperature, pH of water sample and extraction time were optimized. It was aimed to establish a liquid-liquid extraction-gas chromatography-mass spectrometry (GC-MS) method for the simultaneous determination of the 46 SVOCs in water. At first, the effect of nitrogen blowing temperature (30, 35, 40 ℃) was investigated. The results showed that under different nitrogen blowing temperature, the recoveries of the 46 SVOCs were slightly different, but the differences were not significant. Considering the recovery and concentration efficiency, the nitrogen blowing temperature was finally set at 35 ℃. Dichloromethane was selected as the LLE solvent of the SVOCs and its extraction efficiency was investigated. The recoveries of the 46 SVOCs were satisfactory for the determination. Then sample pH (neutral and alkaline condition) was investigated. Most of the SVOCs in this paper have no obvious acid-base property. The extraction effect of water sample under neutral conditions was the best and the most stable, and under alkaline condition, the recovery of each substance was generally low. Finally, extraction time (7, 10, 15 min) was studied. In a certain range, with the increase of extraction time, the recovery also increased, but when the time increased to 15 min, the recovery of some compounds increased or decreased, and the time-consuming was longer, the recovery of most substances could meet the requirements when the extraction time was set to 10 min. The optimized experimental conditions were determined as follows: under neutral conditions, the water sample was extracted by dichloromethane for three times, each extraction time was 10 min, and concentrated at the nitrogen blowing temperature of 35 ℃. GC-MS was used for detection, and internal standard method was used for quantitative analysis. The results showed that the linearity of the method was good in the range of 20-2000 μg/L, the correlation coefficients (r2) were no less than 0.9916, the limits of detection (LODs, S/N=3) ranged from 0.28 to 16.55 ng/L, and the limits of quantification (LOQs, S/N=10) ranged from 0.92 to 55.16 ng/L. The average recovery was 63.6%-125% at three spiked levels of 0.02, 0.2, 0.4 μg/L, with the relative standard deviations (n=6) ranging from 1.03% to 17.0%. This method was applied for the determination of 27 surface water samples in Jinan section of the Yellow River. The pollutants were mainly PAEs and PAHs, while NBs were not detected, only two kinds of OCPs were detected at some sites. The method is simple, universal, accurate and precise, and has low detection limit. It is suitable for the simultaneous determination of the 46 SVOCs in surface water and groundwater.

A discovery program targeting respiratory syncytial virus (RSV) identified C-nucleoside 4 (RSV A2 EC50 = 530 nM) as a phenotypic screening lead targeting the RSV RNA-dependent RNA polymerase (RdRp). Prodrug exploration resulted in the discovery of remdesivir (1, GS-5734) that is >30-fold more potent than 4 against RSV in HEp-2 and NHBE cells. Metabolism studies in vitro confirmed the rapid formation of the active triphosphate metabolite, 1-NTP, and in vivo studies in cynomolgus and African Green monkeys demonstrated a >10-fold higher lung tissue concentration of 1-NTP following molar normalized IV dosing of 1 compared to that of 4. A once daily 10 mg/kg IV administration of 1 in an African Green monkey RSV model demonstrated a >2-log10 reduction in the peak lung viral load. These early data following the discovery of 1 supported its potential as a novel treatment for RSV prior to its development for Ebola and approval for COVID-19 treatment.

Biomass and pig manure have distinct compositions and the co-pyrolysis of them has gained much attention. However, the influence of volatiles interaction on the properties of the char was still unclear. In this study, lignin was selected as the model component of biomass with pig manure for co-pyrolysis at 600 °C. The results indicate that volatiles from co-pyrolysis promoted re-condensation reaction, resulting in the higher char yield (48.0% in co-pyrolysis versus 31.0% in pyrolysis of single manure) and the formation of more aromatics in bio-oil. The co-pyrolysis also facilitated the dehydrogenation and dehydration reactions, which accounted for the elimination of oxygen and nitrogen contents and thus a higher carbon content (64.7% in the co-pyrolysis versus the averaged value of 46.4% from the pyrolysis of single feedstock), higher crystallinity and thermal stability of the char. The in-situ diffuse reflection infrared Fourier transform spectroscopy (DRIFTS) characterization results demonstrated that the functionalities abundances of char with temperature was influenced by volatiles interaction via accelerating the carbonization reaction. In addition, the high heating value (HHV) of char was obviously improved by cross-interaction of volatiles during co-pyrolysis (24.4 MJ/Kg in co-pyrolysis versus averaged value of 15.1 MJ/Kg from single pyrolysis), implying that the co-pyrolysis enhanced the energy density of the resulting char.

Chemical dealloying is an emerging strategy that can be applied to synthesize porous materials. The structure morphologies of the active materials were precisely regulated by designing the various NaOH corrosion solutions. Three-dimensional micro–nanorods-like structure Ni75Cu25O bimetallic oxide with ultra-high electrochemical properties have been obtained, which used Al65Cu15Ni20 precursors through a dealumination strategy. Meanwhile, three-dimensional micro–nanorods-like structure Ni75Cu25O demonstrates an unusual extraordinary specific capacitance (16.96 F cm−2 at 10 mV s−1) and excellent cycling stability (100.8% retention after 5000 cycles at 10 mV s−1). Here, the transition bimetallic oxides by using the dealloying strategy can be applied to develop novel guidances and ideas for the generation of energy storage devices.

Isocitrate dehydrogenase (IDH) mutations are common genetic alterations in myeloid disorders, including acute myeloid leukemia (AML) and myelodysplastic syndrome (MDS). Epigenetic changes, including abnormal histone and DNA methylation, have been implicated in the pathogenic build-up of hematopoietic progenitors, but it is still unclear whether and how IDH mutations themselves affect hematopoiesis. Here, we show that IDH1-mutant mice develop myeloid dysplasia in that these animals exhibit anemia, ineffective erythropoiesis, and increased immature progenitors and erythroblasts. In erythroid cells of these mice, D-2-hydroxyglutarate, an aberrant metabolite produced by the mutant IDH1 enzyme, inhibits oxoglutarate dehydrogenase activity and diminishes succinyl–coenzyme A (CoA) production. This succinyl-CoA deficiency attenuates heme biosynthesis in IDH1-mutant hematopoietic cells, thus blocking erythroid differentiation at the late erythroblast stage and the erythroid commitment of hematopoietic stem cells, while the exogenous succinyl-CoA or 5-ALA rescues erythropoiesis in IDH1-mutant erythroid cells. Heme deficiency also impairs heme oxygenase-1 expression, which reduces levels of important heme catabolites such as biliverdin and bilirubin. These deficits result in accumulation of excessive reactive oxygen species that induce the cell death of IDH1-mutant erythroid cells. Our results clearly show the essential role of IDH1 in normal erythropoiesis and describe how its mutation leads to myeloid disorders. These data thus have important implications for the devising of new treatments for IDH-mutant tumors.

Steam to carbon ratio (S/C) determines the availability of oxygen-containing species during steam reforming, which not only affect the amount of coke formed, but also might impact physicochemical properties of the coke generated. In this study, the effect of S/C on the coke formation in steam reforming of acetic acid was assessed. The results indicated that dissociative absorption of acetic acid generated the intermediates containing both C O and C C groups even at 100 °C. At low S/C, the insufficient ∗OH reacted with carbonaceous intermediates such as CHx to form more carbonyl species, leading to significant coking and lower gas yields. Sufficient ∗OH at high S/C facilitated transformation of the carbonyl-containing species into gases, minimizing coking. The varied amount of coke showed significant effect on the diffraction of metallic nickel phase, the particle size of Ni and the absorption for the Si–O–Si functional groups on spent catalysts. The coke formed at low S/C was more aromatic with high thermal stabilities, while the coke formed at high S/C was more aliphatic with low thermal stabilities. The involvement ∗OH species in coking process determined not only properties but also morphologies of the coke. The coke formed at low S/C showed bamboo-like, dendritic or twisted rope-like structure. While the higher S/C favored the generation of the carbon nanotubes with smooth outer surface.

Polymerization is a major challenge for the upgrading of bio-oil to biofuels, but is preferable for the production of carbon material from bio-oil. Understanding the mechanism for polymerization is of importance for tailoring property of carbon material. This study investigated the characteristics for the polymerisation of furfural, vanillin, their cross-polymerization and the impacts of catalysts on their polymerization. The results indicated that the organic acids like acetic acid and formic acid could catalyze the polymerisation of furfural, while H2SO4 or NaOH as catalyst could drastically enhance the degree of polymerization of furfural. Vanillin showed a higher tendency towards polymerization than furfural and H2SO4 or NaOH significantly facilitated the polymerization of vanillin via shifting the pasty product to solid polymer. The cross-polymerization between furfural and vanillin occurred even in the absence of catalyst, while the presence of H2SO4 or NaOH catalyst resulted in the formation of more solid polymer via cross-polymerization. The polymerisation reactions were accompanied with the consumption of –C=O via aldol addition/condensation reactions. In addition, the morphology and thermal stability of the polymers formed were affected by both the type of the catalysts employed, which can in turn enhance the cross-polymerization between furfural and vanillin.

A Ni-based metal-organic framework (Ni-MOF) modified electrode was fabricated for electrochemical detection of dopamine. The Ni-MOF was synthesized by ionothermal synthesis method using an ionic liquid as a template. The morphology and composition of the Ni-MOF were characterized by scanning electron microscope, X-ray diffraction, thermogravimetric analysis, and attenuated total reflection Fourier transform infrared spectroscopy. Electrochemical responses of the Ni-MOF modified electrode toward dopamine were performed using differential pulse voltammetry. The electrochemical sensing performance of the Ni-MOF modified electrode toward dopamine was improved by the introduction of ionic liquid with a wide linear range (0.2–100 μmol L−1), and a low detection limit (60 nmol L−1). Further studies indicated that the modified electrode exhibited great selectivity to dopamine in complex mixtures, and the Ni-MOF modified electrode also has excellent stability and reproducibility. Moreover, the analysis of real samples confirmed that the modified electrode has a certain reliability.

Transition metal phosphides (TMPs) are a hopeful noble-metal-free catalysts for water splitting. In this study, we used a three-dimensional nanostructure on nickel substrate to easily synthesize a nickel–cobalt phosphide electrocatalyst (NixCoyP, x = 1, 1.5, 2; y = 1, 1.5, 2) through hydrothermal reaction and in situ phosphorylation. The NiCo1.5 P exhibited relatively excellent oxygen evolution activity performance, and it only needed the overpotentials of 123 mV for HER in 1 M KOH to perform the current densities of 10 mA cm−2. It is worth mentioning that the Ni2CoP exhibited better bifunctional electrocatalyst characteristics. As to water splitting, the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) require 197 and 253 mV overpotentials separately to provide a current density of 10 mA cm−2. Its relatively excellent electrochemical performance can be ascribed to the high-density sea urchin-like three-dimensional structure, which provides greater specific surface area and more active site. Besides, Ni2CoP also shows long-term durability lasting 80,000 s, and on this basis, there is no distinct deactivation. This work emphasizes that Ni2P and CoP play a vital role relative to the good activity of HER. Moreover, the unique morphology with self-supported structure provides a larger specific surface area, making it possible the exposure of higher amount of active sites for HER. These self-supported electrocatalysts that do not require a binder could also make the electrode more active and stable. This work, therefore, presents a strategy that is controllable and feasible strategy for the synthesis of bimetallic phosphides with unique morphology and high HER and OER activity.

Context Selenium-containing protein from selenium-enriched Spirulina platensis (Se-SP) (syn. Arthrospira platensis [Microcoleaceae]) showed novel antioxidant activity. However, the protective effect of Se-SP against oxygen glucose deprivation (OGD)-induced neural apoptosis has not been reported yet. Objective To verify whether Se-SP can inhibit OGD-induced neural apoptosis and explore the underlying mechanism. Materials and methods Primary hippocampal neurons were separated from Sprague–Dawley (SD) rats. 95% N2 + 5% CO2 were employed to establish OGD model. Neurons were treated with 5 and 10 µg/mL Se-SP under OGD condition for 6 h. Neurons without treatment were the control group. Neural viability and apoptosis were detected by MTT, immunofluorescence and western blotting methods. Results Se-SP significantly improved neuronal viability (from 57.2% to 94.5%) and inhibited apoptosis in OGD-treated primary neurons (from 45.6% to 6.3%), followed by improved neuronal morphology and caspases activation. Se-SP co-treatment also effectively suppressed OGD-induced DNA damage by inhibiting ROS accumulation in neurons (from 225.6% to 106.3%). Additionally, mitochondrial dysfunction was also markedly improved by Se-SP co-treatment via balancing Bcl-2 family expression. Moreover, inhibition of mitochondrial permeability transition pore (MPTP) by CsA (an MPTP inhibitor) dramatically attenuated OGD-induced ROS generation (from 100% to 56.2%), oxidative damage, mitochondrial membrane potential (MPP) loss (from 7.5% to 44.3%), and eventually reversed the neuronal toxicity and apoptosis (from 57.4% to 79.6%). Discussion and conclusions Se-SP showed enhanced potential to inhibit OGD-induced neurotoxicity and apoptosis by inhibiting ROS-mediated oxidative damage through regulating MPTP opening, indicating that selenium-containing protein showed broad application in the chemoprevention and chemotherapy against human ischaemic brain injury.

The upgrading of ethanol to n-butanol converts abundant bioethanol to a better gasoline replacement; however, as a representative tandem reaction it requires the presence of multiple types of active sites in one catalyst, which imposes a great challenge on the synthesis of catalysts. Although a variety of heterogeneous catalysts have been explored in this reaction, the development of efficient catalysts remains sluggish due to the limited knowledge of active sites. Herein, we demonstrated that by using Cu@UiO-66 catalysts with distinctive structures, two kinds of sites were identified: internal Cu metal sites and Lewis acid–oxygen vacancy pairs (Zr3–□) of Zr nodes in the pores of UiO-66 are the active sites, whereas Cu metal sites and Zr nodes on the external surface of UiO-66 are less involved in the upgrading of ethanol to n-butanol. And the intimate contact between internal Cu metal sites and Zr3–□ dictates the key step reactions, namely ethanol dehydrogenation, acetaldehyde condensation, and crotonaldehyde hydrogenation. Benefiting from this proximity, a high yield of n-butanol (22.2%) with negligible amounts of gaseous products could be obtained, which ranks Cu@UiO-66 catalysts among the best state-of-the-art Cu-based catalysts thus giving them great potential applications in industry.

Preexcitation symptom presents morbidity of 0.1% to 0.3% in the general population, which could lead to deadly events while accompanying arrhythmia. The classical type is Wolff-Parkinson-White (WPW) syndrome characterized as a shorter PR period, longer QRS duration, and δ wave. Radiofrequency catheter ablation (RCA) takes a vital role in treating WPW and has a high success rate. While some patients complain of consecutive chest pain after RCA, which influence their daily life severely. A 45-year-old man went to a hospital for examination because of uncomfortable palpitation. The electrocardiogram (ECG) presenting WPW syndrome (left free wall accessory pathway), then he was admitted to the hospital and scheduled for RCA. The RCA was very successful and the ECG became normal. However, after ablation, he reported consecutive chest pain, accompanied by insomnia and hypertension. No abnormal elevations of cardiac-Troponin I, myoglobin, cytokeratin, creatine kinase MB were found, and the left ventricular ejection fraction was 60%. His mental status was measured by Patient-Health Questionnaire-9, 7-item Generalized Anxiety Disorder Scale-7, Athens Insomnia Scale, indicating depressive status and anxiety status. The predominant managements involved flupentixol-melitracen and duloxetine. His chest pain, depressive, and anxiety symptoms were gradually relieved after 3-month treatment, and the drugs were slowly tapered in the 1½ years' follow-up period. Ultimately, he recovered and worked as before. This case highlights the importance of evaluating psychological status in patients with unexplained chest pain resulting from RCA and adopting antidepressants in those patients that coexist with definite depression or anxiety.

In this work, a new nanocomposite based on octa-amino polyhedral oligomeric silsesquioxanes (POSS), carbon nanotubes (CNTs), and chitosan (CS) was synthesized and used for wastewater treatment. The properties and morphologies of the prepared composite were analyzed by X-ray diffraction, scanning electron microscopy, transmission electron microscope, thermogravimetric, and atomic force microscopy. The results showed that POSS, CNTs, and CS formed a stable composite through intermolecular forces, and the modification of CS by POSS and CNTs improved its stability. In addition, the obtained composite showed good adsorption performance for the degradation of methyl orange and Congo red dyes. The pseudo-first-order model and pseudo-second-order model were used to analyze the adsorption data, and the results showed that the adsorption process conforms to the kinetic model. Moreover, the maximum adsorption capacity of the composite to methyl orange and Congo red reached 63.23 and 314.97 mg/g, respectively. This work provides new ideas for the preparation of self-assembled multi-composite and their potential applications in wastewater treatment.

Summary The stability of perovskite solar cells (PSCs) has been considered as the largest obstacle to their commercialization. Herein, we observed that the main failure mechanism for MAPbI3 perovskite is the escape of methylammonium (MA) iodide at the grain boundaries in an open space or the reconstruction of crystal in a confined small space, as well as the irreversible long-distance ionic migration under the multiple actions of light, heat, and electrical bias. Strengthened with bifunctional organic molecular of 5-ammoniumvaleric acid (5-AVA) iodide at the grain boundaries, the MAPbI3 crystal was localized in the nanoscale, and thus, the decomposition or reconstruction was inhibited and the ionic migration became reversible. As a result, we propose a reliable approach to make PSCs meet stability standards of IEC61215:2016 qualification tests. A printable PSC filled with (5-AVA)XMA1-XPbI3 has been working for more than 9,000 h at a maximum power point of 55°C ± 5°C without obvious decay.

Reactive atmosphere significantly affects pyrolysis of biomass, as the gases such as NH3 involves in the reaction network in pyrolysis. In this study, instead of feeding reactive gas, the impacts of co-feeding ethanol or glycol on the pyrolysis of cellulose were investigated at varied pyrolysis temperatures (400 and 600 °C). The results showed that the co-feeding of the alcohols affected yields of bio-char and tar, evolution of light organics and heavy organics, elemental composition, formation of fused ring structures, crystallinity, thermal stability, distribution of functionalities in the bio-char. The co-feeding of both glycol and ethanol enhanced the formation of the heavy components with the π-conjugated ring structures and affected the production of the light organics such as furfural and glycolaldehyde. Glycol or its derivatives cross-polymerized with the organics in bio-char, increasing bio-char yield and made the bio-char more oxygen-rich. Ethanol, however, showed the converse effects. Co-feeding of the alcohols promoted crystallinity but showed distinct effects on thermal stability of the bio-char at the varied pyrolysis temperatures. Both pyrolysis temperature and structures of the alcohols determined their extents of involvement in the pyrolysis of cellulose.

Attapulgite (ATTP) is an abundant natural magnesium aluminosilicate mineral that can be used as support for manufacturing cost-effective solid acid catalysts. This study mainly focuses on structural change of ATTP and the formation of Bronsted and Lewis acid sites during sulfonation in H2SO4. The results indicate that the sulfonation leads to the drastic change of the crystal phases as sulfuric acid not only plays the roles of grafting the sulfur species but also reacts with the CaO, MgO, Al2O3 and Fe2O3 or their salts in ATTP to form the sulfates, resulting in the substantial change of the porous structure of ATTP. In such a process, the Bronsted acidic sites, which are the main active sites for the conversion of furfuryl alcohol (FA) to ethyl levulinate (EL), are introduced, while the abundance/strength of the Lewis acid sites are enhanced. The yield of EL up to 95.4% is achieved over the H2SO4/ATTP catalyst. The Fe2(SO4)3 and MgSO4 in the catalyst leaches in ethanol but does not affect the catalytic stability. The formed polymer also does not affect much the catalytic activity after their removal via the calcination in air.

Reaction atmosphere is one of the principle parameters affecting pyrolysis characteristics of biomass. In this study, instead of feeding reactive gases, methanol was co-fed in the pyrolysis of saw dust, aiming to understand the impacts of methanol on evolution of functionalities/structures of the major pyrolysis products. The results showed that at low pyrolysis temperature of 350 °C, methanol did not affect much on the charring reactions but promoted the formation of the heavier organics. At 500 or 650 °C, the co-feeding of methanol enhanced the yields of both char and the heavy components of bio-oil, resulting from the reaction of methanol or its derivatives with the organic components on surface of biochar via recombination/condensation reactions. In addition, methanol enhanced evolution of the organics with π-conjugated structures. The co-feeding of methanol also enhanced crystallinity and sizes of the crystal carbon in the biochar, but led to their lower thermal stability. The in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) characterization of saw dust pyrolysis indicated that methanol promoted the aliphatic structures formation on surface of the biochar, leading to the low thermal stability.

A variety of experimental tracer diffusivities of Mg and O in magnesium oxide available in the literature were first assessed. Atomic mobilities including bulk and short-circuit diffusion of Mg and O were then obtained by means of the CALPHAD (Calculation of Phase Diagram) approach. Afterwards, the diffusion-controlled kinetic model of oxidation in a gas-MgO-Mg environment was developed based on the moving boundary model and Fick's law, coupling with the modified thermodynamic description of MgO. A mathematical expression for parabolic rate constant kp of the oxide scale was derived for magnesia and correlated with the thermodynamic and diffusion kinetic information. The evaluated kp results were in line with the experimental data. Finally, the oxidation process of pure magnesium at 673 K was model-predicted, and the predicted evolution of the oxide thicknesses agreed very well with the experimental data. It was indicated that the grain boundaries diffusion of magnesium cations predominated the high temperature oxidation process.

The impregnation of sulfuric acid aqueous solution to silica is a traditional method to prepare the solid acid catalyst (SO42−/SiO2) via bonding of the SO42− with surface atoms of silica to generate Bronsted acidic sites and Lewis acidic sites. The results in this study indicated the introduction of sulfuric acid could also impact the interaction between silica and subsequently loaded nickel species. The impregnation of sulfuric acid (i.e. 0.5 M) to Ni/SiO2 catalyst could enhance the dispersion of nickel via reducing nickel particle size, suppress sintering of nickel and increase abundance of the acidic sites with strong strength, which significantly enhanced the catalytic activity, stability and resistivity towards coking in steam reforming of guaiacol. The acidic sites with the strong strength aided the cracking of guaiacol to facilitate the subsequent reforming over metallic nickel sites. After impregnation of appropriate amount of sulfuric acid (i.e. 0.1 M or 0.5 M), the coke formed in amorphous form with low thermal stability was transformed into the coke in form of carbon nanotube with high thermal stability. The former type of coke induced rapid deactivation of the catalyst, while the latter type of coke did not.

Understanding the potential cross-polymerisation between the main components in bio-oil is essential to develop the method to minimize the coking in hydrotreatment of bio-oil or to maximize the production of carbon material from bio-oil. In this study, the potential cross-polymerisation between furfural and the sugars (xylose and glucose) and the impacts of acid/base catalysts on the polymerisation reactions were investigated. The results indicated that the cross-polymerisation of furfural/xylose and furfural/glucose existed in absence of catalyst, and the extent was more significant for that between furfural and glucose. The strong acid promoted the cross-polymerisation while the weak organic acid like acetic acid and the strong base like NaOH did not. The cross-polymerisation of furfural/sugars produced the more hydrophilic carbonaceous spheres that tended to merge to form bigger particles. The polymerisation of furfural involved opening of the furan ring via hydrolysis, forming oxygen-containing intermediates, while glucose/xylose were more reactive towards polymerisation reaction via dehydration route. The polymers from the sugars were more aliphatic than that from furfural, especially for that from glucose, leading to their lower thermal stabilities. The cross-polymerisation also affected the size/abundance of the π-conjugated structures in the soluble polymers and the relative ratio of the C O/C C in the resulting insoluble polymer.

The high tendency of bio-oil towards polymerization is one of the key challenges in hydrotreatment of bio-oil for production of bio-fuels. However, such properties of bio-oil could be used to produce carbon materials, but the mechanism for the polymerization has not been clarified. Bio-oil contains sugars, derivatives of sugars (i.e. furans et al.), phenolic monomers and oligomers. Among of them, the furans and phenolics are the typical compounds in bio-oil. In this study, the potential cross-polymerization between the furans (furan, furfural and furfuryl alcohol (FA)) and the phenolics (vanillin and guaiacol) in bio-oil was explored in water with/without H2SO4. The furans could polymerize via ring-opening to produce reactive reaction intermediates. Furfural and FA contained branched functionalities in furan ring, which was more reactive towards polymerization, especially for furfuryl alcohol. In general, the furans were more reactive towards polymerization than vanillin and guaiacol. Nevertheless, the cross-polymerization between the furans and phenolics occurred and significantly enhanced its tendency towards polymerization. The reaction intermediates formed via opening of the furan ring were the key initiator for the cross-polymerizations. Additionally, the presence of H2SO4 could enhance consumption of the C O during the polymerization and the thermal stability of the resulting polymer.

The Ni-Cu bimetallic nanoparticles were successfully anchorred on the surface of g-C3N4 nanosheets by a simple heat treatment process which was applied to the photocatalytic hydrogen evolution reaction. In-situ introduction of Ni-Cu could significantly improve the photocatalytic hydrogen evolution performance compared with pure g-C3N4 in the system sensitized by eosin Y under a visible irradiation condition. The hydrogen production activity of the composite reached 104.4 μmol (2088.28 μmol g−1 h−1) after using the Ni Cu double promoter strategy, which was 24.3 times higher than g-C3N4. The excellent electrical conductivity of the bimetallic Ni-Cu and the close interfacial contact between Ni Cu and g-C3N4 played an important role for increasing the charge transfer rate. They were also the reasons of more efficient charge separation, which ultimately led to a significant promotion on the photocatalytic hydrogen production reaction. Ni-Cu/g-C3N4 coupling with a close Schottky interface between metal and semiconductor which enhanced H2-evolution performance and TEOA oxidation kinetics. This work provided a new way to load Ni Cu bimetallic nanoparticles in situ onto g-C3N4 and a reference on relative semiconductor materials.

This study investigated the effects of a series of additives ranging from alkali, alkali earth, transition and rare earth metals (Na, Mg, K, Ca, Sc, Cr, Mn, Fe, Co, Cu, Zn, Zr, La, Ce) on catalytic behaviors of Ni/Al2O3 in steam reforming of acetic acid. The addition of alkali and alkaline metals led to the sintering of alumina and nickel species. Cr, Ce or Zr addition filled pores, while Mn addition enhanced the specific area by creating more pores. Cu and Zn addition probably led to merging of small pores. In addition, K or Na promoted reduction of nickel oxides, promoting the catalytic activity. La, Ce or Co also enhanced activity of the catalysts, while Mg, Ca, Sc, Cu, Zn or Zr decreased the activities. The K or Na modified catalysts was much more stable than that of the La or Ce modified catalysts, although the coking was more serious. The coke formed in K or Na modified catalysts was mainly in fibrous form (probably the catalytic coke), while that in La or Ce modified catalysts was mainly amorphous form (probably the polymeric coke). The fibrous coke did not lead to the fast deactivation of the nickel catalysts as the amorphous coke did. The TG-MS and DRIFTS study showed that the coke contained the aliphatic structures with the functionalities such as methyl group, carbonyl groups, carboxylic structures as well as the structures of aromatic rings. The amorphous coke formed in La or Ce modified catalysts contained more aliphatic structures. The in situ DRIFTS study of steam reforming of acetic acid showed that a number of reaction intermediates including the –OH, C O, aliphatic C C, aromatic C C, COO, C–H, –CH3, aliphatic C–O–C structure, and absorbed CO2 involved in the reforming reaction.

BACKGROUND: The synthesis of solid acid catalysts of recoverable and environmentally friendly nature has gained increasing attention in recent years. The distribution of Bronsted and Lewis acidic sites on the surface of sulfated metal oxides determines the catalytic performance, which is affected by many key factors, such as the concentration of sulfuric acid impregnated and the morphology of the metal oxides used. In this study, TiO₂ nanosheets were successfully synthesized and used as carrier for the preparation of solid acid catalysts. RESULTS: The concentration of sulfuric acid for the impregnation resulted in various distributions of Bronsted and Lewis acidic sites on the surface of sulfated TiO₂. With a medium concentration of sulfuric acid (1 mol L⁻¹) for the impregnation, the highest ratio of Bronsted to Lewis acidic sites can be achieved, and the catalyst showed superior catalytic activity for the conversion of furfuryl alcohol (FA) to ethyl levulinate (EL) in ethanol and the conversion of fructose to 5‐hydroxymethylfurfural (HMF) in dimethyl sulfoxide (DMSO). CONCLUSION: The sulfation of TiO₂ nanosheets induced the formation of both Bronsted and Lewis acidic sites. The Bronsted acidic sites were more effective for catalyzing the conversion of FA or fructose. The poor recyclability of the 1.0‐SO₄²⁻/TiO₂ catalyst in the conversion of FA to EL in ethanol, a protic solvent, was due to the leaching of sulfur species. The deactivation of the catalyst in DMSO was due to coking, which could be resolved via calcination of the coke species in air. © 2019 Society of Chemical Industry

BACKGROUND: Ordinary clay is an abundantly available and widely distributed material, the use of which as supporting material can minimize the cost in manufacturing catalysts. This study investigated the potential for the direct use of ordinary clay and treated clay as supports of copper (Cu)‐based catalysts for hydrogenation of furfural and some phenolic compounds. RESULTS: The catalyst treated with alkali showed better activity at 100 °C whereas the activity of other catalysts was negligible, and when the temperature was raised, the activity of all the catalysts was obviously improved. In addition, the catalysts treated with sodium hydroxide (NaOH) showed fair activity for 5‐hydroxyl methyl furfural, vanillin and benzaldehyde, and the stability of the catalyst also was good: after four cycles of experiments, the yield of furfuryl alcohol could still reach >95%. CONCLUSIONS: Activation of clay with NaOH effectively enhanced not only the surface area and porous structures, but also the alkalinity of the catalyst, suppressing side reactions such as acetalization between furfural and ethanol, and facilitated hydrogenation of furfural. Comparing with clay washed with sulfuric acid or calcined at various temperatures, the clay activated with NaOH showed superior hydrogenation of not only furfural, but also 5‐hydroxyl methyl furfural, vanillin and benzaldehyde, as a result of the presence of abundant mesopores and alkaline sites. The ordinary clay‐supported Cu catalyst also showed acceptable activity for hydrogenation reactions at a higher reaction temperature, which has particular importance for practical applications because the clay can be used directly as supporting material. © 2019 Society of Chemical Industry

Development of an eco-friendly and effective reaction system for production of the platform chemicals like 5-hydroxymethylfurfural (HMF) has always been a hot topic in bio-refinery. In this study, ...

The influence of barium addition to a Ni/Al2O3 catalyst on the reaction intermediates formed, the activity, resistance of the catalyst to coking, and properties of the coke formed after acetic acid steam reforming were investigated in this study. The results showed the drastic effects of barium addition on the physicochemical properties and performances of the catalyst. The solid-phase reaction between alumina and BaO formed BaAl2O4, which re-constructed the alumina structure, resulting in a decrease in the specific surface area and an increase in the resistance of metallic Ni to sintering. The addition of barium was also beneficial for enhancing the catalytic activity, resulting from the changed catalytic reaction network. The in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study of the acetic acid steam reforming indicated that barium could effectively suppress the accumulation of the reaction intermediates of carbonyl, formate, and C=C functional groups on the catalyst surface, attributed to its relatively high ability to cause the gasification of these species. In addition, coking was considerably more significant over the Ba–Ni/Al2O3 catalyst. Moreover, the Ba–Ni/Al2O3 catalyst was more stable than the Ni/Al2O3 catalyst, owing to the distinct forms of coke formed (carbon nanotube form over the Ba–Ni/Al2O3 catalyst, and the amorphous form over the Ni/Al2O3 catalyst).

Reaction atmosphere is one of the principle reaction parameters affecting the pyrolysis of biomass. At elevated temperatures, in addition to gases, organics are also regarded as part of the reaction atmosphere. In this study, the impacts of the co-feeding of formic acid or acetic acid on the pyrolysis behaviour of cellulose were investigated at 400 and 600 °C, respectively. The results showed that the co-feeding of the acids significantly affected properties of both the resulting bio-oil and biochar. Co-feeding of acetic acid remarkably promoted formation of heavier organics with π-conjugated structures, while the presence of formic acid suppressed their evolution, especially at the lower pyrolysis temperature of 400 °C. The co-feeding of the carboxylic acids increased the yields of biochar. Furthermore, the co-feeding of formic acid or acetic acid also affected the elemental composition, the defective structure, the crystallinity and the thermal stabilities of the resulting biochar at varied pyrolysis temperature in the distinct ways. The carboxylic acids or their derivatives interfered with the formation of the volatiles or reacted directly with the organic components on surface of biochar, which substantially modified the physiochemical properties of the biochar.

Selectively hydrogenating the carbonyl of furfural and opening of the furan ring is challenging while crucial for efficient conversion of furfural to pentanediols, the valuable chemicals. In this s...

During the conversion of sugars/furans into the value-added chemicals via acid catalysis, solvent in addition to acid catalyst is deemed as an essential parameter affecting the reaction network. So...

This study investigated the distinct catalytic behaviors of mono Mn, Fe, Co, Ni, Cu and Zn catalysts in the reforming of the small organics including methanol, acetic acid and acetone. The results showed that Mn, Fe or Zn-based catalysts showed almost no activity for steam reforming of either methanol, acetic acid or acetone, due to their low capacity to break the chemical bonds of the organics or to activate steam. Co and Cu-based catalysts were generally active for steam reforming of methanol. Nevertheless, Co-based catalysts promoted methanol decomposition to form a substantial amount of CO. Alumina as a support remarkably influenced catalytic stability of the catalyst. The unsupported Cu catalyst showed a much lower stability than Cu/Al2O3. Nevertheless, the unsupported Ni was more stable than Ni/Al2O3 catalyst, due to its high resistivity towards coking. The unsupported Co, however, was prone to coking. The C/H ratios in the coke formed over the unsupported and alumina-supported Ni or Co catalysts were distinct, indicating the involvement of alumina in the coking process. In addition, Ni and Co catalysts behaved differently. Ni/Al2O3 showed a superior stability than Co/Al2O3 in steam reforming of acetone. The coke formed on Ni/Al2O3 was more aromatic than that over Co/Al2O3 catalysts while morphologies of coke (nanotubes over Ni/Al2O3 versus fibrous coke over Co/Al2O3) were also different.

The photocatalytic decomposition of water to produce hydrogen is an important process, through which solar energy can be converted to chemical energy. Non-precious metal phosphides have quietly attracted attention as an emerging inexpensive photocatalyst. In this study, we reported that a CoP/CeVO4 hybrid photocatalyst exhibited high hydrogen evolution efficiency owing to EY (eosin Y) sensitization under visible light irradiation for the first time, and the amount of generated hydrogen reached 444.6 μmol in 5 h. The CoP/CeVO4 nanohybrids were synthesized by a simple chemical precipitation method. The coupling of CoP and CeVO4 with ZIF-9 as a precursor could be completed in one step. The CeVO4 particles were firmly attached to the surface of the CoP particles to form a “small point” to “big point” heterojunction. The results of X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, EDX, and transmission electron microscopy showed the formation of CoP and CeVO4 nanoparticles and the structure of the composite. Based on a detailed analysis of the Mott-Schottky plot, the UV-vis diffuse reflectance spectra, photocurrent-time (it) curve, Tafel curve, Nyquist curve (EIS), linear volt-ampere curve (LSV), and steady-state fluorescence spectra were studied. The time-resolved photoluminescence measurements indicated that the reason for the high-efficiency hydrogen evolution of CoP/CeVO4 was that the bands of CoP and CeVO4 were bent due to the existence of the Schottky barrier, and a heterojunction was formed between CoP and CeVO4, which generated an internal electric field and accelerated the charge transfer. In addition, the synergistic effect between CoP and CeVO4 provided a new hydrogen-evolution activity center for each of them. The improved carrier separation efficiency and the decrease in the photo-generated recombination rate led to the excellent photocatalytic hydrogen-evolution activity of the CoP/CeVO4 composite catalyst. This work provides a new strategy for modulating the electronic structure and carrier behavior of transition metal phosphide photocatalysts.

Over the past few years, different in vitro and in vivo studies have been highlighting the great potentiality of hyaluronic acid (HA) as a biomaterial in wound healing treatment thanks to its good capability to induce mesenchymal and epithelial cell growth and differentiation, angiogenesis, and collagen deposition. However, the need to improve its mechanical properties as well as its residence time has led scientists to study new functionalization strategies. In this work, chemically modified HA-based hydrogels were obtained by methacrylic and maleic functionalization. Methacrylated (MEHA) and maleated HA (MAHA) hydrogels have shown important physico-chemical properties. The present study provides a deeper insight into the biocompatibility of both synthesized materials and their effects on tissue inflammation using in vitro and in vivo models. To this aim, different cell lines involved in wound healing, human dermal fibroblasts, human adipose-derived stem cells and human umbilical vein endothelial cells, were seeded on MEHA and MAHA hydrogels. Furthermore, an inflammation study was carried out on a murine macrophage cell line to assess the effects of both hydrogels on inflammatory and anti-inflammatory interleukin production. The results showed that both MAHA and MEHA supported cell proliferation with anti-inflammation ability as highlighted by the increased levels of IL-10 (57.92 ± 9.87 pg mL-1 and 68.08 ± 13.94 pg mL-1, for MEHA and MAHA, respectively). To investigate the inflammatory response at tissue/implant interfaces, an in vivo study was also performed by subcutaneous implantation of the materials in BALB/c mice for up to 28 days. In these analyses, no significant chronic inflammation reaction was demonstrated in either MEHA or MAHA in the long-term implantation.

The silica-based materials with varied pore distribution were prepared by adjusting the pH during the self-assembly process and were used as the supporting materials of Cu-based catalysts for hydrogenation of furfural and phenolics. It was found that the pH during the self-assembly process drastically impacted the porous structures of the resulting silica materials. At a lower pH environment (pH = 1.0), the accelerated hydrolysis rate of Na2SiO3 led to the randomly arranged Si species, forming the disordered structures with the pore size of ca. 7 nm. At the higher pH environment (pH = 2.0), the slow hydrolysis rate created the difficulty for grow of silicon precursor on the template, and the disordered mesoporous structures of silica with the pore size of ca. 12 nm were formed. The moderate hydrolysis rate at pH of 1.5 favoured the formation of the ordered pores with the pore size of ca. 3 nm. The results indicated the pores of different sizes induced the distinct steric hindrance, which further affected the efficiency for hydrogenation of the organics with ring structures.

In this study, an effective catalytic system (CoSO4·7H2O/THF) for selective conversion of fructose to 5-hydroxymethylfurfural (HMF; yield: 88%) was developed. The synergistic effects among Co2+, SO42−, crystal water and tetrahydrofuran (THF) were crucial for achieving selective dehydration of fructose to HMF. Co2+ worked as a Lewis acid for catalyzing mainly dehydration of fructose to HMF but not the further decomposition of HMF to levulinic acid. THF could help to retain HMF while CoSO4 could coordinate with HMF, enhancing the thermal stability of HMF in THF. The crystal water in cobalt sulfate could help to coordinate with fructose, which facilitated the conversion of fructose via dehydration reactions. The CoSO4·7H2O/THF catalytic system could also catalyze the conversion of inulin and cellulose into HMF. The main advantages of the CoSO4·7H2O/THF catalytic system are the low cost, the easy recycling of the CoSO4·7H2O catalyst and the easy separation of HMF from volatile THF.

Efficient exogenous DNA integration can be mediated by Cas9 through the non-homology end-joining pathway. However, such integrations are often imprecise and contain a variety of mutations at the junctions between the external DNA and the genomic loci. Here we describe a microhomology-dependent targeted integration method, designated MITI, for precise site-specific gene insertions. We found that the MITI strategy yielded higher knock-in accuracy than Cas9 HITI for the insertion of external DNA and tagging endogenous genes. Furthermore, in combination with negative selection and four different CrRNAs targeting donor vectors and genome-targeted sites with a CrRNA array, MITI facilitated precise ligation at all junctions. Therefore, our Cas12a-based MITI method increases the repertoire of precision genome engineering approaches and provides a useful tool for various gene editing applications. Electronic supplementary material The online version of this article (10.1007/s00018-019-03396-8) contains supplementary material, which is available to authorized users.

Formamidinium lead triiodide (HC(NH2)2PbI3 or FAPbI3) is a promising light absorber for high-efficiency perovskite solar cells because of its superior light absorption range and thermal stability to CH3NH3PbI3 (MAPbI3). Unfortunately, it is difficult to fabricate high-quality FAPbI3 thin films to surpass the MAPbI3-based cells due to easily forming unwanted but more stable yellow δ-phase and thus requiring high annealing-temperature for wanted photovoltaic-active black α-phase. Herein, we reported a novel low-temperature fabrication of highly crystallized α-FAPbI3 film exhibiting uniaxial-oriented nature with large grain sizes up to 2 μm. First-principles energetic calculations predicted that this novel deposition should be ascribed to the formation of a high-energy metastable two-dimensional (2D) intermediate of MAFAPbI3Cl followed by a spontaneous conversion to α-FAPbI3. The ions exchange reaction during this MAFAPbI3Cl-FAPbI3 conversion account for the perovskite film uniaxial-oriented grown along the (1 1 1) direction. This large-grain and uniaxial-oriented grown α-FAPbI3 based solar cells exhibited an efficiency up to 20.4% accompanying with low density-voltage (J-V) hysteresis and high stability.

1. MAK683 (N-((5-fluoro-2,3-dihydrobenzofuran-4-yl)methyl)-8-(2-methylpyridin-3-yl)-[1,2,4]triazolo[4,3-c]pyrimidin-5-amine) is a potent and orally bioavailable EED inhibitor for the potential treatment in oncology. Pharmacokinetics (PK) in preclinical species are characterized by low to moderate plasma clearances, high oral exposure and moderate to high oral bioavailability at dose of 1-2 mg/kg.2. A species comparison of the metabolic pathways of MAK683 has been made using [14C]MAK683 incubations with liver microsomes and hepatocytes from rat, dog, cynomolgus monkey and human. Overall, the in vitro hepatic metabolism pathway of MAK683 in all five species was very complex. A total of 60 metabolites with 19 metabolites greater than 1.5% of the total integrated area in the radiochromatogram of at least one species were identified in five species (rat, mouse, dog, monkey and human).3. The primary in vitro hepatic oxidative metabolism pathway identified in human involved 2-hydroxylation of the dihydrofuran ring to form an alcohol (M28), which was in a chemical equilibrium favoring the formation of its aldehyde form. The aldehyde was then oxidized to the carboxylic acid metabolite (M26) or reduced to the O-hydroxyethylphenol (M29). N-dealkylation (M1), 3-hydroxylation of the dihydrofuran ring (M27), N-oxidation of the pyridine moiety (M53) and sulfate conjugation of M28 to form M19 were also important biotransformation pathways in human hepatocytes. The above major human hepatic metabolic pathways were also observed across the animal species (rat, mouse, dog and monkey) mostly providing precursors for the formation of other metabolites via further oxygenation, glucuronidation, and sulfation pathways.4. No human specific metabolites were observed. In addition, in-vivo biotransformation was also conducted in bile-duct cannulated (BDC) rat. The metabolism in BDC rat was similar to these observed the in vitro hepatocytes.

Lonicerae japonicae flos (LJF) is widely used for the treatment of inflammation-related diseases in traditional Chinese medicine (TCM). To clarify the anti-inflammatory mechanism of LJF, 29 compounds with high content in LJF were selected for network pharmacology. Then, a comprehensive network pharmacology strategy was implemented, which involved compound-inflammation-target construction, protein-protein interaction (PPI) network analysis, and enrichment analysis. Finally, molecular docking and in vitro experiments were performed to verify the anti-inflammatory activity and targets of the key compound. As a result, 279 inflammation-associated proteins were identified, which are mainly involved in the AGE/RAGE signaling pathway in diabetic complications, the HIF-1 signaling pathway, the PI3K-AKT signaling pathway, and EGFR tyrosine kinase inhibitor resistance. A total of 12 compounds were linked to more than 35 targets, including apigenin, kaempferol, quercetin, luteolin, and ferulic acid. The results of molecular docking showed that AKT has the most binding activity, exhibiting certain binding activity with 10 compounds, including vanillic acid, protocatechuic acid, secologanic acid, quercetin, and luteolin; the results of qRT-PCR and WB confirmed that two key compounds, secologanic acid and luteolin, could significantly decrease the secretion of TNF-α and the AKT expression of RAW264.7 murine macrophages stimulated by LPS (lipopolysaccharide). These results demonstrate that the comprehensive strategy can serve as a universal method to illustrate the anti-inflammatory mechanisms of traditional Chinese medicine by identifying the pathways or targets.

The Ce0.8Gd0.2O2−δ (CGO) interlayer is commonly applied in solid oxide fuel cells (SOFCs) to prevent chemical reactions between the (La1−xSrx)(Co1−yFey)O3−δ (LSCF) oxygen electrode and the Y2O3-stabilized ZrO2 (YSZ) electrolyte. However, formation of the YSZ–CGO solid solution with low ionic conductivity and the SrZrO3 (SZO) insulating phase still happens during cell production and long-term operation, causing poor performance and degradation. Unlike many experimental investigations exploring these phenomena, consistent and quantitative computational modeling of the microstructure evolution at the oxygen electrode–electrolyte interface is scarce. We combine thermodynamic, 1D kinetic, and 3D phase-field modeling to computationally reproduce the element redistribution, microstructure evolution, and corresponding ohmic loss of this interface. The influences of different ceramic processing techniques for the CGO interlayer, i.e., screen printing and physical laser deposition (PLD), and of different processing and long-term operating parameters are explored, representing a successful case of quantitative computational engineering of the oxygen electrode–electrolyte interface in SOFCs.