Search

Two novel energetic compounds, 3-nitroxymethyl-5-(4-nitro-furazan-3-yl)-1,2,4-oxadiazole (4) and 3-nitroxymethyl-5-(4-azido-furazan-3-yl)-1,2,4-oxadiazole (5), were synthesized. Both of them were fully characterized, and the structure of 4 was further confirmed by X-ray single crystal diffraction. The thermal behaviors, detonation performances and the sensitivities of 4 and 5 were also investigated by differential scanning calorimetry (DSC), EXPLO5 program and BAM standard techniques. In addition, the electrostatic potential energy surface (ESP) was studied by Multiwfn program and density functional theory at B3LPY/6-31G (d, p). Both compounds have low melt-point, good energetic performance and mechanical sensitivity, which endow them with promising properties as plasticizing ingredients in propellant formulations.

Oximes derivatives have been vastly used in organic synthesis. In this review, C(sp3)−H bond functionalization of oximes derivatives via iminyl radical induced 1,5−hydrogen atom transfer was discussed. According to the different type of products, this review was divided into three parts: (1) C(sp3)−H bond functionalization for C−C bond formation. (2) C(sp3)−H bond functionalization for C−N bond formation. (3) C(sp3)−H bond functionalization for C−S, C−F bond formation.

Inefficient electrocatalysts and high-power consumption are two thorny problems for electrochemical hydrogen (H2) production from acidic water electrolysis. Herein we report the one-pot precise synthesis of ultrafine Au core-PtAu alloy shell nanowires (Au@PtxAu UFNWs). Among them, Au@Pt0.077Au UFNWs exhibit the best performance for formic acid oxidation reaction (FAOR) and hydrogen evolution reaction (HER), which only require applied potentials of 0.29 V and −22.6 mV to achieve a current density of 10 mA cm−2, respectively. The corresponding formic acid electrolyzer realizes the electrochemical H2 production at a voltage of only 0.51 V with 10 mA cm−2 current density. Density functional theory (DFT) calculations reveal that the Au-riched PtAu alloy structure can facilitates the direct oxidation pathway of FAOR and consequently elevates the FAOR activity of Au@Pt0.077Au UFNWs. This work provides meaningful insights into the electrochemical H2 production from both the construction of advanced bifunctional electrocatalysts and the replacement of OER.

Anandamide (AEA) analogs show fair effects in counteracting the deterioration of Alzheimer's disease (AD). Our previous studies demonstrated that AEA analog-N-linoleyltyrosine (NITyr) exerted significant activities. In our current research, the role and mechanisms of NITyr were assessed in APP/PS1 mice mimicking the AD model. NITyr improved motor coordination in the rotarod test (RRT) and ameliorated spatial memory in the Morris water maze (MWM) but did not increase spontaneous locomotor activity in the open field test (OFT). In addition, NITyr protected neurons against β-amyloid (Aβ) injury via hematoxylin-eosin (HE) and Nissl staining. Moreover, the related biochemical indexes showed that NITyr reduced the levels of Aβ40 and Aβ42 in the hippocampus but did not affect the expression of p-APP and β-secretase 1 (BACE1). Furthermore, the autophagy inhibitor 3-methyladenine (3 MA) attenuated the effect of NITyr on animal behaviors and neurons. Meanwhile, NITyr upregulated the expression levels of LC3-II and Beclin-1, which were weakened by AM630 (an antagonist of CB2 receptor and a weak partial agonist of CB1 receptors). AM630 also weakened the role of NITyr in animal behaviors. Thus, NITyr improved behavioral impairment and neural loss by inducing autophagy mainly mediated by the CB2 receptor, and weakly mediated by the CB1 receptor.

The catalytic/electrocatalytic performance of platinum (Pt) nanostructures highly relates to their morphology. Herein, we propose a facile self-template pyrolysis strategy at high temperature to synthesize one-dimensionally holey Pt nanotubes (Pt-hNTs) using PtII-dimethylglyoxime complex (PtII-DMG) nanorods as the reaction precursor. The coordination capability of DMG results in the generation of PtII-DMG nanorods, whereas the reducibility of DMG at high temperature leads to the reduction of PtII species in PtII-DMG nanorods. During the reaction process, the inside-out Ostwald ripening phenomenon leads to the hollow morphology of Pt-hNTs. Benefiting from the physical characteristics of hollow and holey structure, Pt-hNTs with clean surface show superior electroactivity and durability for catalyzing ethanol electrooxidation as well as hydrogen evolution reaction in alkaline media. Under optimized experimental conditions, the constructed symmetric Pt-hNTs||Pt-hNTs ethanol electrolyzer only requires an electrolysis voltage of 0.40 V to achieve the electrochemical hydrogen production, demonstrating a highly energy saving strategy relative to traditional water electrolysis.

The nitrate electroreduction reaction (NO3--ERR) is an efficient and green approach for nitrate remediation, which requires a highly active and selective electrocatalyst. In this work, porous and amorphous cobalt phosphide nanoshuttles (CoP PANSs) are successfully synthesized by using Mg2+ ion-doped calcium carbonate nanoshuttles (Mg-CaCO3 NSs) as the initial reaction precursor via precipitation transformation and a high-temperature phosphidation strategy. Various physical characterizations show that CoP PANSs have porous architecture, amorphous crystal structure, and big surface area. Electrochemical measurements reveal for the first time that CoP PANSs have outstanding electroactivity for NO3--ERR in a neutral electrolyte. At an applied potential of -0.5 V vs reversible hydrogen electrode, CoP PANSs can achieve a high Faraday efficiency (94.24 ± 2.8%) and high yield rate (19.28 ± 0.53 mg h-1 mgcat-1) for ammonia production, which exceeds most reported values at various electrocatalysts for NO3--ERR. Thus, the present result indicates that cobalt phosphide nanomaterials have promising application for NO3--ERR.

Background Retrospective studies have shown that adjuvant treatment improves survival of patients with stage IIB–III esophageal squamous cell carcinoma, but there is no evidence from prospective trials so far. Materials and Methods Patients with pathological stage IIB–III esophageal squamous cell carcinoma were randomly assigned to receive surgery alone (SA), postoperative radiotherapy (PORT), or postoperative concurrent chemoradiotherapy (POCRT). PORT patients received 54 Gy in 27 fractions; the POCRT group received 50.4 Gy in 28 fractions, plus concurrent chemotherapy with paclitaxel (135–150 mg/m2) and cisplatin or nedaplatin (50–75 mg/m2) every 28 days. The primary endpoint was disease-free survival (DFS), and the secondary endpoint was overall survival (OS). Results A total of 172 patients were enrolled (SA, n = 54; PORT, n = 54; POCRT, n = 64). The 3-year DFS was significantly better in PORT/POCRT patients than in SA patients (53.8% vs. 36.7%; p = .020); the 3-year OS was also better in PORT/POCRT patients (63.9% vs. 48.0%; p = .025). The 3-year DFS for SA, PORT, and POCRT patients were 36.7%, 50.0%, 57.3%, respectively (p = .048). The 3-year OS for SA, PORT, and POCRT patients were 48.0%, 60.8%, 66.5%, respectively (p = .048). Conclusion PORT/POCRT (especially POCRT) may significantly improve DFS and OS in stage IIB–III esophageal squamous cell carcinoma. Implications for Practice The results of this phase III study indicated that postoperative radiotherapy/postoperative concurrent chemoradiotherapy (PORT/POCRT) could significantly improve disease-free survival and overall survival in stage IIB–III esophageal squamous cell carcinoma compared with surgery alone with acceptable toxicities. In-field and out-of-field recurrences were comparable between the POCRT and PORT groups, which demonstrates the rationality and safety of the radiation field used in this study. The postoperative regimens in this trial might be accepted as standard treatment options for pathological stage IIB–III esophageal cancer. Larger sample size prospective randomized trials to identify the value are warranted.

Methanol electrolysis is a promising strategy to achieve energy-saving and efficient electrochemical hydrogen (H2) production. In this system, the advanced electrocatalysts with high catalytic performance for both the methanol oxidation reaction (MOR) and hydrogen evolution reaction (HER) are highly desirable. Inspired by the complementary catalytic properties of rhodium (Rh) and palladium (Pd) for MOR and HER, herein, several Pd core-RhPd alloy shell nanodendrites (Pd@RhPd NDs) are synthesized through the galvanic replacement reaction between Pd nanodendrites (Pd NDs) and rhodium trichloride. For MOR, Pd@RhPd NDs exhibit Rh content-determined catalytic activity, in which Pd@Rh0.07Pd NDs have an optimal combination of oxidation potential and oxidation current due to the synergistic catalytic process of Pd/Rh double active sites. For HER, the introduction of Rh greatly improves the catalytic activity of Pd@RhPd NDs compared to that of Pd NDs, suggesting that Rh is the main activity site for HER. Unlike MOR, however, the HER activity of Pd@RhPd NDs is not sensitive to the Rh content. Using Pd@Rh0.07Pd NDs as robust bifunctional electrocatalysts, the as-constructed two-electrode methanol electrolysis cell shows a much lower voltage (0.813 V) than that of water electrolysis (1.672 V) to achieve electrochemical H2 production at 10 mA cm-2, demonstrating the application prospect of methanol electrolysis for H2 production.

A CuI-TbIII heterometallic MOF, namely 1·DMF, was obtained via a coordination assembly process of isonicotinic acid with CuI and TbIII. 1·DMF can be switched to 1·MeOH in methanol with a luminescent emission response. Meanwhile, 1·MeOH exhibits a reversible single-crystal transformation to 1·DMF after immersion in DMF. Both MOFs have superior physicochemical stability. The 1·DMF-based biosensor has a remarkable sensing performance toward penicillin.

The sluggish reaction kinetics of the anodic oxygen evolution reaction increases the energy consumption of the overall water electrolysis for high-purity hydrogen generation. In this work, ultrathin cobalt sulfide nanosheets (Co3S4-NSs) on nickel foam (Ni-F) nanohybrids (termed as Co3S4-NSs/Ni-F) are synthesized using cyanogel hydrolysis and a sulfurization two-step approach. Physical characterizations reveal that Co3S4-NSs with a 1.7 nm thickness have abundant holes, implying the big surface area, abundant active edge atoms, and sufficient active sites. Electrochemical measurements show that as-synthesized Co3S4-NSs/Ni-F have excellent electrocatalytic activity and selectivity for ethanol oxidation reaction and hydrogen evolution reaction. Due to their bifunctional property of Co3S4-NSs/Ni-F nanohybrids, a symmetric Co3S4-NSs/Ni-F∥Co3S4-NSs/Ni-F ethanol electrolyzer can be effectively constructed, which only requires a 1.48 V electrolysis voltage to reach a current density of 10 mA cm-2 for high-purity hydrogen generation at the cathode as well as value-added potassium acetate generation at the anode, much lower than the electrolysis voltage of traditional electrochemical water splitting (1.64 V).

The novel composite, Fe3O4@SiO2@mSiO2-PW12/Ag, was successfully prepared by in situ loading Ag nanoparticles (Ag NPs) on the surface of grafted phosphotungstate (denoted as PW12) Fe3O4@SiO2@mSiO2via a photoreduction deposition method. PW12 not only acts as a reducing agent and stabilizer for Ag NPs but also as a bridge to link Ag NPs and the SiO2 shell in the loading process. Its activity toward the photodegradation of methyl orange (MO) and photoreduction of Cr2O72- anions was evaluated. Experimental results showed that Fe3O4@SiO2@mSiO2-PW12/Ag with 5.3 wt% Ag loading and 18.65 wt% of PW12 exhibits the highest photocatalytic efficacy, and complete degradation of MO and 91.2% photoreduction of Cr(vi) were realized under simulated sunlight for 75 min, respectively. The enhanced catalytic activities of the composite are due to its high specific surface area, the synergistic effect among the components and the formation of a heterojunction of PW12/Ag. The possible enhanced photocatalytic mechanism is proposed. The catalyst is durable and can be easily recovered using a magnet for recycling without a significant loss of catalytic activity.

Co-regulation of the crystal plane and composition is a powerful strategy to effectively enhance the catalytic properties of nanomaterials. Herein, high-quality PtxRu nanocubes (PtxRu-NCs) with an adjustable composition and exposed (100) planes are synthesized by a simple hydrothermal method. For the ammonia electrooxidation reaction (AOR), Pt6Ru-NCs show obviously higher mass activity (192 mA mgPt−1) and specific activity (1.02 mA cm−2) than other PtxRu-NCs, Pt-NCs and commercial Pt nanocrystals. Density functional theory calculations demonstrate that the Pt6Ru (100) plane is more energetically favourable for the AOR than the Pt (100) plane due to the stronger binding of *NH2 and *NH. For the hydrogen evolution reaction (HER), the optimized Pt6Ru-NCs also deliver the smallest overpotential (37.6 mV) at 10 mA cm−2. The high activity of bifunctional Pt6Ru-NCs for both AOR and HER can be attributed to the crystal surface effect and Pt-Ru bimetallic interactions. A symmetric ammonia electrolyzer constructed here with Pt6Ru-NCs as the cathode and anode only requires 0.72 V electrolysis voltage for electrochemical hydrogen production.

A practical and eco-friendly method for the controllable aerobic oxygenation of sulfides by electrochemical catalysis was developed. The switchable preparation of sulfoxides and sulfones was effectively controlled by reaction time, in which both molecular oxygen and water can be used as the oxygen source under catalyst and external oxidant-free conditions. The electrochemical protocol features a broad substrate scope and excellent site selectivity and is successfully applied to the modification of some sulfide-containing pharmaceuticals and their derivatives.

A family of cyano-bridged 3d-4f 1D chain compounds, {RE[TM(CN)6(2-PNO)5]}·(H2O)4 {RE = YIII, TM = [FeIII]LS (1); RE = DyIII, TM = CoIII (3); RE = ErIII, TM = [FeIII]LS (4), CoIII (5); 2-PNO = 2-picoline-N-oxide} and {RE[TM(CN)6(2-PNO)5]} {RE = DyIII, TM = [FeIII]LS (2)}, were synthesized and characterized. Single-crystal X-ray diffraction studies reveal that compounds 1 and 3-5 are isostructural, while compound 2 has a similar 1D chain structure with a different chain to chain arrangement. An axially-elongated pentagonal bipyramidal (D5h) coordination geometry is formed with five 2-PNO ligands in the equatorial plane and two [TM(CN)6]3- on the apical sites around the rare earth ions in these compounds. A comparison of the magnetic relaxation behaviour in detail reveals that it is more favorable for the Er (4 and 5) than the Dy analogues (2 and 3) to exhibit SIM properties in this axially-elongated D5h coordination environment. Under zero dc field, ac susceptibility measurements show that the Dy analogues have no magnetic relaxation behaviour, while the Er analogues exhibit frequency dependence despite the strong QTM effect. Under a 1 kOe dc field, the Er analogues generally show 1-2 orders of magnitude longer relaxation time at each selected temperature and a higher relaxation energy barrier than the Dy analogues. And the RECo compounds (3 and 5) show a more suppressed QTM effect than the corresponding REFe (2 and 4) compounds, which may be ascribed to the elimination of the fluctuation field from the neighbouring [FeIII]LS ions. The ab initio calculations indicate the misplacement between the orientation of the main magnetic axis and the structural axis in the Dy analogues, and the relative consistency in the Er analogues, which should be the source of the Er analogues showing better SIM properties than the Dy analogues.

This minireview highlights some recent advances in the rational design of precise Cu nanoclusters supported on microporous materials, including zeolites and metal-organic frameworks. The development of comprehensive characterisation techniques enables scientists to elucidate the structure-activity relationship of these catalysts, which aids the subsequent engineering of more superior catalytic systems at an atomistic perspective.

Background Preoperative chemoradiotherapy (CRT) followed by surgery is the most common approach for patients with resectable esophageal cancer. Nevertheless, considerable numbers of esophageal-cancer patients undergo surgery as the first treatment. The benefit of neoadjuvant therapy might only be for patients with a pathologic complete response, so stratified research is necessary. Postoperative treatments have important roles because of the poor survival rates of patients with stage-IIB/III disease treated with resection alone. Five-year survival of patients with stage-IIB/III thoracic esophageal squamous cell carcinoma (TESCC) after surgery is 20.0–28.4%, and locoregional lymph-node metastases are the main cause of failure. Several retrospective studies have shown that postoperative radiotherapy (PORT) and postoperative chemoradiotherapy (POCRT) after radical esophagectomy for esophageal carcinoma with positive lymph-node metastases and stage-III disease can decrease locoregional recurrence and increase overall survival (OS). Using intensity-modulated RT, PORT reduces locoregional recurrence further. However, the rate of distant metastases increases to 30.7%. Hence, chemotherapy may be vital for these patients. Therefore, a prospective randomized controlled trial (RCT) is needed to evaluate the value of PORT and concurrent POCRT in comparison with surgery alone (SA) for esophageal cancer. Method This will be a phase-II/III RCT. The patients with pathologic stage-IIB/III esophageal squamous cell carcinoma will receive concurrent POCRT or PORT after radical esophagectomy compared with those who have SA. A total of 120 patients in each group will be recruited. POCRT patients will be 50.4 Gy concurrent with paclitaxel (135–150 mg/m2) plus cisplatin or nedaplatin (50–75 mg/m2) treatment every 28 days. Two cycles will be required for concurrent chemotherapy. The prescription dose will be 54 Gy for PORT. The primary endpoint will be disease-free survival (DFS). The secondary endpoint will be OS. Other pre-specified outcome measures will be the proportion of patients who complete treatment, toxicity, and out-of-field regional recurrence rate between PORT and POCRT. Discussion This prospective RCT will provide high-level evidence for postoperative adjuvant treatment of pathologic stage-IIB/III esophageal squamous cell carcinoma. Trial registration clinicaltrials.gov (NCT02279134). Registered on October 26, 2014.

A direct injection compression ignition engine fueled by diesel blended with 10% or 30% mass proportion of 2-methylfuran was experimentally studied. The in-cylinder combustion pressure, regulated emissions and particulate matter emissions at different pilot injection timings and masses were investigated under the exhaust gas re-circulation mode. It was found the blending with methylfuran increased the peak in-cylinder pressure and retarded the combustion phase at different pilot injection timings. The addition of 30% methylfuran increased the peak in-cylinder pressure and heat release rate gradually along with the advancement of pilot injection timing. The NOx, HC, and CO emissions increased with the advancement of pilot injection timing when the pilot injection proportion was fixed at 20%, and the blending with methylfuran reduced HC and CO emissions but increased NOx emissions considerably. The 30% methylfuran addition could significantly reduce nucleation mode and accumulation mode particles at different pilot injection timings and masses compared with pure diesel. In addition, the particulate mass con-centration of 30% methylfuranaddition remained at very low levels under all experimental conditions.

Purpose Tizanidine hydrochloride (TZN) is a centrally acting α2-adrenergic agonist. In this study, we aimed to explore the role of TZN on human lung cancer and to elucidate its underlying mechanisms. Methods The effect of TZN treatment in A549 cell proliferation, migration, invasion and apoptosis was evaluated by CCK8, transwell and flow cytometer assays. The expression of apoptosis-related proteins and the activation of AKT and Wnt3a/β-catenin pathways were detected by Western blot. From the data of DrugBank, TZN could act as an agonist to target Nischarin in humans. We next investigated the function of Nischarin receptor in lung cancer and its role in the anti-tumor activity of TZN. Results The treatment of TZN inhibited the proliferation, migration and invasion of A549 cells, and induced apoptosis. These results were further confirmed by that TZN treatment increased the Bax/Bcl-2 ratio in A549 cells. We also observed that TZN treatment changed the expression and phosphorylation of proteins of AKTand Wnt3a/β-catenin signaling pathway members. By bioinformatics analysis, we found that Nischarin was down-regulated in human lung cancer tissues and patients with high Nischarin expression had a better survival. Moreover, Nischarin functioned as a tumor suppressor in the survival and metastasis of A549 cells through the regulation of AKT and Wnt3a/β-catenin pathways. Knockdown of Nischarin promoted the proliferation, invasion, migration of A549 cells and inhibited the apoptosis, which were reversed by the TZN treatment. Conclusion Summary, our data revealed that treatment of TZN inhibited the growth of lung cancer cell line A549 and may be used as a novel strategy for lung cancer therapy.

Anandamide (AEA) played potent neuroprotective activities via cannabinoid type 1 (CB1) and 2 (CB2) receptor. N-Linoleyltyrosine (NITyr), as an AEA analogue, was synthesized in our laboratory and evaluated the neuroprotective effects and mechanisms for the first time. NITyr was synthesized via substitution reaction. The neuroprotective effects of NITyr were evaluated in a gerbil model of transient cerebral ischemia. Each gerbil was subjected to open field test (OFT), Rotard rod test (RRT), Morris water maze (MWM) successively and executed after animal behaviors. Part of the brain was stained with hematoxylin and eosin (HE) and Nissl staining, and the rest for biochemical analysis. NITyr could not increase spontaneous locomotor activity and ameliorate the anxiety behavior in the OFT but could improve the motor coordination in the RRT and the spatial memory impairment in the MWM. Immunohistochemically, NITyr could attenuate the ischemia-induced neural loss in the hippocampus. The Enzyme-linked immunosorbent assay (ELISA) suggested that NITyr ameliorated the inflammation and oxidative stress. Consistently, NITyr could up-regulate the expressions of p-phosphadylinositol 3-kinase (PI3K) and p-Akt but not PI3K and Akt in the hippocampus. In addition to oxidative stress, CB2 receptor antagonist AM630 but not CB1 receptor antagonist AM251 could reverse the above phenomena. However, CB1 receptor antagonist AM251 could reverse oxidative stress. Accordingly, NITyr could up-regulate the expressions of CB2 but not CB1. NITyr could improve the motor coordination, learning and memory impairments, neural loss in the hippocampus and the inflammation of the mice via CB2 receptor involvement of PI3K/Akt signaling pathway.

A new structural type for melt cast materials was designed by linking nitrotetrazole ring with 1,2,4-oxadiazole through a N-CH2-C bridge for the first time. Three N-CH2-C linkage bridged energetic compounds, including 3-((5-nitro-2H-tetrazol-2-yl) methyl)-1,2,4-oxadiazole (NTOM), 3-((5-nitro-2H-tetrazol-2-yl)methyl)-5-(trifluoromethyl)-1,2,4 -oxadiazole (NTOF) and 3-((5-nitro-2H-tetrazol-2-yl)methyl)-5-amine-1,2,4-oxadiazole (NTOA), were designed and synthesized through a two-step reaction by using 2-(5-nitro-2H-tetrazole -2-yl)acetonitrile as the starting material. The synthesized compounds were fully characterized by NMR (1H, 13C), IR spectroscopy and elemental analysis. The single crystals of NTOM, NTOF and NTOA were successfully obtained and investigated by single-crystal X-ray diffraction. The thermal stabilities of these compounds were evaluated by DSC-TG measurements, and their apparent activation energies were calculated by Kissinger and Ozawa methods. The crystal densities of the three compounds were between 1.66 g/cm3 (NTOA) and 1.87 g/cm3 (NTOF). The impact and friction sensitivities were measured by standard BAM fall-hammer techniques, and their detonation performances were computed using the EXPLO 5 (v. 6.04) program. The detonation velocities of the three compounds are between 7271 m/s (NTOF) and 7909 m/s (NTOM). The impact sensitivities are >40 J, and the friction sensitivities are >360 N. NTOM, NTOF and NTOA are thermally stable, with decomposition points > 240 °C. The melting points of NTOM and NTOF are 82.6 °C and 71.7 °C, respectively. Hence, they possess potential to be used as melt cast materials with good thermal stabilities and better detonation performances than TNT.

Precisely tuning the nuclearity of supported metal nanoclusters is pivotal for designing more superior catalytic systems, but it remains practically challenging. By utilising the chemical and molecular specificity of UiO-66-NH2 (a Zr-based metal–organic framework), we report the controlled synthesis of supported bi- and trinuclear Cu-oxo nanoclusters on the Zr6O4 nodal centres of UiO-66-NH2. We revealed the interplay between the surface structures of the active sites, adsorption configurations, catalytic reactivities and associated reaction energetics of structurally related Cu-based ‘single atoms’ and bi- and trinuclear species over our model photocatalytic formic acid reforming reaction. This work will offer practical insight that fills the critical knowledge gap in the design and engineering of new-generation atomic and nanocluster catalysts. The precise control of the structure and surface sensitivities is important as it can effectively lead to more reactive and selective catalytic systems. The supported bi- and trinuclear Cu-oxo nanoclusters exhibit notably different catalytic properties compared with the mononuclear ‘Cu1’ analogue, which provides critical insight for the engineering of more superior catalytic systems., The controlled synthesis of novel bi- and trinuclear Cu-oxo nanoclusters supported on UiO-66-NH2 that show notably different catalytic properties in the photocatalytic formic acid decomposition reaction is reported.

Hawthorn, a commonly used traditional Chinese medicine, has been suggested to have therapeutic effects on cardiovascular disease. However, effective fractions of hawthorn extract in the treatment of cardiovascular disease, together with possible therapeutic mechanisms, remain unclear. This study aimed to investigate the effects of four different polar fractions of hawthorn extract on blood stasis model rats, and explore the possible metabolic mechanisms by using a liquid chromatography-mass spectrometry metabolomics approach. Evaluation of hemorheology and fibrinogen showed that n-butanol and ethyl acetate fractions of hawthorn extract had significant therapeutic effects on blood stasis model rats. Furthermore, metabolomics analysis showed that n-butanol and ethyl acetate fractions of hawthorn extract could reverse imbalanced biomarkers in plasma and urine of blood stasis model rats. Additionally, metabolic pathway analysis revealed that plasma biomarkers were responsible for several important pathways, including d-glutamine and d-glutamate metabolism, phenylalanine, tyrosine and tryptophan biosynthesis, alanine, aspartate, and glutamate metabolism, sphingolipid metabolism, and arginine biosynthesis. Meanwhile, urine biomarkers were responsible for some important pathways, including phenylalanine metabolism, tyrosine metabolism, and lysine degradation. This study demonstrated that n-butanol and ethyl acetate fractions of hawthorn extract had significant therapeutic effects on blood stasis model rats, and the underlying mechanisms involved multiple metabolic pathways.

In this work, a simple one-step thermal oxidation process was established to achieve a significant surface increase in {110} and {111} nanofacets on well-defined, pure and Pr-doped, ceria nanocubes. More importantly, without changing most of the bulk properties, this treatment leads to a remarkable boost of their enzymatic activities: from the oxidant (oxidase-like) to antioxidant (hydroxyl radical scavenging) as well as the paraoxon degradation (phosphatase-like) activities. Such performance improvement might be due to the thermally generated sawtoothlike {111} nanofacets and defects, which facilitate the oxygen mobility and the formation of oxygen vacancies on the surface. Finally, possible mechanisms of nanoceria as artificial enzymes have been proposed in this manuscript. Considering the potential application of ceria as artificial enzymes, this thermal treatment may enable the future design of highly efficient nanozymes without changing the bulk composition., This work has been supported by the Ministry of Science, Innovation and Universities of Spain with Reference Numbers of ENE2017-82451-C3-2-R, MAT2016-81118-P and MAT2017-87579-R. The research projects funded by the Natural Science Foundation of Shandong Province (Grant ZR2017LB028), Key R&D Program of Shandong Province (Grant 2018GSF118032), and Fundamental Research Funds for the Central Universities (Grant 18CX02125A) in China are also acknowledged. TEM/STEM data were obtained at DMEUCA node of the Spanish Unique Scientific and Technological Infrastructure (ICTS) of Electron Microscopy of Materials ELECMIM. M. Tinoco thanks the FPU Scholarship Program (Grant AP2010-3737) from Ministry of Education of Spain. H. Pan is grateful for financial support (Grant 201406140130) from the Chinese Scholarship Council to accomplish her Ph.D. study at the University of Cadiz (Spain). J. M. Gonzalez, G. Blanco, and X. Chen are also grateful for the financial support from the joint project (Proyectos Integradores, Grant PI20201) in IMEYMAT of the University of Cadiz.

Aim: Chitinase 3-like 1 (CHI3L1) has the potential to prompt proliferation and angiogenic formation. Interleukin-13 receptor α2 (IL-13Rα2) was regarded as a receptor of CHI3L1; however, it is unknown whether CHI3L1 adjusts the neovascularization in late atherosclerotic lesions of apoE−/− mice via IL-13Rα2.Methods: Silicone collars were placed around one of the common carotid arteries of apoE−/− mice fed with a high-fat diet. The mice were further injected with Ad.CHI3L1 alone or Ad.CHI3L1 + Ad.IL-13Rα2 shRNA through the caudal vein. The plaque areas in the whole aorta and aortic root were evaluated by Oil Red O staining and H&E staining. The contents of CD31, CD42b, and collagen in carotid plaques were investigated by immunohistochemistry and Masson trichrome staining. The role of CHI3L1 in migration and tube formation of human umbilical vein endothelial cells (HUVECs) was determined by transwell and Matrigel tests. The effect of CHI3L1 on the expression of AKT and extracellular signal-regulated kinase (ERK) was evaluated with the Western blot.Results: The plaque loads in the aorta were significantly more extensive in apoE−/− mice injected with Ad.CHI3L1 than those with Ad.CHI3L1 + Ad.IL-13Rα2 shRNA. CHI3L1 significantly increased the contents of CD31 and CD42b and decreased the element of collagen in late-stage atherosclerotic lesions of the carotid arteries. The effects of CHI3L1 on migration, tube formation, and upregulation of phospho-AKT and phospho-ERK of HUVECs were prohibited by inhibitors of phosphatidylinositol 3-kinase (PI3K) and mitogen-activated protein kinase kinase (MEK) as well as IL-13Rα2 shRNA.Conclusion: To some extent, CHI3L1 promotes migration and tube formation of HUVECs and neovascularization in atherosclerotic plaques possibly mediated by IL-13Rα2 through AKT and ERK signal pathways.

The adenomatous polyposis coli (APC) is a frequently mutated tumour suppressor gene in cancers. However, whether APC is regulated at the epitranscriptomic level remains elusive. In this study, we analysed TCGA data and separated 200 paired oesophageal squamous cell carcinoma (ESCC) specimens and their adjacent normal tissues and demonstrated that methyltransferase-like 3 (METTL3) is highly expressed in tumour tissues. m6A-RNA immunoprecipitation sequencing revealed that METTL3 upregulates the m6A modification of APC, which recruits YTHDF for APC mRNA degradation. Reduced APC expression increases the expression of β-catenin and β-catenin-mediated cyclin D1, c-Myc, and PKM2 expression, thereby leading to enhanced aerobic glycolysis, ESCC cell proliferation, and tumour formation in mice. In addition, downregulated APC expression correlates with upregulated METTL3 expression in human ESCC specimens and poor prognosis in ESCC patients. Our findings reveal a mechanism by which the Wnt/β-catenin pathway is upregulated in ESCC via METTL3/YTHDF-coupled epitranscriptomal downregulation of APC., The epitranscriptomic regulation of adenomatous polyposis coli (APC) tumour suppressor gene in cancers is unclear. Here the authors show that N6-methyladenosine methylation writer METTL3 downregulates APC by recruiting YTHDF2 for APC mRNA degradation, and that this promotes glycolysis and tumour growth in oesophageal cancers.

Flexible Zn-air battery (ZAB) depicts promising prospects for the eventual realization of next-generation flexible electronic devices. However, developing such flexible power sources with high efficiency and durability remains a great challenge, largely due to the low effectiveness of the key components within the ZAB configuration. Herein, we demonstrate an efficient, flexible and rechargeable ZAB by integrating an active Co-N-C reversible electrocatalyst and a highly conductive alkalined polyacrylate hydrogel. The active sites for the oxygen reduction and evolution reactions (ORR-OER) within the catalyst are carefully identified and facily tuned, enabling the engineered catalyst to deliver much better bifunctional activities than the noble-metal counterparts yet with only approximately 7% cost of the latter. The alkalined hydrogel affords preeminent ionic conductivity and water retention capability, well satisfies the role for solid-state electrolyte. Impressively, the thus fabricated solid-state flexible ZAB exhibits an open circuit voltage of 1.45 V, a peak power density of 144.6 mW cm−2, a round trip efficiency of 62%, a stable rechargebility for over 400 cycles at 2 mA cm−2 along with excellent flexibility, which even outperform those from many aqueous ZABs, highlighting its great potential as flexible power source for next-generation electronics.

YKL-40 is recently regarded as a pro-inflammatory cytokine involved in the pathological process of atherosclerosis and lipid metabolism. However, whether YKL-40 can directly influence the development of atherosclerosis and levels of lipid parameters is unknown. The aim of this study is to explore the effects of YKL-40 on atherosclerotic features, the levels of serum lipids, and biomarkers in apolipoprotein (E)-deficient (ApoE-/-) mice fed a high-fat diet. ApoE-/- mice were injected with a recombinant adenovirus expressing mouse YKL-40 or control adenovirus through the caudal vein. The levels of serum YKL-40, interleukin-6 (IL-6), tumour necrosis factor-alpha (TNF-alpha), matrix metalloproteinase-9 (MMP-9), and soluble vascular cell-adhesion molecule 1 (sVCAM-1) were measured by ELISA. Lipid metabolism parameters were measured using immunoturbidimetric assay. The size of plaque area in aorta was evaluated by Oil Red O and hematoxylin/eosin (HE) staining. The content of collagen fibers was stained with Masson, and the content of macrophages and smooth muscle cells (SMCs) in atherosclerotic lesions was investigated by immunohistochemistry. The serum levels of total cholesterol and triglycerides were similar between these two groups. Compared with the control, the levels of serum YKL-40, IL-6, TNF-alpha, MMP-9, plaque size, and macrophages in plaques were significantly increased in mice with adenovirus overexpressing YKL-40. However, the content of collagen fibers and SMCs was remarkably decreased in mice with adenovirus overexpressing YKL-40 than that in control. YKL-40 prompts the progress of atherosclerosis maybe involved with its role of pro-inflammation, but does not affect lipid metabolism in ApoE-/- mice fed a high-fat diet.

In this research, titanium carbide was fabricated onto carburized AISI 1020 steel through thermo-reactive diffusion (TRD) with salt bath processing at 900 °C for 3 h. The researchers investigated the microstructure and the wear resistance of the as-obtained coating. Results showed that the as-received coating was of 7.5 ± 0.3 μm with surface micro-hardness of approximately 1885 ± 121 HV0.025. The coating presented excellent adhesion to the substrate as evidenced by a bonding force between the coating (carbide layer) and substrate of approximately 52 N. During the sliding test, its friction coefficient (0.45–0.56) tended to decrease in the final stage. In comparison with the bare substrate, the specific wear volume loss for the titanium carbide–coated specimen decreased by 78%.

Fe-N-C materials, when prepared as single-atom catalysts (SAC), display excellent activities in oxidation reactions. The systematic investigation of the iron coordination mode revealed that Fe-N4C catalysts are the most active for C-H bond oxidation. However, many of these catalysts are synthesized through pyrolysis, which is characterized by a lack of control and structures with heterogeneous composition, rarely presenting only atomically dispersed Fe−N−C as active sites. Herein, an alternative, reliable and easily reproducible method to obtain highly active Fe SACs (atomically dispersed) with Fe-N4 sites is presented, which is based on ion exchange of sodium from high crystalline sodium poly(heptazine imide) (Na-PHI) by other ions. The obtained catalyst can photocatalytically oxidize C-H bonds selectively toward ketones using only dioxygen. Detailed mechanism investigations indicate that the active species in the C-H bond oxidation are highly valent Fe(IV)/Fe(V)-oxo species, which are further activated by the holes generated at the PHI support under light irradiation.

The direct formate fuel cells in alkaline medium is attracting more and more attention, because of their reasonable power density, facile power system, and low formate crossover. Herein, we successfully prepare the XC-72 carbon-supported PdRh alloy nanocrystals (PdRh/XC-72 nanocomposites) with different Pd/Rh atomic ratios by precipitation–reduction strategy. The as-prepared Pd5Rh1/XC-72 nanocomposites show the excellent electrocatalytic mass activity (4.5 A mg–1) for the formate oxidation reaction (FOR) in a KOH medium, which is 2.3-fold mass activity enhancement over commercial Pd/C anodic catalyst (1.9 A mg–1) for the FOR in a KOH medium. The obvious activity enhancement can be ascribed to the high dispersibility, the electronic effect, and the suitable OHad species. Meanwhile, the Rh atoms in the PdRh alloy also can weaken the CO accumulation during the FOR and simultaneously enhance the electrochemical self-stability of catalyst, resulting in excellent electrocatalytic durability of Pd5Rh1/XC-72 nano...

TiO2 is modified by Fe-doping reduction method to regulate the pore structure of TiO2. When the Fe/Ti molar ratio of 0.05, the Fe–Mn/TiO2 (0.05Fe) catalyst shows an almost 100% NO conversion and N2 selectivity in the range of 170–250 °C. The catalyst exhibits a catalytic activity above 95% even in the presence of SO2 and water. The N2 adsorption–desorption, XRD, H2-TPR, XPS, TG and TEM are used to characterize the catalysts. The results show that the modification of Fe in the TiO2 carrier enlarges the catalysts’ BET surface area, increases the proportion of the high valence states of Mn on the surface, and promotes more defect of the lattice oxygen, and makes TiO2 be coated and protected. All these modification keeps the catalyst having a high and stable SCR activity and sulfur and water resistance at low temperature.

Supercapacitors have received considerable attention owing to high power density, high safety and great cycling performance. Great efforts have been devoted to hunting new materials for supercapacitor applications. In this work, we report a novel nanomaterial of LaB 6 nanowires (NWs) on carbon fiber cloth serving as active electrochemical materials for supercapacitors. The LaB 6-carbon fiber cloth electrodes could work in two different electrolytes including 1 M Na2SO4 and 1M H2SO4. The as-prepared LaB6 NWs electrode delivered a significant areal capacitance as high as 17.34 mF cm−2 in 1.0 M Na2SO4 solution at a current density of 0.1 mA cm−2. Moreover, the LaB6 NWs electrode displayed outstanding cycling stability after 10,000 charging/discharging cycles. The electrochemical charge/discharge mechanism in 1M Na2SO4 was studied. This work lay the foundations for developing LaB6 NWs as supercapacitor electrode and open the door to the design of boride nanomaterials for energy storage applications.

Heteroatom-doped carbon nanomaterials are highly promising cost-effective electrocatalysts for replacing noble metal nanomaterials in many energy-related electrocatalytic fields. Herein, the nitrogen-doped graphene aerogels (N-GA) with tunable nitrogen content are synthesized by the pyrolysis of the graphene aerogels-polyallylamine (GA-PAA) hybrids. By changing the molecular weight of PAA in the GA-PAA hybrids, the nitrogen content of the N-GA can be regulated from 0.58% to 2.07%. The electrocatalytic activity of the N-GA increases with the nitrogen content for the oxygen reduction reaction (ORR) in the alkaline media. The three-dimensionally porous interconnected structure and the nitrogen doping endow the N-GA with excellent electrocatalytic activity and durability for the ORR in the alkaline media.

Optimizing the shape, structure, and interface of noble metal bimetallic nanostructures significantly improves their catalytic properties. Recently, Au@Pd core–shell bimetallic nanostructures have ...

The first double-walled bimetal-organic framework [Cd4K4(TADA)4(H2O)12]·6DMF (1, TADA = 3,3'-((6-hydroxy-1,3,5-triazine-2,4-diyl)bis(azanediyl)) dibenzoate) has been successfully constructed. In virtue of its high porosity and abundant basic sites, MOF 1 can be served as a high-efficiently size-selective heterogeneous catalyst for Knovenagel condensation reaction. Remarkably, 1 also exhibits excellent luminescent detectability for metronidazole (MDZ) with the highest quenching constant ( Ksv) of 1.16 × 105 M-1. The results demonstrate that 1 can be served as a unique bifunctional platform for antibiotics sensing and size-selective catalysis.

This mini-review highlights some recent progress in the engineering of single-atom catalysts (SACs) through metal-organic frameworks (MOFs) and derivatives. The inherent molecular and chemical specificities within the MOFs and derivatives can offer stabilisation of the SACs with high atomic isolation and dispersion. As MOFs are often considered an infinite array of self-assembled molecular catalysts, specifically designed structures can provide further functionalities to suit the needs of different catalytic applications. In brief, we can divide the preparation approaches into three main categories: (1) fabrication onto functional groups of the ligands, (2) fabrication onto Lewis acid sites of nodal centres, and (3) synthesis via a pyrolysis-mediated technique. Through these approaches, strong metal-support interactions can be established to aid the fine-tuning of the catalytic properties. We also discuss how recent progress in the development of state-of-the-art microscopic, spectroscopic, and crystallographic techniques has enabled scientists to elucidate the structure-activity relationship.

Purpose This study aimed to determine if both ubiquitous and heterogeneous somatic mutations could be detected in circulating cell-free DNA (cfDNA) in patients with esophageal squamous cell carcinoma (ESCC). Methods Paired multi-regional tumor tissues, cfDNA, and white blood cells (WBCs) were collected from five ESCC patients before treatment, as part of an ongoing prospective study (NCT02395705). Samples from Cohort 1 were sequenced by whole-exome sequencing and samples from Cohort 2 were sequenced by targeted capture sequencing. Somatic single-nucleotide variations (SNVs) were detected by comparing solid tumor or cfDNA with matched WBCs, with a minimum variant allele frequency (VAF) of 0.1% and P value Results Genomic DNA (gDNA) and plasma-derived cfDNA from 26 samples were sequenced successfully. In Cohort 1, a significant linear relationship between the tumor and cfDNA VAFs (R2= 0.78, P Conclusions Both sequencing approaches revealed high intratumoral heterogeneity in ESCC, and enabled the detection of both ubiquitous and heterogeneous mutations in cfDNA.

Background To study the protective effect of berberine (BBR) on cisplatin-induced acute kidney injury (AKI) and its effect on mitophagy. Methods (I) Male C57BL/6 mice aged 6-8 weeks were randomly divided into control group (saline), cisplatin group (cisplatin), and cisplatin + BBR (5, 10 mg/kg) groups. In the cisplatin group and BBR groups, mice were injected intraperitoneally with 15 mg/kg of cisplatin. Mice in BBR groups were given BBR at 72, 48, 24, 0.5 h before and 24, 48 h after cisplatin injection. Mice were sacrificed 72 h after cisplatin injection, and blood were collected for detecting serum creatinine (SCr) and blood urea nitrogen (BUN) levels. Kidneys were collected for detecting protein expression levels of Kidney injury molecule 1 (KIM-1), LC3 II/LC3 I, p62, PINK 1, Parkin in the renal tissue by Western blotting. The pathological changes in renal tissues were observed using periodic acid-Schiff (PAS) staining. (II) Renal tubular epithelial cells (RTECs) were pretreated with different concentrations (1, 2, and 4 µM) of BBR, and then incubated with cisplatin. Changes in autophagy proteins LC3 II/LC3 I, p62, PINK 1, and Parkin were detected by Western blotting, and changes in cellular reactive oxygen species (ROS) and mitochondrial membrane potential (MMP) were detected by flow cytometry. Results (I) Mice treated with BBR at dosage of 5 and 10 mg/kg for 6 days showed significant reduction in SCr and BUN compared to that in mice treated with cisplatin. PAS staining and immunohistochemistry showed that BBR ameliorated cisplatin-induced nephrotoxicity and reduced cisplatin-induced increase in protein expression levels of KIM-1. Compared to cisplatin-treated mice, the mice treated with BBR showed increased LC3 II/LC3 I, PINK 1, and Parkin, and decreased p62 protein expression. (II) Compared to cisplatin-incubated RTECs, cells pretreated with BBR for 24 h exhibited increased protein expressions of LC3 II/LC3 I, PINK1, and Parkin and decreased protein expression of p62. BBR reversed cellular ROS and cell MMP level induced by cisplatin. Conclusions BBR plays a protective role in cisplatin-induced AKI by up-regulating mitophagy in RTECs.