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To develop efficient ionic liquid (IL)-based separation processes like extractive distillation, the knowledge of IL-involved vapor–liquid equilibria (VLE) is necessary. Since experimental measureme...

Synergistic flame-retardant effect of aluminum diethyl phosphinate (AlPi) in intumescent flame retardant polypropylene (PP/IFR) system and the flame-retardant mechanism were investigated. The flame retardancy of PP/IFR/AlPi (the mass ratio of IFR to AlPi is 2 : 1) was the best, which was proved by the results of the limiting oxygen index (LOI) test, UL-94 test, and cone calorimeter test ( CCT) test. Here, the LOI value of the sample was as high as 34% and passed the V–0 rating in UL–94 test. The peak heat release rate (PHRR) decreased by 92.57%, the total heat release (THR) reduced by 90.52%. Thermogravimetric (TGA) data showed that the introduction of AlPi improved thermal stability and changed the thermal degradation behavior of PP/IFR composites. Interestingly, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDXS) and laser Raman spectroscopy (LRS) proved that PP/IFR/AlPi had formed more residual carbon, but the flame retardancy was worse than PP/IFR/AlPi. This is because when the mass ratio of IFR to AlPi is 2 : 1, the synergy between IFR and AlPi was significant, gas-phase flame retardant and condensed-phase flame retardant reached a balance and obtained the best flame retardant effect.

Phosphatase and tensin homolog (PTEN) is known to be involved in the pathogenesis of intracranial aneurysm (IA). This study investigated the molecular mechanism of exosomal miR-144-5p (ex-miR-144-5p) and PTEN in IA. Ex-miR-144-5p expression was assessed in serum from individuals with ruptured intracranial aneurysm (RA) or unruptured intracranial aneurysm (UA), and healthy controls (HC). Vascular endothelial cells (VECs) were co-cultured with exosomes isolated from mesenchymal stem cells (MSCs) with transfection of miR-144-5p mimic or miR-144-5p inhibitor. IA rats were induced by combing systemic hypertension and intrathecal elastase injection. VECs were transfected with miR-144-5p mimic or inhibitor to verify the impacts of miR-144-5p on cell viability and proliferation. The connection between miR-144-5p and PTEN was verified by luciferase activity assay. Our data proved that ex-miR-144-5p was decreased in both UA and RA patients. MiR-144-5p overexpression in MSCs-derived exosome promoted VEC viability, inhibited VEC proliferation of VEs, and decreased the protein levels of matrix metalloproteinase-9 (MMP-9), proliferating cell nuclear antigen (PCNA) and osteopontin (OPN). IA rats injected with ex-miR-144-5p mimic showed significant luminal dilation, declined smooth muscle layers, and thinned vascular wall. Besides, inhibited cell apoptosis and decreased protein expressions were also observed. However, ex-miR-144-5p inhibitor had the opposite effects both in vivo and in vitro. We validated that miR-144-5p directly targeted PTEN. MiR-144-5p mimic increased cell viability and proliferation and reduced protein expressions, which could be blunted by PTEN overexpression. This study suggests that miR-144-5p elevates PTEN expression, thereby boosting apoptosis and attenuating viability of VECs in IA.

2-Ethylhexyl acrylate (2-EHA) is one of the most widely used acrylates in the polymer industry, which is synthesized via Fisher esterification that is limited by chemical equilibrium. To intensify the esterification process, in this work, reactive extraction concept is proposed, with halogen-free deep eutectic solvent (DES [Im:2PTSA]) as dual solvent-catalyst that consists of imidazole (Im) and p-toluenesulfonamide (PTSA). The bifunctional effects of the DES [Im:2PTSA] are evaluated by thermodynamic analysis and experimental study. Favorable phase splitting is verified by σ-potential analysis predicted by COSMO-RS theory, combined with experiments, and the optimal acid-to-alcohol molar ratio is set to 1.2. The esterification kinetics is then experimentally determined and fitted using the molar-based and activity-based pseudo-homogeneous (PH) models, respectively. The activity-based PH model, that considers the bifunctional roles of the DES, proves to be more accurate with small RMSD of 0.0344. The stability of DES after recycling is validated to further confirm the industrial prospects of DES [Im:2PTSA] in 2-EHA production.

The pathogenesis of osteoporosis is considered extremely intricate. Osteoblast differentiation and angiogenesis can greatly affect bone development and formation, given their coupling role in these processes. Exosome-mediated miRNA regulates cellular senescence, proliferation, and differentiation. However, whether senescent osteoblasts can regulate the senescence of vascular endothelial cell by miRNA through exosomal pathway remains unclear. In this study, senescent osteoblasts could regulate endothelial cell function, promote cell senescence and apoptosis, and decrease cell proliferation via exosomal pathway. miR-139-5p showed high expression in senescent osteoblasts and their exosomes. After senescent osteoblast-derived exosome treatment, miR-139-5p was also upregulated in endothelial cells. Furthermore, transfection of miR-139-5p mimic promoted the senescence and apoptosis of vascular endothelial cells and inhibited their proliferation and migration, whereas transfection of miR-139-5p inhibitor rescued the effect of D-galactose. Using double luciferase assay, TBX1 was confirmed to be a direct target gene of miR-139-5p. In conclusion, senescent osteoblast-derived exosome-mediated miR-139-5p regulated endothelial cell function via exosomal pathway. Our study revealed the role of osteoblast-derived exosomes in the bone environment during aging, providing a clue for inventing a new target therapy.

We have developed a new radical-mediated alkoxypolyhaloalkylation of styrenes with polychloroalkanes and alcohols for the facile synthesis of complex polyhaloalkanes. 4-Methoxybenzenediazonium tetrafluoroborate is a good radical initiator for this transformation. This protocol is well applied to the late-stage functionalization of complex molecules, including vitamin E, estrone and cholesterol derivatives.

A three-component photoredox 1,2-alkylamination of styrenes involving functionalization of C(sp3)–H bonds in alkyl halides instead of functionalization of C-halogen bonds is disclosed. A variety of commercialized C(sp3)–H alkanes, including dichloromethane, acetonitrile, and acetone, used as alkyl radical precursors and solvents, were compatible with this methodology. The mechanistic study shows that alkyl radicals are generated by hydrogen atom transfer (HAT) between aryl radicals and alkyl halides.

A cobalt-promoted electrochemical 1,2-diarylation of alkenes with electron-rich aromatic hydrocarbons via direct dual C-H functionalizations is described, which employs a radical relay strategy to produce polyaryl-functionalized alkanes. Simply by using graphite rod cathode instead of platinum plate cathode, chemoselectivity of this radical relay strategy is shifted to the dehydrogenative [2+2+2] cycloaddition via 1,2-diarylation, annulation, and dehydrogenation cascades leading to complex 11,12-dihydroindolo[2,3-a]carbazoles. Mechanistical studies indicate that a key step for the radical relay processes is transformations of the aromatic hydrocarbons to the aryl sp2 -hybridized carbon-centered radicals via deprotonation of the corresponding aryl radical cation intermediates with bases.

Emerging evidence has demonstrated that long non-coding RNAs (lncRNAs) are related to the pathogenesis of atherosclerosis (AS). We aimed to investigate the roles and molecular mechanisms of myocardial infarction-associated transcript (MIAT) in the proliferation, migration and invasion of oxidized low-density lipoprotein (ox-LDL)-induced vascular smooth muscle cells (VSMCs). Quantitative real-time polymerase chain reaction (qRT-PCR) was conducted to determine the levels of MIAT, microRNA490-3p (miR-490-3p) and Intercellular Adhesion Molecule 1 (ICAM1). Cell Counting Kit-8 (CCK-8) assay was carried out to assess cell proliferation. Transwell assay was employed to evaluate cell migration and invasion. Western blot assay was performed to measure the protein levels of proliferating cell nuclear antigen (PCNA), N-cadherin, matrix metalloprotein-9 (MMP9) and ICAM1. Dual-luciferase reporter, RNA immunoprecipitation (RIP) and RNA pull-down assays were conducted to verify the relationship between miR-490-3p and MIAT or ICAM1. MIAT was elevated in AS patients' serum and ox-LDL-induced VSMCs. MIAT knockdown suppressed cell proliferation, migration and invasion in ox-LDL-stimulated VSMCs. MIAT acted as a sponge of miR-490-3p and miR-490-3p deficiency overturned the inhibition of MIAT knockdown on VSMC proliferation, migration and invasion. ICAM1 was a direct target of miR-490-3p and ICAM1 silencing repressed the proliferation, migration and invasion of ox-LDL-stimulated VSMCs. Moreover, ICAM1 overexpression reversed the impacts of MIAT knockdown on ox-LDL-induced VSMC proliferation, migration and invasion. MIAT knockdown could depress cell proliferation, migration and invasion via miR-490-3p/ICAM1 axis in ox-LDL-induced VSMCs.

The photoelectrochemical (PEC) water splitting determines by the light absorption and charge extraction/injection. Here, we dispersedly modified the core-shell structured Ni@Niy Fe1-y (OH)2 on Si photoanodes and in-situ electrochemically converted it to Ni@Niy Fe1-y OOH to form a Si/SiOx /Ni@Niy Fe1-y OOH assembly, exhibiting the adjustable band bending and catalytic ability in water oxidation depending closely on the composition of Niy Fe1-y OOH. Combining with the island-like dispersed distribution to maximize the light absorption and the Ni@Niy Fe1-y shell as a high work function and a catalytic layer to simultaneously enlarge charge extraction and injection, the Si/SiOx /Ni@Ni0.7 Fe0.3 OOH assembly achieved an onset potential of 1.0 VRHE , a saturated current density of 35.4 mA cm-2 and a more than 50 h stability in an electrolyte with pH 9 under AM1.5G simulated sunlight irradiation. Our findings suggested that regulating the charge energetics at Si-electrolyte interface by discontinuously modifying a composition-adjustable core-shell structure is a potential route to develop highly efficient PEC devices.

Heterocyclic compounds, especially N-heterocycles and O-heterocycles, are prominent structural motifs present in numerous natural products and medically and/or economically important compounds. This review aims to describe the development of transition-metal-catalyzed cycloaddition reactions of functionalized m-atom partners with alkynes to access a wide range of five-, six-, and seven-membered heterocycles, that is functionalized N-heterocycles and O-heterocycles such as azepines, isoquinolines, isocoumarins, spiroheterocycles, indoles, furans, and pyrroles, in a selectively controlled manner with an emphasis on scope and limitations and with a discussion of the mechanisms.1 Introduction2 Intermolecular Cycloaddition To Construct Azepine Derivatives2.1 [5+2] Cycloaddition2.2 [3+2+2] Cycloaddition2.3 [3+2]/[5+2] Cycloaddition3 Intermolecular [4+2] Cycloaddition To Construct Isoquinolines or Isocoumarins4 Intermolecular [3+2] Cycloaddition To Construct Spirohetero­cyclic Compounds, Indoles, Furans, and Pyrroles5 Summary and Outlook

Montan resin (MR) is a by-product produced during the refinement process of montan wax extracted from lignite and has no usage yet. Chemical modification is an effective method to change the material property for expanding or converting the application area of the material itself. Our previous study found that the high hydrophobicity of MR is the primary limiting factor for its utilization in agriculture. Based on this point, this study attempted to chemically modify MR using the oxidation of peracetic acid, resulting that the MR hydrophilicity was significantly improved, and a water-soluble product (WSP) was obtained. The optimized oxidation conditions of MR, including the reaction temperature (X1), reaction time (X2), weight ratio of oxidant and montan resin (X3), and oxidant concentration (X4), were determined using single-factor experiments and response surface analysis. The modification degree was evaluated using elemental and oil-water partition coefficient analyses, infrared (IR) spectroscopy, and gas chromatography-mass spectrometry (GC-MS), revealing that the oil-water partition coefficient of the modified product decreased and that the number of chemical constituents with oxygen-containing functional groups clearly increased after modification. Furthermore, the WSP was tested its effects on germination and seedling growth of the wheat seed. Compared with the control group, the WSP showed a promoting effect on the growth and germination of wheat. The WSP concentrations of 600 mg·L−1 and 300 mg·L−1 had the most substantial effect on the root and seedling growth of wheat, respectively. Implications: Montan resin, a useless by-product produced from crude montan wax, was chemically modified via oxidation of peracetic acid. Its hydrophilicity was significantly improved, and a water-soluble product was obtained after the chemical modification. The optimized oxidation conditions of montan resin were determined using single-factor experiments and response surface analysis. The amount of chemical constituents with oxygen-containing functional groups increased in the modified products after modification, as determined by IR and GC-MS analysis, among other methods. The water-soluble modified product showed an obvious effect in promoting growth and germination of wheat at 600 mg·L-1 and 300 mg·L-1, respectively.

Imidazole (Im) and benzenesulfonic acid (BSA) formed deep eutectic solvents (DESs) were used as acidic catalyst and solvent for the dehydration of fructose to 5-hydroxymethylfurfural (5-HMF). The DES formation involved an acid–base neutralization to produce equimolar salt from BSA and Im, and subsequent interaction between equimolar salt as hydrogen bond acceptor and excessive BSA as hydrogen bond donor. The BSA-rich DES [Im:1.5BSA] with a 1:1.5 molar ratio of Im:BSA and 10% dosage exhibited high catalytic activity for fructose dehydration with a 5-HMF yield of 90.1% at 100 °C after a very short reaction time (3 min). The bifunctionality of [Im:1.5BSA] for promoting reaction rates and catalytic activity of fructose dehydration has been identified by tuned acidity of DESs and hydrogen bond interaction among fructose, 5-HMF, and DESs demonstrated by conductor-like screening model for real solvents (COSMO-RS) theory.

For the first time, we employed the halogen-free deep eutectic solvent (DES) into the Knoevenagel condensation between aromatic aldehydes and active methylene compounds at room temperature. The DESs [3Im:PTSA] and [4Im:PTSA] were prepared by imidazole (Im) and p-toluenesulfonic acid (PTSA), which were experimentally screened from a series of organic acids with imidazole. α, β-Unsaturated carbonyl compounds were obtained in good to excellent yields under solvent-free conditions with fast reaction rate. These two DESs can be reused for multiple times with no loss of catalytic activity.

The separation of 1,3-butadiene (1,3-C4H6) and 1-butene (n-C4H8) is quite challenging due to their close boiling points and similar molecular structures. Extractive distillation (ED) is widely regarded as a promising approach for such a separation task. For ED processes, the selection of suitable entrainer is of central importance. Traditional ED processes using organic solvents suffer from high energy consumption. To tackle this issue, the utilization of ionic liquids (ILs) can serve as a potential alternative. In this work, a high-throughput computational screening of ILs is performed to find proper entrainers, where 36,260 IL candidates comprising of 370 cations and 98 anions are involved. COSMO-RS is employed to calculate the infinite dilution extractive capacity and selectivity of the 36,260 ILs. In doing so, the ILs that satisfy the prespecified thermodynamic criteria and physical property constraints are identified. After the screening, the resulting IL candidates are sent for rigorous process simulation and design. 1,2,3,4,5-pentamethylimidazolium methylcarbonate is found to be the optimal IL solvent. Compared with the benchmark ED process where the organic solvent N-methyl-2-pyrrolidone is adopted, the energy consumption is reduced by 26%. As a result, this work offers a new IL-based ED process for efficient 1,3-C4H6 production.

Garlic skin, a by-product of garlic processing, was supposed to improve the fermentation quality of high-moisture silages because of its low moisture content and active compounds. Thus, fermentation and microbial characteristics of high-moisture Pennisetum hydridum ensiled with the addition of 0, 10, 20, and 30 wt% garlic skin (on a fresh matter basis) were analyzed during a 60-days fermentation. Results showed that the addition of garlic skin increased the dry matter content and lactic acid production, and decreased the pH and ammonia-N content of the silage. Adding garlic skin changed the relative abundance of bacterial communities with an increase in Lactobacillus and a decrease in Clostridium relative abundance. In conclusion, co-ensiling of high-moisture Pennisetum hydridum with garlic skin could be a simple approach to improve the silage quality and nutrients preservation.

The dynamic analysis and optimal design of reactive extraction are challenging due to high nonlinearity of model equations and tough decision of judging criteria. In this work, a dynamic rate-based method is developed on gPROMS platform to get easy access to the solutions of reactive extraction with phase splitting. Based on rigorous criteria, dynamic analysis from initial state to final equilibrium (e.g., evolution of phase composition, mass transfer rate and reaction rate) and optimal design of operating conditions (e.g., extractant dosage and feed molar ratio) are achieved. To illustrate the method, the esterification of n-hexyl acetate is taken as an example. The approach proves to be reliable in the analysis and optimization of the exemplified system, which provides instructive reference for further process design and simulation of reactive extraction.

Interface engineering has been regarded as a promising strategy for enhancing the catalytic activities of heterojunction photocatalysts. Herein, we have adopted an in situ etching sulfurization method to construct a Zn2GeO4−x/ZnS intimate heterojunction, which exhibited excellent photocatalytic H2 production in the absence of a Pt co-catalyst. Distinctively, TEM and HRTEM measurements showed that the interface of the Zn2GeO4−x/ZnS heterojunction became rough (topologically) due to in situ etching sulfurization, and etching was found to be strongly dependent on the crystal orientation. Moreover, the surface of the Zn2GeO4 nanorods from flat (100) planes evolved into an irregular coastline-like structure topologized with (110) and (113) high-index planes. ICP and elemental distribution measurements indicated that during the precipitation of ZnS via in situ etching sulfurization, the migration and dissolution of Zn and Ge ions on the Zn2GeO4(100) plane led to the roughening of the interface and the evolution of crystal planes. XPS and EPR analyses showed that Zn2GeO4−x/ZnS contained more oxygen vacancies with structural evolution. The theoretical calculations demonstrated that oxygen defects were prone to be generated on the Zn2GeO4(113) plane and formed the Ge3c3+–VO complexes. Compared to the inactive (100) plane, etching caused the Zn2GeO4(110) planes to have a higher number of threefold coordinated germanium (Ge3c4+) and (113) high-index planes that possessed abundant active sites (Ge3c3+–VO complexes), which dramatically decreased the barrier and reaction energy of H2O dissociation. This work not only provides fundamental insights into the topological interface evolution and facet-dependent defect distribution but also offers a strategy for the design of efficient photocatalysts for H2 production without the use of Pt as a co-catalyst based on a multifunctional interface.

Butyl hexanoate (BuHE) is currently synthesized through the Fischer esterification with mineral acid as catalyst, which suffers from the problems of side reaction, difficult recycling, and corrosion. To overcome these disadvantages, ionic liquid 1-butyl-3-methylimidazolium hydrogen sulfate ([BMIm][HSO4]) is employed as dual catalyst-solvent for the esterification of hexanoic acid (HeAc) with n-butanol (BuOH) in a reactive extraction process. The dual functions of [BMIm][HSO4], extraction and catalysis, were confirmed by liquid-liquid equilibria for the two systems {[BMIm][HSO4] + HeAc + BuHE} and {[BMIm][HSO4] + BuOH + BuHE}, and by the comparison of esterifications with or without [BMIm][HSO4], respectively. Moreover, the optimal reactive extraction conditions for BuHE formation were obtained. Finally, the possible mechanism of intensification of [BMIm][HSO4] on BuHE formation in reactive extraction process was proposed.

Currently, it is still a huge challenge to prepare flame-retardant polymeric materials with excellent fire safety, high strength, good durability and processability. We here propose a H-bonding cross-linking strategy that can simultaneously endow polymers with excellent flame retardancy, non-dripping behavior and enhanced strength. In this work, a novel benzimidazole monomer, 2-(4-methoxycarbonyl-phenyl)-1H-benzimidazole-5-carboxylic acid methyl ester (PBM) has been designed as a H-bonding cross-linking monomer to prepare poly(ethylene terephthalate)-based copolyesters (PET-co-PBMs). Interestingly, along with the hydrogen bonding, the π-π stacking interactions from the benzimidazole groups also exist. Due to the formation of physical crosslinking network via hydrogen bonding and π-π stacking, the melt strength of copolyesters are greatly improved. Combining with char forming ability of benzimidazole, PET-co-PBMs display excellent fire safety. Moreover, PET-co-PBMs also exhibit higher glass transition temperature, higher mechanical strength and good processability. This work provides a promising strategy to design polymers with high strength, good processability, excellent flame retardance and anti-dripping performance.

In present study, the poisoning mechanism of Cl on V/TiO2 catalyst for SCR removal of NOx using NH3 as the reductant was explored by in situ DRIFT technique. The experimental results revealed that the existence of Cl did not change the SCR reaction mechanism over V/TiO2 catalyst, which was mainly under the control of both E-R and L-H mechanisms. The deactivation of V/TiO2 catalyst by Cl was mainly resulted from the inhibited adsorption of NH3 and NOx species, accompanied by the decrease of the reactivity of adsorbed NH3 species.

Tumor complexity makes the development of highly sensitive tumor imaging probes an arduous task. Here, we construct a peptide-based near-infrared probe that is responsive to fibroblast activation protein-α (FAP-α), and specifically forms nanofibers on the surface of cancer-associated fibroblasts (CAFs) in situ. The assembly/aggregation-induced retention (AIR) effect results in enhanced accumulation and retention of the probe around the tumor, resulting in a 5.5-fold signal enhancement in the tumor 48 h after administration compared to that of a control molecule that does not aggregate. The probe provides a prolonged detectable window of 48 h for tumor diagnosis. The selective assembly of the probe results in a signal intensity over four- and fivefold higher in tumor than in the liver and kidney, respectively. With enhanced tumor imaging capability, this probe can visualize small tumors around 2 mm in diameter.

A sequence of Cr-modified CeZr2Ox catalysts were synthesized through the co-precipitation way and applied in selective catalytic reduction (SCR) of NOx with ammonia. The optimal catalyst (Cr1CeZr2Ox) exhibited the excellent NH3-SCR activity and high SO2 resistance. From the characterization results, Cr species in Cr1CeZr2Ox could suppress the formation of ZrO2 crystals, which could also contribute to stronger surface acidity and reducibility. Besides, more Ce3+ and surface adsorbed oxygen species were observed on Cr1CeZr2Ox catalyst. On the basis of in situ DRIFT experiments, it could be confirmed that the NH3-SCR process on Cr1CeZr2Ox was promoted through Langmuir-Hinshelwood (L-H) mechanism. Besides, the improved NO oxidation and more ad-NOx and ad-NH3 also played a vital role for the superior low-temperature SCR activity of Cr1CeZr2Ox.

Sb-modified Mn/TiO2 catalyst synthetized by sol–gel method exhibited outstanding performance in simultaneous Hg0 oxidation and NO reduction under SCR conditions at low temperature. NO removal (>90%) and Hg0 oxidation (>80%) were simultaneously obtained over MnSb/TiO2-0.25 catalyst in 200–300 °C with a GHSV of 54,000 h−1. Moreover, MnSb/TiO2-0.25 catalyst exhibited excellent tolerance to SO2 and H2O. Characterization results suggested that the well-dispersed Mn, Sb and Ti species, along with the enriched Mn4+ and surface oxygen species on Mn-Sb/TiO2-0.25 catalyst should play a critical role in its excellent catalytic performance. The formed HgO had little inhibition effect on NO reduction over MnSb/TiO2-0.25 catalyst. And the coexistence of NO and O2 has a promotion effect on Hg0 oxidation, while NH3 exhibited an inhibition effect on oxidation of Hg0. In SCR reaction process, the Hg0 oxidation efficiency was suppressed, but this effect could be basically eliminated by using a relatively low GHSV value. Thus using MnSb/TiO2-0.25 for simultaneous Hg0 oxidation and NO reduction in SCR reactor may be workable in coal-burning power plants. Based on the results of experiments and characterizations, the mechanism of synchronous removal of Hg0 and NO on MnSb/TiO2-0.25 catalyst could be described as:Hg0(ad)+Oα(Oβ)→HgO(ad), NO(g)+NO2(ad)+NH3(ad)→N2+H2O.

Air, water, and DINCH (Di-isononyl-cyclohexane-1,2-dicarboxylate) were selected as the cooling media to prepare polypropylene hollow fiber membranes by melt spinning. The effects of various cooling ways with different cooling rates on the row-nucleated lamellar crystallization were investigated. The crystallinity, orientation and arrangement of the crystals were examined by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and small-angle X-ray scattering (SAXS). Membrane morphology was observed by SEM. The less uniform pores, a layer of amorphous phase, and only a small part of slit-shaped pores were observed on the surface of samples when water and DINCH were used as the heat transfer medium because the fast cooling rate froze the surface molecules and decreased the crystallinity and orientation. However, when air was used as the cooling medium, the higher crystallinity and the better orientation of the annealed hollow fibers were obtained mainly due to the slow cooling rate. Corresponding hollow fiber membranes prepared by stretching had better interconnectivity of pores and larger pure water flux. Thus this study explains why air was selected as the cooling medium to prepare polypropylene hollow fiber membranes which can have larger pure water flux. Also, it provides new insights into the structure control of polypropylene hollow fiber membranes by stretching in order to prepare membranes with high strength.

Polypropylene (PP)/poly(ethylene-co-vinyl alcohol) (EVOH) blends were prepared by melt blending using PP-g-MAH as a compatabilizer. The microstructure and rheological behavior of PP/EVOH blends were studied. The results showed the that EVOH particles were uniformly dispersed in the PP matrix and inhibited the mobility of PP chains. The isothermal crystallization kinetics and morphology development of PP/EVOH blends were compared with that of pure PP. It was found that the EVOH essentially acted as an effective nucleating agent for PP, which could significantly increase the nucleation rate because the EVOH molecules in PP/EVOH blends aggregated together to form interface. Therefore, the introduction of EVOH increased the overall rate of isothermal crystallization compared with pure PP, although the PP molecular chains would be hindered seriously if excessive amounts of EVOH were added. X-ray diffraction showed that pure PP and PP/EVOH blends exhibited an identical crystal structure, and the crystallinity of the PP phase in the blends was not significantly different from that of pure PP.

Expressed in macrophages and endothelial cells, the receptor for angiopoietin, tyrosine kinase with immunoglobulin and epidermal growth factor homology-2 (Tie2), is required for the reconstruction of blood vessels in tumor recurrence after chemotherapy. Thus, small therapeutic peptides that target and block Tie2 activity are promising as a therapeutic for the prevention of tumor relapse after chemotherapy. However, such small peptides often have low bioavailability, undergo rapid enzymatic degradation, and exhibit a short circulation half-life, making them ineffective in cancer therapy. Herein, we designed a dual-responsive amphiphilic peptide (mPEG1000-K(DEAP)-AAN-NLLMAAS) to modify the small peptide T4 (NLLMAAS) as a Tie2 inhibitor, endowing it with the ability to endure in circulation and specifically target tumor tissue. The ultimate nanoformulation (P-T4) releases T4 in response to the combination of the acidic tumor microenvironment and the presence of legumain, which is commonly overexpressed in tu...

Developing highly efficient heterojunction photocatalysts, especially ternary heterojunctions, is a promising strategy to enhance hydrogen (H2) production activity in the photocatalytic process. The compatibility of components and the matching of electronic structure are main challenges in constructing novel photocatalytic activity ternary heterojunctions which include sufficient light absorption, controlled electronic transmission, and high electron utilization efficiency. In this research, the electronic structure of carbon nitride (CN) was regulated continuously by selecting different nitrogen-rich precursors and changing calcination methods, and then CN/CN isotype heterojunctions were constructed to improve the compatibility of components. Next the CN/CN isotype heterojunctions were composited with Pt–TiO2 to design and construct different models of ternary heterojunctions successfully. The different effects of components alignment, band structure and light absorption on photoelectrical and photocatalytic activities were studied systematically in ternary heterojunctions. Among them, the efficient melamine-derived carbon nitride (CN-M)/urea-derived carbon nitride (CN-U)/Pt-TiO2 (CN-M/CN-U/Pt-TiO2) ternary heterojunction has outstanding photocatalytic activity in which the H2 production rate reaches a maximum of approximately 1735 μmol h−1 g−1 using triethanolamine (TEOA) as the sacrificial reagent under visible light irradiation. The H2 production rate is about 4.9 times that of the pure CN-U component, 2.2 times that of the CN-M/CN-U isotype heterojunction and 3.5 times that of the CN-U/Pt-TiO2 binary heterojunction. By means of high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), fluorescence emission spectra, photoelectrochemical and other measurements, the outstanding performance attributed to the well compatible and composited sequence of components, rational energy level alignment and favorable band offset. It is confirmed to result in sufficient light absorption, high efficiency of photo-induced charge separation, and efficient electronic continuous and directional transmission (prolonging the electron lifetime). The study took advantage of the controllability of the electron structure in CN photocatalyst, and provides a facile approach to designing highly efficient visible light responding CN-based ternary heterojunctions for multi-functional applications in the photocatalytic research field.

The no-reflow phenomenon induced by ischemia-reperfusion (I/R) injury seriously limits the therapeutic value of coronary recanalization and leads to a poor prognosis. Previous studies have shown that luteolin (LUT) is a vasoprotective factor. However, whether LUT can be used to prevent the no-reflow phenomenon remains unknown. Positron emission tomography perfusion imaging, performed to detect the effects of LUT on the no-reflow phenomenon in vivo, revealed that LUT treatment was able to reduce the no-reflow area in rat I/R models. In vitro, LUT was shown to reduce the hypoxia-reoxygenation injury-induced endothelial permeability and apoptosis. The levels of malondialdehyde, reactive oxygen species and NADPH were also measured and the results indicated that LUT could inhibit the oxidative stress. Western blot analysis revealed that LUT protected endothelial cells from I/R injury by regulating the Wnt/β-catenin pathway. Overall, we concluded that the use of LUT to minimize I/R induced microvascular damage is a feasible strategy to prevent the no-reflow phenomenon.

In this study, the ability of Yarrowia lipolytica to produce the recombinant lipase CalB from Candida antarctica, used as a model protein has been compared across different bioreactor processes using glycerol, a byproduct from the biodiesel industry as the main carbon source. Batch, pulsed fed-batch (PFB), and continuous fed-batch (CFB) strategies were first compared using classical stirred tank (STR) bioreactors in terms of biomass production, carbon source uptake, and lipase production. Additionally, an in situ fibrous bed bioreactor (isFBB) was developed using sugarcane bagasse as a cell immobilization support. The maximum lipase titer achieved using the isFBB culture mode was 38%, 33%, and 49% higher than those obtained using the batch, PFB, and CFB cultures, respectively. The lipase productivity in isFBB mode (142U/mL/h) was 1.4-fold higher than that obtained using batch free cell cultures. These results highlight that isFBB is an efficient technology for the production of recombinant enzymes.

An effective tumor vaccine vector that can rapidly display neoantigens is urgently needed. Outer membrane vesicles (OMVs) can strongly activate the innate immune system and are qualified as immunoadjuvants. Here, we describe a versatile OMV-based vaccine platform to elicit a specific anti-tumor immune response via specifically presenting antigens onto OMV surface. We first display tumor antigens on the OMVs surface by fusing with ClyA protein, and then simplify the antigen display process by employing a Plug-and-Display system comprising the tag/catcher protein pairs. OMVs decorated with different protein catchers can simultaneously display multiple, distinct tumor antigens to elicit a synergistic antitumour immune response. In addition, the bioengineered OMVs loaded with different tumor antigens can abrogate lung melanoma metastasis and inhibit subcutaneous colorectal cancer growth. The ability of the bioengineered OMV-based platform to rapidly and simultaneously display antigens may facilitate the development of these agents for personalized tumour vaccines., Outer membrane vesicles (OMVs), non-replicative particles secreted by Gram-negative bacteria, are known for their immunostimulatory and adjuvant properties. Here, by employing a Plug-and-Display technology, the authors engineer OMVs to display tumor antigens on the surface, a platform that promotes anti-tumor immune responses in preclinical cancer models.

This study investigated the effect of methyl-CpG-binding protein 2 (MeCP2) on miRNA transcription. Our results of miRNA chip assay and ChIP-seq showed that MeCP2 inhibited the expressions of numerous miRNAs by binding to their upstream elements, including not only the promoter but also the distal enhancer. Among the affected miRNAs, miR-22 was identified to remarkably suppress gastric cancer (GC) cell proliferation, arrest G1–S cell cycle transition, and induce cell apoptosis by targeting MeCP2, MTHFD2, and MTHFR. Understanding GC metabolism characteristics is the key to developing novel therapies that target GC metabolic pathways. Our study revealed that the metabolic profiles in GC tissues were altered. SAM (S-adenosylmethionine), a universal methyl donor for histone and DNA methylation, which is specifically involved in the epigenetic maintenance of cancer cells, was found increased. The production of SAM is promoted by the folate cycle. Knockdown of MTHFD2 and MTHFR, two key enzymes in folate metabolism and methyl donor SAM production, significantly suppressed GC cell proliferation. MiR-22 overexpression reduced the level of endogenous SAM by suppressing MTHFD2 and MTHFR, inducing P16, PTEN, and RASSF1A hypomethylation. In conclusion, our study suggests that miR-22 was inhibited by MeCP2, resulting in deficiency of endogenous SAM, and ultimately leading to tumor suppressor dysregulation.

Oxygen-glucose deprivation and reoxygenation (OGD/R)-induced impairment of astrocytes may lead to neuronal dysfunction in the central nervous system (CNS). Apremilast is a phosphodiesterase 4 (PDE4) inhibitor primarily used for the treatment of psoriasis and psoriatic arthritis that has demonstrated certain neuroprotective properties. PDE4 is an isoenzyme that degrades 3'-5'-cyclic adenosine monophosphate (cAMP), which serves as a neuroprotective agent by promoting neuronal recovery through protein kinase (PKA)-mediated phosphorylation of cAMP response element-binding protein (CREB) and subsequent expression of the neurotrophic factor brain-derived neurotrophic factor (BDNF) and anti-apoptotic B cell lymphoma (Bcl-2). However, the effects of apremilast in astrocytes have not been elucidated. In the present study, we employed an in vitro model of ischemic stroke using oxygen-glucose deprivation and reoxygenation (OGD/R)-challenged astrocytes to investigate the effects of apremilast against apoptosis (the flow cytometry assay), cell death (the lactate dehydrogenase release assay), oxidative stress (2', 7' dichlorofluorescin diacetate staining), and the expression of the key neuroprotective factors CREB and BDNF (Western blot analysis). Our findings show that treatment with apremilast could significantly reduce astrocyte apoptosis and cell death induced by OGD/R as evidenced by reduced release of glial fibrillary acidic protein (GFAP) and improvement of the Bax/Bcl-2 ratio. The results of MTT assay, measurement of lactate dehydrogenase (LDH) release, and flow cytometry confirmed the improvement in cell viability mediated by apremilast. Importantly, we found that CREB phosphorylation was required for the increases in BDNF and Bcl-2 induced by apremilast as well as the decrease in astrocyte apoptosis. These preliminary findings indicate that apremilast may have the potential to prevent astrocyte cell death and promote neuronal healing in cerebral ischemic injury. Further in vivo research will expand our understanding of these promising results.

One-dimensional hydroxyapatite (HA) particularly mimics the structure of mineralized collagen fibrils and displays superior mechanical properties such as toughness. Herein, we report Se-doped HA/chitosan (Se-HA/CS) biopapers constructed with self-assembled Se-doped HA nanowires and chitosan. The Se-HA/CS biopapers with high flexibility and manufacturability can not only be further processed into arbitrary shapes by folding or using scissors but also display high performances in in vitro/vivo anti-bone tumor studies. The Se-HA/CS biopapers are more inclined to inhibit the growth of tumor cells (HCS 2/8 and SJSA cells) than that of normal human bone marrow stromal cells (hBMSCs). The potential mechanisms of this meaningful anti-tumor effect were investigated, such as reactive oxygen species accumulation and the activation of apoptosis and the underlying signal pathway involved (including caspase family, Bcl-2 family and JNK/STAT3). The results demonstrate that Se-HA/CS biopapers may inhibit the growth of HCS 2/8 and SJSA cells by synchronously inducing JNK activation and STAT3 inhibition and consequently promote the apoptosis of these cells. Furthermore, the in vivo anti-tumor studies confirm that the Se-HA/CS biopapers obviously suppress the growth of patient-derived xenograft tumor models.

Potassium, as one of the alkali metals, could cause significant deactivation on the Ce-based SCR catalysts. In this work, Zr-doping was found to efficiently enhance the K tolerance of Ce/TiO2 catalyst. The BET, XRD, Raman, XPS, H2-TPR, NH3-TPD, O2-TPD and NOx-TPD were adopted for exploring the mechanism of the promoted anti-K-poisoning property of Ce/TiO2 catalyst. The obtained results demonstrated that Ce/TiO2 with the addition of Zr exhibited larger specific surface area, higher dispersion of Ce species, higher redox property and more acid sites. As a result, the factors mentioned above could efficiently enhance the K tolerance of Ce/TiO2 catalyst. By virtue of the in situ DRIFT analysis, the SCR reaction over Ce/TiZrOx catalyst was accelerated via Langmuir-Hinshelwood (L-H) mechanism.

Removal of NO and Hg0 simultaneously was achieved on Nb-modified MnTiOx catalyst. Experimental results revealed that high NO conversion (>95%) and Hg0 oxidation (>95%) in 200–300 °C were available on Mn0.15Nb0.02TiOx catalyst with a GHSV of 108,000 h−1. The excellent catalytic performance of Mn0.15Nb0.02TiOx catalyst should be originated from its high reducibility and massive surface chemisorbed oxygen species. Moreover, the introduction of Nb into MnTiOx catalyst greatly enhanced its resistance to SO2 and H2O. Neither gaseous Hg0 nor HgO formed on catalyst surface could affect the NH3-SCR reaction. NO had a promotion effect on Hg0 oxidation, while NH3 was detrimental to Hg0 oxidation owing to the inhibited adsorption of Hg0 by NH3. Under SCR reaction conditions, an inhibition impact on Hg0 oxidation could be detected, but this negative effect could be avoided by using more catalyst sample.

Waste streams have emerged as potential feedstocks for biofuel production via microbial bioconversion. Metabolic engineering of the microalga Phaeodactylum tricornutum in its lipid biosynthetic pathways has been conducted with an aim to improve lipid production. However, there has been only limited achievement in satisfying biofuel demands by utilising extracellular organic carbons from low-cost waste streams. Herein, we present a successive staged cultivation mode, based on a previously engineered strain that co-overexpresses two key triacylglycerol biosynthesis genes. We first optimised microalgal biomass and lipid production by using food waste hydrolysate and crude glycerol as the cultivation media. Food waste hydrolysate (5% v/v) is a low-cost organic carbon source for enhanced microalgal biomass production, and the resulting lipid concentration was 1.08-fold higher with food-waste hydrolysate than that of the defined medium. Additionally, the resultant lipid concentration after using crude glycerol (100 mM) was 1.24-fold higher than that using the defined medium. Two carbon feeding modes (hybrid and sequential) were also performed to investigate the potential of engineered P. tricornutum with preliminary mechanistic analyses. The biodiesel properties of lipids produced in the hybrid mode were evaluated for potential application prospects. Collectively, this study demonstrates a waste stream utilisation strategy for efficient and sustainable microalgal biofuel production.

2,4-Dichloro-6-nitrophenol (DCNP) is a toxic nitrated byproduct of 2,4-dichlorophenol (2,4-DCP) commonly found in agriculturally impacted waters (e.g., paddy waters). DCNP has both genotoxicity and developmental toxicity and can cause endocrine disrupting effects on aquatic species. Herein, we investigated the photolysis of DCNP under UV254 irradiation in aqueous solutions. Results show that the anionic form of DCNP (DCNP−) is more photoreactive than the neutral form (DCNP0) due to its higher molar absorption coefficient and quantum yield. The presence of Suwannee River natural organic matter (SRNOM) inhibits the direct photolysis of DCNP through light screening. A series of photoproducts were identified by solid phase extraction (SPE) and high resolution-mass spectrometry (HR-MS) analysis. The photolysis of DCNP generates several photoproducts, including photoreduction, photonucleophilic substitution, photoionization, and dimerization intermediates. The primary photochemical mechanisms include photoionization from the singlet state and heterolytic C–Cl bond splitting in the triplet state. This contribution may shed some light on the photochemical transformation and fate of DCNP in UV-based engineering systems or natural sunlit surface waters.

In this study, NH3 treatment of CeO2 was found to significantly enhance its NH3-SCR performance. The NH3-treated CeO2 was characterized by BET, XRD, TPR and XPS. The obtained results revealed the excellent SCR activity and stability of CeO2 catalyst treated by NH3 should be originated from the dropped crystallinity, better reducibility, along with the production of more Ce3+ and surface adsorbed oxygen. Furthermore, in situ DRIFT study has been carried out and the results indicated that the Langmuir-Hinshelwood (L-H) mechanism could be applied for explaining the SCR reaction route over CeO2-N.

Constructing p-n junctions is an efficient strategy to resolve the narrow light absorption range and rapid electron-hole recombination problems of single photocatalysts. However, the promotion effect is greatly limited by poor interfacial contact between the p-type and n-type semiconductors. Herein, a facile surface charge-induced electrostatic self-assembly strategy is developed to construct BiOI/TiO2 heterostructures, in which the positively charged TiO2 nanosheets are spontaneously and uniformly assembled on the negatively charged BiOI nanosheets under pronounced electrostatic interaction in formic acid, acetic acid, or aminopropyltriethoxysilane (APTES) aqueous dispersion. Though featuring identical sufficient interfacial contact, BiOI/TiO2 heterostructures obtained in each dispersion medium, show extraordinary different visible light photocatalytic performance for methyl orange (MO) and phenol. Using multiple characterization techniques, the superior photocatalytic activity of BiOI/TiO2 heterostructures obtained in formic acid or acetic acid aqueous dispersion, can be ascribed to the enhanced photogenerated charge transportation and separation efficiency, which is attributed to the synergistic effects between the internal electric field induced by the formation of p-n junctions and sufficient interfacial contact. However, due to the remaining APTES goes against the formation of p-n junctions, BiOI/TiO2 heterostructure obtained in an APTES aqueous dispersion, shows fairly low photogenerated carriers separation efficiency and rather poor visible-light photocatalytic performance. This work may provide a rational and facile strategy to construct highly efficient p-n heterojunction photocatalysts toward environmental purification and solar energy conversion.

To improve the flame retardant efficiency of aromatic Schiff base (BA), and adjust the crosslinking temperature of imine groups, a cyano group, an electron-drawing group has been introduced into the chemical structure of aromatic Schiff base to obtain a third monomer for poly(ethylene terephthalate) (PET), named as dimethyl-5-[(2-cyanobenzylidene)amino]-isophthalate (CBAA). Thermogravimetry-differential scanning calorimetry (TG-DSC) and dynamic rheological results prove that the PET-based copolyester containing CBAA (CBAAnPETs) can cross-link at higher temperature than that containing BA, which will not affect the preparing and processing of PET. DSC and wide angle x-ray diffraction (WAXD) results demonstrate CBAAnPETs remain good crystallization ability. Owing to the two types of cross-linking reactions, i. e. the reactions between Schiff base ( CH N-) and cyano group (-C≡N), and among -CH N- units, CBAA plays an important role in solid phase as well as gaseous phase endowing CBAAnPETs with excellent flame retardancy. With a low CBAA content (only 6.7 mol%), the copolyesters self-extinguish in 5 s with no melt drips in UL-94 vertical test, and its LOI value also increases to 31.0%. The peak heat release rate and total smoke release of the copolyesters obtained from cone calorimetry also observably decrease.