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Dendritic cell (DC) vaccines have shown promising effects in cancer management, while low cell activity and low migration rate to lymph nodes limit their clinical application. Here, this work reports a bioink DC vaccine, synthesized by 3D printing methacryloyl gelatin to encapsulate DCs and tumor cellular vesicles overexpressing programmed cell death protein 1 (PD1‐CVs), for cancer immunotherapy. Compared with a traditional hydrogel, the porous 3D scaffold significantly improves the viability of DCs from ∼16% to ∼70% after 7 days of cell culture and increases the proportion of released DCs from the scaffold into lymph nodes by about fourfold. The PD1‐CVs stimulate DC maturation and block PD ligand‐1 (PD‐L1) in mature DCs and tumor cells, synergistically boosting DC‐mediated antitumor immunity. In breast tumor mouse models, this personalized 3D DC vaccine developed for site‐specific filling after tumor resection significantly suppress tumor recurrence and extend median survival time to 45 days. This 3D printed vaccine offers a simple, safe, and robust strategy for enhanced cell‐based cancer immunotherapy. [ABSTRACT FROM AUTHOR]

(1) Background: A rise in intraocular pressure (IOP) and decreased retinal ganglion cells are frequent indicators of effective modeling of chronic ocular hypertension in mice. In this study, the sensitivity of the mouse model to pharmaceutical therapy to reduce intraocular tension was assessed, the model's safety was confirmed using a cytotoxicity test, and the success rate of the mouse model of ocular hypertension was assessed by assessing alterations in IOP and neurons in the ganglion cell layer. (2) Methods: A mouse model of chronic ocular hypertension was produced in this study by employing photocrosslinkable sericin hydrogel injection and LED lamp irradiation. The eyes of 25 C57BL/6 male mice were subjected to 405 nm UV light from the front for 2 min after being injected with 5 μL of sericin hydrogel in the anterior chamber of the left eye. IOP in the mice was measured daily, and IOP rises greater than 5 mmHg were considered intraocular hypertension. When the IOP was lowered, the intervention was repeated once, but the interval between treatments was at least 2 weeks. The right eyes were not treated with anything as a normal control group. Mice eyeballs were stained with HE, Ni-type, and immunofluorescence to assess the model's efficacy. Two common drugs (tafluprost eye drops and timolol eye drops) were provided for one week after four weeks of stable IOP, and IOP changes were assessed to determine the drug sensitivity of the mouse model of chronic ocular hypertension. Furthermore, CellTiter 96® AQueous One Solution Cell Proliferation Assay (MTS) was utilized to investigate the safety of the ocular hypertension model by evaluating the deleterious effects of photocrosslinkable sericin hydrogel on cells. (3) Results: Before injection, the basal IOP was (9.42 ± 1.28) mmHg (1 kPa = 7.5 mmHg) in the experimental group and (9.08 ± 1.21) in the control group. After injection, cataract occurred in one eye, corneal edema in one eye, endophthalmitis in one eye, iris incarceration in one eye, and eyeball atrophy in one eye. Five mice with complications were excluded from the experiment, and twenty mice were left. Four weeks after injection, the IOP of the experimental group was maintained at (19.7 ± 4.52) mmHg, and that of the control group was maintained at (9.92 ± 1.55) mmHg, and the difference between the two groups was statistically significant (p < 0.05). Before the intervention, the IOP in the experimental group was (21.7 ± 3.31) mmHg in the high IOP control group, (20.33 ± 2.00) mmHg in the tafluprost eye drops group, and (20.67 ± 3.12) mmHg in the timolol maleate eye drops group. The IOP after the intervention was (23.2 ± 1.03) mmHg, (12.7 ± 2.11) mmHg, and (10.4 ± 1.43) mmHg, respectively. Before and after the intervention, there were no significant differences in the high-IOP control group (p > 0.05), there were statistically significant differences in the timolol eye drops group (p < 0.05), and there were statistically significant differences in the tafluprost eye drops group (p < 0.05). One week after drug withdrawal, there was no significant difference in IOP among the three groups (p > 0.05). In the high-IOP group, the protein (sericin hydrogel) showed a short strips or fragmented structure in the anterior chamber, accompanied by a large number of macrophages and a small number of plasma cells. The shape of the chamber angle was normal in the blank control group. The number of retinal ganglion cells decreased significantly 8 weeks after injection of sericin hydrogel into the anterior chamber, and the difference was statistically significant compared with the blank control group (p < 0.05). After the cells were treated with photocrosslinkable sericin hydrogel, there was no significant difference in the data of the CellTiter 96® assay kit of MTS compared with the blank control group (p > 0.05). (4) Conclusions: A mouse model of chronic intraocular hypertension can be established successfully by injecting sericin in the anterior chamber and irradiating with ultraviolet light. The model can simulate the structural and functional changes of glaucoma and can effectively reduce IOP after the action of most antihypertensive drugs, and it is highly sensitive to drugs. Sericin has no obvious toxic effect on cells and has high safety. [ABSTRACT FROM AUTHOR]

Carbon dots modified iridium nanowires (Ir NWs/CDs) show high catalytic activity and stability for acidic hydrogen evolution/oxidation reactions, which are attributed to the large compression stress generated in Ir NWs and the fast proton/electron transfer ability and good conductivity of CDs. [Display omitted] • One-dimensional Ir nanowires modified with carbon dots are employed as catalysts for HER/HOR. • The Ir nanowires show a high compressive strain intensity of −0.563%. • CDs act as a bridge connecting hydrogen proton and electron with Ir active sites. • Ir NWs/CDs-15 requires 18 mV to obtain a current density of −10 mA cm−2 for HER. • Ir NWs/CDs-15 shows anti-CO ability which is twice the level of the PtRu/C. The effective harnessing of hydrogen energy relies on the development of bifunctional electrocatalysts that facilitate hydrogen evolution/oxidation reactions (HER/HOR) with high catalytic activity. The design of such electrocatalysts requires the consideration of not only the volcano relationship with hydrogen binding energy (HBE) or hydrogen adsorption Gibbs free energy (ΔG H) but also the regulation of catalytic kinetics such as interfacial proton/electron transfer. In this work, unique one-dimensional iridium nanowires with compressive stress are successfully prepared and combined with carbon dots (Ir NWs/CDs). Acting as an electrocatalyst for HER in 0.5 M H 2 SO 4 , the optimal Ir NWs/CDs only requires an 18 mV overpotential to achieve a current density of −10 mA cm−2. Furthermore, the optimal Ir NWs/CDs shows high HOR performance with a mass activity (@ 50 mV versus RHE) 1.5 times that of 20% Pt/C and excellent anti-CO toxicity ability which is twice the level of the PtRu/C catalyst. Ir NWs/CDs exhibit enhanced HER/HOR activity due to (1) the appropriate modulation of the binding energy to hydrogen intermediate facilitated by the compressive stress applied to the Ir structure and (2) the improved proton/electron transfer kinetics by optimizing the electronic properties and surface structures through tailored CDs. This study delivers a new strategy for designing and synthesizing efficient acidic HER/HOR bifunctional catalysts. [ABSTRACT FROM AUTHOR]

The performances of lignin-based dye dispersant largely rely on the molecular weight and phenolic hydroxyl content of lignin. In order to evaluate their impacts, dye dispersants with different molecular weight and different phenolic hydroxyl content were prepared by fractionation, sulfonation, and etherification. Experimental results indicated that relatively high molecular weight benefits the dispersion performance. The staining grade of the dispersant to the fiber raised from 3 to 4.5 with the decrement of phenolic hydroxyl content, Noteworthily, the dispersant with Mw of 13,556 Da contains 0.91 mmol g−1 of phenolic hydroxyl and 1.55 mmol g−1 of sulfonic group, exhibiting superior heat stability at 130 °C and slight fiber staining (grade 4.5). Furthermore, the dye uptake of the dispersant with Mw of 13,556 Da reached the highest value of 84.8% in all those samples. Etherification is a promising method to raise the molecular weight of lignin and to reduce the content of phenolic hydroxyl groups, which improves the performances of lignin-based dye dispersants. [ABSTRACT FROM AUTHOR]

Reconstructed temperature field will provide critical input for monitoring the aerodynamic heating on the thermal protection system (TPS). In this paper, a novel data-driven method is proposed that allows real-time reconstruction of the 3D transient non-uniform temperature field in a TPS ceramic tile. The measured temperature is obtained by embedding sparse sensors at different layers of the tile. The spatial feature bases and time projection coefficients of the non-uniform temperature fields are extracted using the multi-parameter proper orthogonal decomposition (POD) method. The Fully-connected Long Short-Term Memory (FC-LSTM) networks are used to establish the prediction relationship between the measurements and the full-field temperatures. The problem to estimate the projection coefficients of the spatial feature bases is solved by optimizing the loss function using Adam algorithm. The numerical examples show an approximation error less than 5% and the reconstruction time-consuming less than 1 s in 3D temperature field reconstruction (TFR). The proposed reconstruction method is robust at different measurement noise levels and tested point arrangements. [ABSTRACT FROM AUTHOR]

Nowadays, graph convolutional networks (GCNs) are getting more attention in hyperspectral image classification (HSIC), and various algorithms based on GCNs have been proposed. However, because of hyperspectral images’ (HSIs) complex spatial texture information, the long-range graph convolution (GConv) and short-range GConv may cause inaccurate or oversmoothed feature extraction of some nodes. Thus, a multiscale short- and long range graph convolutional network (MSLGCN) is proposed for HSIC. First, MSLGCN not only extracts spatial information of ground objects at different scales but also simultaneously captures global and local spectral features, which preserves objects’ fine boundaries. Then, the rich multiscale information is complementary, enabling the MSLGCN to take full advantage of texture structures of varying sizes. In addition, a method to determine the superpixel scale by the intrinsic properties of HSIs is proposed to ensure that the segmentation boundary depicts the texture structure of the object accurately. Finally, the short–long graph convolution (SLGConv) is designed to fuse the advantages of global and local features, enabling the MSLGCN to extract accurate spatial–spectral features of nodes at any location. Experiments on three HSI datasets indicate that the MSLGCN can obtain better classification performance when compared with the other 11 state-of-the-art methods. [ABSTRACT FROM AUTHOR]

Convolutional neural networks are widely used in the field of hyperspectral image classification because of their excellent nonlinear feature extraction ability. However, as the sampling position of the regular convolution kernel is unchangeable, the regular convolution cannot distinctively extract the spatial and spectral information around the central pixel, which makes the classification results at the boundaries of ground objects over-smoothed and the classification performance degraded. Thus, we propose a novel superpixel guided deformable convolution network (SGDCN) for hyperspectral image classification. Firstly, the superpixel region fusion filter (SRF-Filter) is designed to fuse the initial superpixel region segmented by the simple linear iterative clustering (SLIC), making the fused superpixel region have a high homogeneity and also contain spatial features of diverse scales. Then, the superpixel guided deformable convolution (SGD-Conv) is proposed to make the shape of deformable convolution consistent with the real shape of land covers, and the SGD-Conv can extract pure neighborhood spatial-spectral features. Finally, a superpixel joint bilateral filter (SPJBF) is designed to solve the pixel-level and region-level misclassification problem, which can effectively utilize the superpixel region’s homogeneity and improve the classification accuracy. Experiments on three HSI datasets indicate that the SGDCN can obtain better classification performance when compared with other twelve state-of-the-art methods. [ABSTRACT FROM AUTHOR]

Background. Pulmonary fibrosis (PF) is a devastating lung disease, resulting in gas exchange dysfunction until death. The two drugs approved by the FDA, pirfenidone and nintedanib, have obvious side effects. Wen-yu-jin (WYJ), one of the commonly used herbs in China, can treat respiratory diseases. The potential effects and the underlying mechanism of WYJ against PF are unclear. Purpose. Employing network pharmacology, molecular docking, and in vivo and in vitro experiments to explore the potential effects and underlying mechanisms of WYJ in the treatment of PF. Methods. Ultra-high pressure liquid chromatography combined with linear ion trap-orbital tandem mass spectrometry (UHPLC-LTQ-orbital trap) was used to identify compounds of WYJ. We got PF-related targets and WYJ compounds-related targets from public databases and further completed critical targets exploration, network construction, and pathway analysis by network pharmacology. Molecular docking predicted binding activity of WYJ compounds and critical targets. Based on the above results, in vivo and in vitro experiments validated the potential effects and mechanisms of WYJ against PF. Results. 23 major compositions of WYJ were identified based on UHPLC-LTQ-Orbitrap. According to the results of network pharmacology, STAT3, SRC, IL6, MAPK1, AKT1, EGFR, MAPK8, MAPK14, and IL1B are critical therapeutic targets. Molecular docking results showed that most of the compounds have good binding activities with critical targets. The results of in vivo and in vitro experiments showed that WYJ alleviated the process of fibrosis by targeting MAPK and STAT3 pathways. Conclusion. Network pharmacology, molecular docking, and in vivo and in vitro experiments showed the potential effects and mechanisms of WYJ against PF, which provides a theoretical basis for the treatment of WYJ with PF. [ABSTRACT FROM AUTHOR]

This paper studies the energy efficiency optimization problem for coordinated multipoint (CoMP)-enabled and backhaul-constrained ultra-dense small-cell networks (UDNs). Energy efficiency is an eternal topic for future wireless communication networks; however, taking actual bottleneck of the backhaul link and the coordinated network architecture into consideration, it is difficult to find an effective way to improve the energy efficiency of the network. Aiming at this problem, we propose to combine cell association, subchannel allocation, backhaul resource allocation, and sleep/on of the cells together to develop an optimization algorithm for energy efficiency in UDN and then solve the formulated energy efficiency optimization problem by means of improved modified particle swarm optimization (IMPSO) and linear programming in mathematics. Simulation results indicate that nearly 13 % energy cost saving and 21 % energy efficiency improvement can be obtained by combining IMPSO with linear programming, and the backhaul link data rate can be improved by 30 % as the number of small cells increases. From the results, it can be found that by combining IMPSO with linear programming, the proposed algorithm can improve the network energy efficiency effectively at the expense of limited complexity. [ABSTRACT FROM AUTHOR]

Highly reactive polyols were prepared from modified acetic acid lignin (AAL) by a two‐step combination of mild hydrothermal degradation and hydroxylation. The AAL‐based polyols became relatively reactive and compatible with diisocyanate, with a reduction in the number average molecular weight (Mn) from 2923 to 684 g/mol and an increase in the hydroxyl content from 5.21 to 9.13 mmol/g. The mechanical performance and thermal properties of the AAL‐based polyurethane elastomers (LPUEs) strongly depended on the molecular weight and hydroxyl content of the AAL‐based polyols in the partial substitution of polytetramethylethylene ether glycol (PTMEG). This study proposed the prospective utilization of AAL as an alternative resource in the synthesis of polymers and biomaterials. © 2021 Society of Industrial Chemistry and John Wiley & Sons Ltd. [ABSTRACT FROM AUTHOR]

Target localisation is one of the key technologies and a performance metric in underwater acoustic sensor networks. A number of range‐free and range‐based localisation algorithms are proposed. Among them a range‐based localisation algorithm: weighted centroid localisation (WCL) is widely used due to the relatively simple implementation and better localisation. The accuracy of WCL, however, is reduced when the sensor nodes are farther from the centre or inappropriate nodes are selected to perform the localisation. This study proposes a novel and an efficient node optimisation algorithm based on received signal strength and weighted centroid. The proposed algorithm consists of three stages: (a) to estimate a rough region of the target node using bearing line and azimuth; (b) to calculate the optimal localisation region by the optimal localisation region function, and then (c) compare the overlap area of the rough region of the target node and the optimal localisation region to select the optimal localisation node. Simulation experiments show that the proposed optimal localisation region function can accurately represent the optimal localisation region of the geometrical figure, composed of different nodes. The study compares the performance of our proposed algorithm with the typical WCL algorithm, and clearly shows significant improvement in the localisation accuracy. [ABSTRACT FROM AUTHOR]

Design of catalysts with advanced structures has been extensively studied. Mesocrystal structure with the uniform crystal orientation shows special properties in electrocatalysis. Herein, PtRu mesocrystal was synthesized on F doped graphene by wet chemical method. In this reaction system, silicon nanowires and hydrofluoric acid were used to form Si - H bonds, which served as reducing agents to reduce Pt and Ru ions and grow PtRu particles on reduced graphene oxide (rGO). The electrochemical results showed that the PtRu/rGO catalyst had a favourable electrocatalytic performance on methanol oxidation reaction. The corresponding mass activity reached 739 mA mg−1 Pt , which was 2.23 times as large as 20% commercial platinum carbon (Pt/C, 332 mA mg−1 Pt). Its stability and toxicity resistance were also much better than those of commercial Pt/C, showing a great prospect in practice applications. Furthermore, the forming mechanism of PtRu mesocrystal is discussed, which has general implications for the design of superstructure catalysts. [ABSTRACT FROM AUTHOR]

• Push-out tests of innovative connections for timber–concrete composite systems. • Effects of shear connector type and arrangements on the load carrying capacity. • Slip modulus and ductility of the innovative connections. A series of innovative connections with the different combinations of steel plates and screws was developed for timber–concrete composite (TCC) system in this paper. Several groups have introduced vulcanized rubber layer to the jointing steel plate, which was used to be glued onto the timber beam surface. Push-out tests were carried out on the proposed connections and three replicates were prepared for each series. The study focused on the load carrying capacity, slip modulus, ductility and the role of some factors of the innovative connections. Moreover, the load-slip behaviour was evaluated based on an existing non-linear model and parametric analysis was also conducted. The research results showed that this connecting system looks suitable for structural application. [ABSTRACT FROM AUTHOR]

The rutile phase IrO2, as a promising catalyst for oxygen evolution reaction (OER), still falls short of satisfactory activity. Here, a novel 1D monoclinic phase iridium‐ruthenium oxide solid solution (m‐IrxRu1‐xO2) is reported. For m‐IrxRu1‐xO2 with different metal proportions, the optimal m‐Ir0.91Ru0.09O2‐δ catalyst exhibits excellent OER activity under acidic conditions with an overpotential of 180 mV at 10 mA cm−2. As an anode catalyst in a proton exchange membrane electrolyzer, m‐Ir0.91Ru0.09O2‐δ with a low catalyst loading (0.1 mg cm−2) can operate ≈256 h at 1.8 V with a high current density over 900 mA cm−2 at room temperature. Such a satisfied stability may have originated from the specific morphology and crystal structure, which is confirmed by the transient potential scanning test. Density functional theory calculations show that the Ru in the m‐IrxRu1‐xO2 facilitates decreasing the OER overpotentials due to the electron transfer from Ru to Ir. [ABSTRACT FROM AUTHOR]

The increasing popularity of proton exchange membrane electrolysis technology for hydrogen production has brought attention to the electrolytic water reaction. However, the slow kinetics of the oxygen evolution reaction (OER) at the anode have great influence on the overall efficiency of the reaction. While iridium oxide shows excellent stability under acidic conditions, its OER activity still needs to be improved. Here, we synthesized two‐dimensional amorphous iridium oxide (Am−IrO2) nanosheets with the thickness of only 6 nm by a mixed molten salt method. Such nanosheets show an ultralow overpotential of only 230 mV at 10 mA cm−2 in 0.5 M H2SO4. The overpotential increases only 40 mV after 90 hours of the stability test at this current density. Am−IrO2 can maintain the current density of ~400 mA cm−2 after 120 hours of test at 1.8 V in the PEM device, demonstrating good industrial prospects. Density functional theoretical calculations show that the oxygen vacancies, together with the upshift of the O 2p band center, are responsible for the improvement of OER in Am−IrO2. [ABSTRACT FROM AUTHOR]

Thermal degradation behaviors of poly(hexamethylene carbonate) (PHC) were investigated by means of thermogravimetric analysis (TGA), proton nuclear magnetic resonance ( 1 H NMR), gel permeation chromatography (GPC) and pyrolysis–gas chromatography/mass spectrometry (Py-GC/MS). Six types of PHC samples with different end groups and molecular weights were synthesized to systematically investigate the thermal degradation mechanism. Thermal degradation behaviors of the PHC samples were examined under both isothermal and non-isothermal conditions. The PHC samples showed distinct thermal degradation behaviors from other aliphatic polycarbonates (poly(propylene carbonate), poly(trimethylene carbonate) and poly(butylene carbonate)). The results indicated that the chain-end structure makes a slight effect on the thermal stability of PHC regardless of the molecular weight. During the non-isothermal degradation of PHC, four main reactions were illustrated: unzipping, intramolecular transesterification, β-H transfer and decarboxylation reactions. Intramolecular transesterification reaction dominantly occurs below 300 °C accompanying with unzipping reaction which can only be induced by hydroxyl end group, and releasing cyclic hexamethylene carbonate monomer and dimer. Above 300 °C, the four degradation reactions take place simultaneously. [ABSTRACT FROM AUTHOR]

The connection between the active components and supports in a catalyst is important for the high activity and long‐term stability during catalysis. Here, Co3O4 nanoparticles embedded in F, N‐doped graphene (Co3O4/F, N‐doped G) are synthesized by silicon‐hydrogen bond reduction. F and N atoms doped graphene interacts with Co3O4 nanoparticles to optimize oxygen reduction reaction (ORR) catalytic activity. The optimal Co3O4/F, N‐doped G‐2 catalyst with Co loading of 3.38 wt% shows a half‐wave potential of 0.852 V vs RHE in 0.1 M KOH solution. Furthermore, Co3O4/F, N‐doped G‐2 catalyst outputs an extremely high open circuit voltage of 1.47 V and an excellent power density of 280 mW cm−2 at current density of 450 mA cm−2 when applied to the primary Zn‐air batteries. Due to the synergetic effects from Co3O4 and supports (F, N‐doped G), Co3O4/F, N‐doped G‐2 catalyst also shows excellent stability and anti‐toxicity, and has good practical application prospects. [ABSTRACT FROM AUTHOR]

Electrochemical two‐electron oxygen reduction reaction (2 e− ORR) to produce hydrogen peroxide (H2O2) is a promising alternative to the energetically intensive anthraquinone process. However, there remain challenges in designing 2 e− ORR catalysts that meet the application criteria. Here, we successfully adopt a microwave‐assisted mechanochemical‐thermal approach to synthesize hexagonal phase SnO2 (h‐SnO2) nanoribbons with largely exposed edge structures. In 0.1 M Na2SO4 electrolyte, the h‐SnO2 catalysts achieve the excellent H2O2 selectivity of 99.99 %. Moreover, when employed as the catalyst in flow cell devices, they exhibit a high yield of 3885.26 mmol g−1 h−1. The enhanced catalytic performance is attributed to the special crystal structure and morphology, resulting in abundantly exposed edge active sites to convert O2 to H2O2, which is confirmed by density functional theory calculations. [ABSTRACT FROM AUTHOR]

Electrochemical two‐electron oxygen reduction reaction (2 e− ORR) to produce hydrogen peroxide (H2O2) is a promising alternative to the energetically intensive anthraquinone process. However, there remain challenges in designing 2 e− ORR catalysts that meet the application criteria. Here, we successfully adopt a microwave‐assisted mechanochemical‐thermal approach to synthesize hexagonal phase SnO2 (h‐SnO2) nanoribbons with largely exposed edge structures. In 0.1 M Na2SO4 electrolyte, the h‐SnO2 catalysts achieve the excellent H2O2 selectivity of 99.99 %. Moreover, when employed as the catalyst in flow cell devices, they exhibit a high yield of 3885.26 mmol g−1 h−1. The enhanced catalytic performance is attributed to the special crystal structure and morphology, resulting in abundantly exposed edge active sites to convert O2 to H2O2, which is confirmed by density functional theory calculations. [ABSTRACT FROM AUTHOR]

• Small sized PdRu particles uniformly loaded on carbon are synthesized by Si-H bond. • PdRu interface is formed under the function of SiO. • The interface enhances ORR activity and anti-poisoning performance. • Zinc-air battery with Pd 9 Ru 1 /C as an air cathode exhibits the remarkable performance with power density 240 mW cm−2. PdRu bimetallic catalyst is synthesized by simple stirring heating method with the help of Si-H bond. The as-prepared product shows an excellent ORR performance and amazing resistance to a variety of poison systems. This outstanding performance may due to the bimetallic interface engineering between Pd and Ru. [Display omitted] Developing a highly efficient and robust poison tolerance catalyst for oxygen reduction reaction (ORR) is significantly critical for sustainable energy convert systems. Herein, an interfacial engineered PdRu/C is prepared by reduction of silicon-hydrogen bonds. The interface between Pd and Ru is beneficial for exposing the active site, enhancing charge transfer and adjusting the adsorption energy barrier, resulting in the excellent ORR performances. Compared with commercial Pt/C (0.84 V) and commercial Pd/C (0.84 V), the optimal Pd 9 Ru 1 /C demonstrates high electrocatalytic activity with half-wave potential up of 0.86 V in 0.1 M KOH solution. Meanwhile, the experimental results indicate that bimetallic interface engineering can greatly enhance toxicity resistance to various poisons, including CO, methanol, NO x , SO x and PO x. When they are applied to zinc-air battery as an air cathode, the battery exhibits an open circuit voltage of 1.48 V. Interestingly, the power density reaches up to 240 mW cm−2, which is superior to those of commercial Pt/C (219 mW cm−2) and commercial Pd/C (128 mW cm−2). This work opens up an effective strategy to conceive interfacial hybrid for electrocatalysis. [ABSTRACT FROM AUTHOR]

Poly(isosorbide carbonate) (PIC) was synthesized by melt polycondensation of dimethyl carbonate (DMC) and isosorbide using lithium acetylacetonate (LiAcac) as the catalyst. The reaction conditions were optimized to achieve PIC with relatively high number-average molecular weight ( Mn) of 28,800 g/mol and isosorbide conversion of 95.2%. A series of poly(aliphatic diol- co-isosorbide carbonate)s (PAICs) were also synthesized by melt polycondensation of DMC with isosorbide and equimolar amounts of aliphatic diols (1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,4-cyclohexane dimethanol) in the presence of LiAcac and the TiO2/SiO2-based catalyst (TSP-44). PAICs with Mn values ranging from 18,700 to 34,400 g/mol and polydispersities between 1.64 and 1.69 were obtained. The 13C NMR analysis revealed the random microstructure of PAICs. The differential scanning calorimetry results demonstrated that all the PAICs were amorphous with a unique Tg ranging from 46 to 88 °C. The dynamic analysis results showed that the incorporation of linear or cyclohexane structure changed the dynamic mechanical properties of PIC drastically. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013 [ABSTRACT FROM AUTHOR]

Abstract: Thermal degradation mechanism of poly(butylene carbonate) (PBC) was elucidated by means of thermogravimetric analysis (TGA), 1H nuclear magnetic resonance (1H NMR) and pyrolysis-gas chromatography mass spectrometry (Py-GC/MS). The results indicated that there are three main pathways for the thermal degradation of PBC, including unzipping, β-H transfer and decarboxylation reactions. The unzipping reaction can be facilely induced at low temperature of 200 °C, and all of the three reactions occur at high temperature above 300 °C. TGA results suggested the thermal stability order: hydroxyl-terminated PBC < acetyl-terminated PBC < methyl carbonate terminated PBC. The hydroxyl end group can induce the unzipping reaction, while methyl carbonate chain-end depresses the occurrence of it. [Copyright &y& Elsevier]

A series of high molecular weight poly(butylene-co-hexamethylene carbonate) (PBHC) copolycarbonates were synthesized by copolymerizations of dimethyl carbonate (DMC), 1,4-butanediol (BD) and 1,6-hexanediol (HD) via a two-step melt polycondensation method. Microstructure analysis determined by high-resolution 13C-NMR showed that butylene carbonate (BC) units and hexamethylene carbonate (HC) units of the synthesized copolymers take a random distribution along the polymer chains. Analyses of the formed byproducts indicated that sublimation of oligomer and thermal degradation of polymer happen during the aliphatic polycarbonate polycondensation. The thermal properties and crystalline structure of the copolymers were studied by DSC, TGA and WAXD. WAXD patterns showed that the copolymers with 11 and 91 mol% HC units form poly(butylene carbonate) (PBC) and poly(hexamethylene carbonate) (PHC) crystals, respectively, while the three other copolymers with intermediate HC unit contents are completely amorphous. The results indicated that the BC and HC units are incompatible in each crystal lattice, and that cocrystallization cannot take place. TGA results indicated that the thermal stability of the obtained PBHC random copolymers is higher than that of PBC and increases with increasing the HC unit content. The enzymatic degradation study revealed that the biodegradation rate of the PBHC copolymers mainly depends not only on the degree of crystallinity and melting temperature but also on the type of crystalline structure, while the composition and microstructure dependences of biodegradability are negligible. [ABSTRACT FROM AUTHOR]

• Clarifying the therapeutic effect of Vitamin D 3(VD3) during the significant period of IPF. • Using proteomics technology to determine PSAT1 as the target of VD3 in the treatment of IPF. • Combining with comprehensive analysis of clinical samples to determine MAPK as the therapeutic pathway. • Clarifying the therapeutic mechanism of VD3 through transfection experiment and luciferase assays. Idiopathic pulmonary fibrosis (IPF) is a progressive and fatal fibrotic lung disease. However, there are insufficient drugs available for IPF treatment, and the currently used drugs are accompanied by many adverse reactions. Deficiency of vitamin D3 (VD3) in the development of IPF and the potential role of VD3 in the treatment of IPF have attracted increasing attention. In vivo experimental results showed that VD3 could increase the survival rate in bleomycin (BLM)-induced models, relieve lung inflammation, reduce hydroxyproline content, and inhibit collagen deposition and cell apoptosis. We further performed proteomics analysis and screened 251 target proteins that reflect VD3 intervention in BLM-induced animal models. These target proteins were involved in acute inflammation, oxidative stress, antioxidant activity and extracellular matrix binding. Combined with the comprehensive analysis of clinical samples, PSAT1 was screened out as a candidate target related to IPF disease and VD3 treatment. Through further computational analysis, the MAPK signaling pathway was considered to be the most probable candidate pathway for VD3 function targeting IPF. In in vivo experiments, VD3 inhibited BLM-induced expression of PSAT1 and phosphorylation of p38 and ERK1/2 in mouse lung tissue. The experiments of cell proliferation and western blot confirmed that VD3 inhibited the expression of PSAT1 and the activation of the mitogen-activated protein kinase (MAPK) pathway in human pulmonary fibroblasts (HPF). Furthermore, experiments with transfection plasmids overexpressing PSAT1 proved that VD3 could attenuate the proliferation and differentiation of HPF by suppressing the effect of PSAT1 on the MAPK signaling pathway. Finally, we confirmed that vitamin D receptor (VDR) could occupy the PSAT1 promoter to reveal the transcriptional regulation effect of VD3 on PSAT1. In conclusion, VD3 exerted a therapeutic effect on IPF by down-regulating the MAPK signaling pathway via targeting the expression of PSAT1. [ABSTRACT FROM AUTHOR]

The title calixarene, dimanganese thiacalix[4]arene tetrasulfonate, was prepared and its crystal structure was determined. [Mn(H2O)6]2[thiacalix[4]arene tetrasulfonate]·0.5H2O crystallizes in the monoclinic system, P2(1)/m space group, with a=13.014 (6), b=14.146 (9), c=13.184 (7) A˚, β=113.307 (10)°, V=2229 (2) A˚3 and Dc=1.710 gcm−3, Z=2. The title calixarene exists in the solid state as bilayer structure. The hydrophobic organic layer consists of thiacalix[4]arene tetrasulfonate in an up-down fashion, whereas, the hydrophilic inorganic layer consists of hexaaquamanganese (II) which is linked to the former through a second-sphere coordination. [Copyright &y& Elsevier]

The SO 3 -CDs/NiFe LDH was synthesized through electrochemical and hydrothermal methods. The P-SO 3 -CDs/NiFe LDH catalyst work electrode was obtained via polarized by an electric field of 10,000 V/cm for 30 mins. After that, sulfonate functional groups selectively enrich at the surface of catalysts. Such sulfonate functional groups have a strong ability to capture proton, exhibit excellent OER performances as confirmed by DFT calculation and experimental results. [Display omitted] • NiFe LDH/CDs composite was employed as OER catalysts. • Electric field polarization is used to regulate the exposed functional groups. • H+ captured from *OH or *OOH species by the sulfonated groups on CDs. • The overpotential is 200 mV@10 mA cm−2 and Tafel slope is 55.2 mV dec−1. • Polarized catalysts reach a high current density than the unpolarized one. Interfacial design and regulation for electrocatalysts can effectively enhance the performance of oxygen evolution reaction (OER). It is still a challenge to search for a simple and easy way to controllably adjust the interface of catalysts. Here we report a new strategy, electric field polarization to regulate the charged functional groups of nickel–iron layered double hydroxide (NiFe LDH)/carbon dots (CDs) composite catalysts. The selectively exposed sulfonate functional groups on CDs under the electric field have regulated the interfacial environment of the composite catalyst. The density function theory (DFT) calculation also reveals that the high electrocatalytic activity can be attributed to H+ capture from *OH or *OOH species by the sulfonated groups on the surface of CDs. Thus, the synergistic effect between the catalytic activity of NiFe LDH and the functional group-modified CDs enhances the OER performance of the composite catalyst, showing low overpotential of 200 mV at 10 mA cm−2 and outstanding kinetics with Tafel slope of 55.2 mV dec−1. Moreover, the polarized composite catalysts can reach a high current density of 51.7 mA cm−2 at 1.46 V vs. reversible hydrogen electrode (RHE), which is 9.2 times higher than the unpolarized one (5.6 mA cm−2). [ABSTRACT FROM AUTHOR]

In order to reduce the residual stress of the GH4169 alloy, the effect and micro-mechanism of the tensile deformation were studied. The residual stress, dislocation density, and distribution of the GH4169 alloy were analyzed by X-ray residual stress tester, X-ray diffractometer (XRD), and electron backscatter diffraction (EBSD). The results show that: with the increase of tensile deformation, the residual stress relief first increases and then decreases. When the tensile deformation is 3%, the reduction rate of residual stress reaches the maximum, which is 90%. The mechanism of residual stress relief by the tensile treatment is that the dislocation group in the alloy is activated by tensile treatment, and the dislocation distribution in the alloy is more uniform by dislocation movement, multiplication, and annihilation so that the residual stress can be eliminated. [ABSTRACT FROM AUTHOR]

There is a strong interest in developing environmentally friendly synthesis approaches for making polyurethane elastomers (PUE) with desirable mechanical performance and flame retardancy suitable for a variety of applications. Hence, in this study, a novel nano functionalized lignin nanoparticle (Nano-FL) containing nitrogen (N) and phosphorus (P) moieties was developed via mild grafting reactions combined with the ultrasound method. The Nano-FL incorporated in the PUE acted as both crosslinking agents and flame retardants. The novel Nano-FL showed good compatibility and dispersibility in the PUE matrix, thereby overcoming the weakening effect of adding traditional lignin flame retardants on the mechanical properties of the PUE materials. PUE/Nano-FL exhibited strong tensile properties. Compared with control neat PUE, with 10 wt% of Nano-FL addition, the PUE attained a limiting oxygen index as high as 29.8% and it also passed the UL-94 V-0 rating. Furthermore, Cone Calorimetry Test (CCT) showed that the addition of Nano-FL not only reduced the heat release rate and the total heat release but also decreased the total smoke production rate during combustion. The char residues of PUEs with Nano-FL showed a high oxidation resistance with dense and continuous structural morphologies. The combined barrier and quenching effects of the char layer provided excellent flame retardancy performance. The novel Nano-FL developed in this study showed excellent promises as green functional additives for enhancing mechanical, thermal and flame retardancy performance of a wide range of polymers. [Display omitted] [ABSTRACT FROM AUTHOR]

• Janus Pd-Au NPs are loaded on graphene oxide through reduction of Si-H bonds. • XRD patterns reveal that Pd is under an average tensile strain of +0.32%. • TEM image demonstrates Pd near the Pd-Au interface under +4% tensile strain. • Tensile strain is beneficial to decrease the reaction energy barrier for ORR. • Zinc-air battery catalyzed by Pd-Au/GO exhibits a peak power density up to 276 mW·cm−2. Strain existed in the bimetallic electrocatalysts may modulate the performance of oxygen reduction reaction (ORR). The density function theory calculation here indicates that the tensile strain originated from the mismatch of lattice spacing between Au and Pd is beneficial to decrease the reaction energy barrier for ORR. Pd-Au nanoparticles were uniformly loaded on graphene oxide (Pd-Au/GO) through the reduction of the Si-H bond. The epitaxial growth of Pd on Au leads to Janus nanostructure. X-ray powder diffraction patterns reveal that Pd is under an average tensile strain of +0.32%, while high resolution transmission electron microscopy image demonstrates Pd near the Pd-Au interface under +4% tensile strain. Better ORR performance of Pd-Au/GO is obtained than the commercial Pt/C in the alkaline medium. The tensile strain enables Pd-Au/GO with a half-wave potential of 0.90 V and a high mass activity of 0.526 A mg Pd −1 at 0.9 V, which both are higher than those of the commercial 40 wt% Pt/C and 20 wt% Pt/C. Meanwhile, the zinc-air battery catalyzed by Pd-Au/GO also exhibits a high peak power density up to 276 mW·cm−2 and a long-term durability than those of Pt/C. The preparation of Janus Pd-Au nanoparticles with the strain effect mentioned in this paper may provide ideal path for the synthesis of other types of materials. [ABSTRACT FROM AUTHOR]

• Experimental work of timber–concrete composite beams is conducted with innovative connections. • A comparison between theoretical and experimental results is proposed. • Some timber–concrete composite beams are reinforced at the tensile side with prestressed tendon. This paper presents a summary of the experimental programmes and theoretical analysis of the bending performance of non-prestressed and prestressed timber-concrete composite (TCC) beams. Two non-prestressed and three prestressed composite beams were selected, and their flexural behaviour was evaluated. Three types of ductile fabricated connections were applied to the prestressed composite beams, whereas two types were applied to the non-prestressed beams. The concrete slabs with embedded steel plates and timber beams were connected together using coach screws. On the surfaces of the embedded steel plates, the portions in contact with the wooden beam were interspaced with a vulcanized rubber layer to improve the mechanical performance of shear connections and composite beams. A series of four-point bending experiments were performed until collapse failure occurred in a simply-supported scheme. The test results demonstrated that the TCC beams using steel plate + screw connections exhibited excellent structural performance. The flexural capacity of the prestressed specimens was improved by approximately 110% compared with the non-prestressed specimens. Due to the addition of the rubber layer in the TCC connections, the flexural capacity of the prestressed composite beams was improved by 25.2%. Based on the 'γ–method', a theoretical analysis was proposed for calculating the flexural capacity and bending stiffness for both non-prestressed and prestressed TCC beams. The theoretical results showed good agreement with the experimental evidence. [ABSTRACT FROM AUTHOR]

Summary: Aiming at further improving the energy efficiency of system while meeting the data rate requirement of the users, in this paper, a network energy efficiency optimization problem by jointly optimizing the resource allocation of macrocells and small cells is formulated and proven to be an NP‐hard problem, which cannot be worked out by direct methods in polynomial time. Considering the effectiveness of the modified particle swarm optimization (MPSO) algorithm, an MPSO‐based resource allocation and cell association algorithm is employed to solve the proposed joint optimization problem where the frequency resource partitioning of the macrocells, the transmission power, and the cell‐association bias of the small cells are jointly optimized. During the implementation of the optimization algorithm, the cell association alters with the transmission power and cell‐association bias adjustment, and the small cells where there are no active users associating with them will be turned off. The data rate requirement of the users is an indispensable metric in the communication system. Taking no account of the data rate requirement of the users, the frequency resource partitioning and cell association alteration will deteriorate the data rate of a few of users. Under such circumstances, we take the users' data rate requirement as a constraint of the joint optimization problem. The system level simulation results show that, by jointly optimizing the resource allocation of macrocells and small cells while guaranteeing the users' data rate requirement, the energy efficiency and system throughput can be further improved, and energy consumption can be further reduced. [ABSTRACT FROM AUTHOR]

Main observation and conclusion: Ethanol is considered a better fuel than methanol in direct alcohol fuel cells because of the high energy density and low toxicity. Compared with noble metal catalysts, nickel‐based catalysts are much cheaper in price. However, present nickel‐based catalysts still surfer from some disadvantages such as low activity and high overpotential. In this paper, we show a new and high efficient nickel‐ based catalyst for ethanol oxidation. A layer of anodized nickel passivation film (Ni‐APF) was formed on the surface of nickel sheet by anodic oxidation method with carbon dots (CDs) as co‐catalyst. At the current density of 110 mA·cm−2, the potential for Ni‐APF/CDs was only 0.541 V (vs. Ag/AgCl), which was 18.8% lower than that of Ni‐APF. Low overpotential could reduce electrode thermal loss and increase output energy. Ni‐APF/CDs showed 144.4 mA∙cm−2 peak current density at peak potential 0.662 V (vs. Ag/AgCl), which was 31% higher than that of Ni‐APF (110.3 mA∙cm−2). In this system, CDs mainly function in the increase of charge‐transfer capacity and the promotion oxidation of carbonaceous intermediates. [ABSTRACT FROM AUTHOR]

The utilization of two-dimensional (2D) nanosheets as catalysts is promising due to their atomic-scale thickness and extensive surfaces. The development of a high-quality, flexible Pt-based nanosheet with an efficient synthesis method is imperative. In this study, we present a 2D Pt2Pd porous alloy nanosheet synthesized through a novel process involving molten-alkali mechanochemical and borane morpholine complex reduction methods. This nanosheet exhibits a pristine 2D active surface, serving as an efficient catalyst for the oxygen reduction reaction (ORR). The Pt2Pd porous alloy nanosheet catalyst displays a high half-wave potential of 0.956 V versus the reversible hydrogen electrode (RHE), along with remarkable mass and specific activities of 1.38 A mg−1Pt and 3.70 mA cm−2 (at 0.9 V versus the RHE). When applied as the cathode in a zinc–air battery, it achieves a power density of 0.31 W cm−2 and demonstrates outstanding durability. This research introduces an innovative strategy for advancing high-quality, flexible 2D Pt-based materials. [ABSTRACT FROM AUTHOR]

Pt is the ideal anode catalyst in fuel cells. In this paper, in order to increase the utilization of Pt, the PtAu nanowire networks (NWNs) with ultralow content of Pt are fabricated by a simple silicon monoxide (SiO) reduction method without any capping agent. PtAu NWNs supported on carbon black with Pt content of 1 wt% (Pt 0. 05 Au NWNs) are employed as catalysts for formic acid oxidation (FAO) and methanol oxidation reaction (MOR), whose mass activities are as high as 4998.9 and 2282.3 mA∙mg Pt −1, respectively. The network structure facilitates the electron transfer and increases the stability of the catalysts. The PtAu composite experiences compressive lattice strain as confirmed by X-ray powder diffraction (XRD). The Pt 0. 05 Au NWNs catalyst with low Pt content results in the largest strain variation compared with PtAu composited of other ratios, which may downshift the d-band center of Pt and lead to the higher electrocatalytic activity in oxidation reaction. • PtAu nanowire networks are fabricated by a simple Si–H bond reduction method. • The network structure facilitates the electron transfer and increases the stability. • Pt 0. 05 Au/C with Pt content of 1 wt% shows high mass activities to FAO and MOR. • The lattice strain of PtAu is formed during the fabrication process. [ABSTRACT FROM AUTHOR]

The construction of high-performance bifunctional self-supported electrodes is significant for promoting the activity and stability of water splitting. The self-supported electrode not only has a strong structural characterization but also avoids the negative effects of using binders. Herein, we fabricated a self-supported electrode (Ni 2 P/MoP@CNTs-CC), which is composed of carbon nanotubes (CNTs) directly grown on carbon cloth (CC) filled with transition metal-based phosphide composite nanoparticles. The optimized Ni 2 P/MoP@CNTs-CC electrode exhibits promising hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) electrocatalytic performance. Ni 2 P/MoP@CNTs-CC shows a low overpotential of 87 mV at − 10 mA cm−2 and 360 mV at 40 mA cm−2 for HER and OER, respectively. Besides, the Ni 2 P/MoP@CNTs-CC electrode was also used as an anode and cathode, simultaneously, showing a cell voltage of 1.89 V at 50 mA cm−2 and excellent stability at 50 mA cm−2 for more than 100 h. This work provides a facile method for preparing a low-cost and robust self-supported electrode for water splitting. • Individual Ni 2 P/MoP nanoparticles were successfully encapsulated in the cavity of CNTs. • The dynamic bubble escape behavior on the surface of the self-supporting electrode was monitored and analyzed. • Ni 2 P/MoP@CNTs-CC shows considerable water splitting performance. [ABSTRACT FROM AUTHOR]

[Display omitted] Transition metal borides (TMBs) or phosphides (TMPs) have attracted great attention to the design of bifunctional electrocatalysts for energy storage. The superaerophobicity and superhydrophilicity of the catalytic electrode surface are crucial factors to determine the reaction process of the gas electrode. Herein, we report a self-supported electrode of carbon nanotube (CNTs) array grown on carbon cloth (CC) modulated together by boron-doped cobalt phosphide (CoP-B/CNTs/CC). The electrode requires the overpotential of 73.8 mV and 189.5 mV at the current density of ±10 mA cm−2 for hydrogen and oxygen evolution reactions in an alkaline electrolyte (1.0 M KOH), respectively, meanwhile maintaining outstanding long-term durability for more than 300 h. The excellent activity of CoP-B/CNTs/CC is attributed to boron doping regulating its electronic structure and further enriching active sites. The attractive stability of CoP-B/CNTs/CC is due to the unique geometric structure of the self-supported electrode. Furthermore, the superaerophobicity and superhydrophilicity of the electrode surface also accelerate the reaction process of the gas electrode. Expectedly, water splitting cells assembled using CoP-B/CNTs/CC electrodes as cathode and anode, respectively, require a cell voltage of 1.54 V at 10 mA cm−2, which is lower than that of the Pt/C/CC||RuO 2 /CC couple (1.69 V at 10 mA cm−2). Importantly, CoP-B/CNTs/CC||CoP-B/CNTs/CC achieve stable cell voltage under the step current changes (10 mA cm−2, 50 mA cm−2, and 100 mA cm−2) over 300 h. This work highlights a new path to understanding the effects of the static and dynamic behavior of bubbles on the surface of self-supporting electrodes on catalytic performance. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • A non-isocyanate route to novel DMC-derived poly(carbonate urethane) (PCU). • Mechanism research and prevention of the crosslinking reaction. • PCUs with high molecular weight and competitive mechanical properties. Abstract A series of non-isocyanate linear poly(carbonate urethanes) (PCUs) were prepared through an environmentally-friendly route based on dimethyl carbonate, 1,6-hexanediol and 1,6-hexanediamine. Bis-1,6-hexamethylencarbamate (BHC) was first synthesized from diamine and excess dimethyl carbonate. To prevent the detrimental crosslinking problem, a new "hard segment first" route was developed. In this route, the polyurethane diol was first prepared by the reaction between BHC and 1,6-hexanediol. Polycarbonate diol was obtained by the reaction of dimethyl carbonate and 1,6-hexanediol. The subsequent polycondensation of polyurethane diol and polycarbonate diol led to linear PCUs. The polymers were characterized by GPC, FT-IR, 1H NMR, 13C NMR, DSC, WAXD, TGA and tensile testing. The results indicated that the PCUs possessed a linear structure and high molecular weight with a number-average molecular weight of up to 60,000 g/mol. It should be noted that the PCUs exhibited good thermal properties with a composition-dependent melting point ranging from 60 °C to 137 °C, and a good mechanical strength, with tensile strength values lying between 17 MPa and 29 MPa and elongation at break varying from 665% to 26%. Considering the green procedure and raw materials as well as the good processability and mechanical properties of the resultant PCUs, this kind of aliphatic thermoplastic PCU offers great potential to be industrialized and applied in the biomedical field such as tissue scaffolds and cardiovascular implants. [ABSTRACT FROM AUTHOR]

[Display omitted] • The porous rhodium nanosheets with tunable compressive strain were successfully obtained by directly annealing metastable trigonal rhodium oxide. • The record HzOR performance. • A clear strain effect and catalytic mechanism for alkaline HzOR in single-metal-element systems. Electrocatalytic water decomposition is an essential pathway for large-scale preparation of high-purity hydrogen, while the conventional oxygen evolution reaction (OER) with a kinetically sluggish four-electron process becomes a huge challenge for its further application. Hydrazine oxidation reaction (HzOR) is considered an effective strategy to replace the sluggish OER process, attributed to its lower thermodynamic oxidation potential. Here, porous rhodium nanosheets (Rh-NSs) with tunable lattice strain are successfully obtained by directly annealing metastable trigonal rhodium oxide (Tri-RhO 2) in a hydrogen atmosphere. More importantly, ligand and synergetic effects can be effectively avoided in a single-metal-element system, providing an ideal model electrocatalyst for understanding the correlation between reactivity and lattice strain. The electrochemical results show that the optimal Rh-NSs-300 (the Tri-RhO 2 precursor is annealed at 300 °C) may deliver ultralow working potential (vs. RHE) of −103 mV at the current density of 10 mA cm−2 with a Tafel slope of 15.4 mV dec-1 for HzOR. In addition, the working potential (vs. RHE) of Rh-NSs-300 only drops 35 mV after the 72 h test by chronopotentiometry method at the constant current density of 10 mA cm−2. Density functional theory (DFT) calculations indicate that HzOR can more easily occur on Rh-NSs with tunable compressive strain than pure Rh. [ABSTRACT FROM AUTHOR]

Herein, the carbon dots bridges nickel oxide and manganese trioxide through the oxygen-containing group of carbon dots (NiO-Mn 2 O 3 -CDs) is successfully constructed and as an advanced bifunctional oxygen electrocatalysts. The CDs covalently bridging Ni and Mn atoms can reprogram the electronic structure of active sites and enhance charge transfer. Consequently, the optimal NiO-Mn 2 O 3 -CDs yields outstanding bifunctional activities for ORR and OER. Importantly, the rechargeable zinc-air battery test with NiO-Mn 2 O 3 -CDs as the air cathode delivers the excellent performances, outperforming the commercial Pt/C + IrO 2. [Display omitted] • NiO-Mn 2 O 3 -CDs yield remarkable electrocatalytic activity for ORR and OER. • The introduction of CDs reprograms the electronic structure of active sites. • Rechargeable Zn-air battery with NiO-Mn 2 O 3 -CDs shows power density of 287 mW cm−2. The development of high-efficiency, low-cost and durable bifunctional oxygen electrocatalysts is of great significance for the large-scale application of rechargeable zinc-air batteries. Herein, the carbon dots bridging nickel oxide and manganese trioxide through the oxygen-containing group of carbon dots (NiO-Mn 2 O 3 -CDs) for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is proposed. The optimal NiO-Mn 2 O 3 -CDs yields remarkable electrocatalytic activity with low overpotential (298 mV) to derive the 10 mA·cm−2 for OER and a high half wave potential (0.84 V vs. RHE) for ORR. The outstanding performances are attributed to the CDs covalently bridging Ni and Mn atoms, which reprogram the electronic structure of active sites and enhance charge transfer. Consequently, the rechargeable zinc-air battery test with NiO-Mn 2 O 3 -CDs as the air cathode deliver the excellent performances, including a high open voltage (1.51 V), a maximum power density (287 mW∙cm−2 @ 0.35 A∙cm−2) and robust cycling life, outperforming the commercial Pt/C + IrO 2. This work presents an efficient strategy to construct the highly active and stability bifunctional air cathodes for electrochemical energy devices. [ABSTRACT FROM AUTHOR]

Direct electrosynthesis of hydrogen peroxide (H2O2) via two‐electron pathway oxygen reduction reaction (2e− ORR) is crucially essential for a sustainable green economy. However, catalysts inevitably undergo four‐electron pathway oxygen reduction reaction (4e− ORR), resulting in low selectivity and economic benefits. The current challenge is to provide a feasible design strategy for obtaining satisfactory 2e− ORR catalysts with high selectivity. In this work, carbon dots (CDs) act as a cocatalyst to regulate the electron transport kinetics of In2O3/CDs, and the influence of CDs on the ORR pathways of In2O3/CDs is also studied. The electron transfer kinetics on In2O3/CDs composites are studied and analyzed using the transient photo‐induced voltage (TPV) technology. Combining the TPV results and kinetics analysis, it is shown that the electron transport on the In2O3 interface is obviously weakened after the addition of CDs, resulting in a high H2O2 selectivity. It is also demonstrated that CDs can effectively enhance the selectivity of H2O2, and the H2O2 selectivity of In2O3/CDs–10 is in close proximity to 100%, which is much higher than that of pure In2O3 (72%). This work will provide a new understanding and insight into addressing the challenge of low H2O2 selectivity for 2e− ORR catalysts. [ABSTRACT FROM AUTHOR]

The hydrazine oxidation reaction (HzOR) has been considered as a more energy-efficient alternative to the oxygen evolution reaction in water electrolysis. To design efficient electrocatalysts for HzOR, precise engineering of materials is required to increase active sites and build electronic structures. Herein, nitrogen contained face-centered cubic rhodium (N-fcc-Rh) nanosheets are prepared by directly annealing metastable trigonal rhodium oxide precursor in the ammonia atmosphere. Benefiting from the abundant active sites and unique electronic structure, the optimal N-fcc-Rh-300 electrocatalyst achieves an ultra-low working potential of − 81 mV (vs. RHE) at 10 mA cm−2 in 1.0 M KOH/0.5 M N 2 H 4. Density functional theory calculations suggest the N element in the N-fcc-Rh electrocatalyst enables to the reduction of the formation energy of the potential-determining step from *NH 2 NH 2 to *NHNH 2 for the HzOR process. This work reveals a new strategy to prepare advanced metal electrocatalysts for various electrochemical applications. [Display omitted] • Nitrogen contained face-centered cubic rhodium nanosheets. • Excellent HzOR activity with working potential of − 81 mV (vs. RHE) at 10 mA cm−2. • N elements into Rh leads to a shift of the d-band center away from the Fermi level. [ABSTRACT FROM AUTHOR]

Transition metal electrocatalysts with high activity and long durability are desired for methanol oxidation reaction (MOR). Here, the surface fluorinated nickel-graphene nanocomposites (F–Ni–G) are synthesized via the reduction of Si–H bonds produced by silicon and ammonium fluoride in hydrothermal condition. During this process, ionic nickel-F bonds and semi-ionic C–F bonds are introduced to the catalysts as confirmed by X-ray photoelectron spectroscopy. When F–Ni–G nanocomposites are employed as MOR catalysts, the surface fluorination is contributed to the formation of nickelic, which can increase the activity and kinetics for MOR. The onset oxidation potential of F–Ni–G-2 for methanol oxidation is 53 mV lower than that of the Ni/G catalyst without fluorine. The mass activity of F–Ni–G-2 (2493.3 A g−1) is 3.90 folds than that of Ni/G (638.5 A g−1). In addition, the density functional theory calculation indicates that the modified fluorine in graphene results in the decreased reaction energy barrier from ∗CO to ∗COOH step in MOR. The strong electronegativity of F atom makes intermediates easier to attract OH− groups and repel protons, which is conductive to decrease the reaction energy barrier for MOR. Such a facile method for the fabrication of the surface fluorinated catalytic system may be extended to the preparation of other transition metal electrocatalysts. The surface fluorination effect of nickel-graphene nanocomposites is not only contributed to the formation of nickelic, but also decreases the reaction energy barrier for methanol oxidation reaction. [Display omitted] • The surface fluorinated Ni-graphene is synthesized via the reduction of Si–H bonds. • Ionic Ni–F bonds and semi-ionic C–F bonds are introduced to the F–Ni–G catalysts. • The onset oxidation potential of F–Ni–G-2 for MOR is lower than that of the Ni/G. • The mass activity of F–Ni–G-2 is 3.90 folds than that of Ni/G. • Fluorine results in the decreased reaction energy barrier from ∗CO to ∗COOH. [ABSTRACT FROM AUTHOR]

3R-phase iridium oxide with superior ORR activity was obtained by intercalating a tiny amount of Pt into its interlayers. A mechanism that intercalates Pt atoms into the interlayer of 3R-IrO 2 enables to activate the ORR activity of the passivated Ir atoms in 3R-IrO 2 is proposed to further understand the real active center for precious metal-intercalated metal oxide electrocatalysts. [Display omitted] • Pt-intercalated 3R-phase iridium oxide is fabricated at normal temperature. • 3R-IrO 2 with high ORR activity by intercalating 3.6 %Pt into the interlayers. • The active center of Pt-3R-IrO 2 in ORR is the Ir sites rather than the Pt sites. Iridium oxide (IrO 2) has traditionally been considered to exhibit limited oxygen-reducing capacity. An effective approach to improve the oxygen reduction reaction (ORR) activity in parent catalytic materials is through atomic intercalation. However, the challenge lies in achieving a delicate balance between high ORR activity, structural stability, and minimizing the use of precious metals. Herein, we fabricate 3R-phase iridium oxide (3R-IrO 2) with superior ORR activity by intercalating a tiny amount of Pt (3.6 wt% Pt) into the interlayers of 3R-IrO 2 (3.6 wt% Pt-3R-IrO 2). When employed as an acidic ORR electrocatalyst, 3.6 wt% Pt-3R-IrO 2 shows a high half-wave potential (E 1/2) of 0.92 V (vs. RHE) in O 2 -saturated 0.1 M HClO 4 electrolyte, much better than those of Pt/C (0.850 V), 3R-IrO 2 (0.616 V), and Pt nanoparticles on 3R-IrO 2 surface (3.6 wt% Pt@3R-IrO 2) (0.618 V) electrocatalysts. It achieves high mass activity of 0.170 A mg Ir −1 at the potential of 0.9 V, which is 5.5 and 11.3 times than that of Pt/C (0.031 A mg Ir −1) and 3.6 wt% Pt@3R-IrO 2 (0.015 A mg Ir −1), respectively. Density functional theory (DFT) calculations and experiment results co-jointly demonstrate that the active center of Pt-3R-IrO 2 is anchored to the activated Ir atoms of the 3R-IrO 2 rather than Pt atoms. The d -band center of Ir 5 d orbitals of Pt-3R-IrO 2 is simultaneously regulated, which optimizes the energy barrier of adsorption/desorption toward the ORR process. Intriguingly, the intercalation of Pt atoms into trigonal rhodium oxide (Tri-RhO 2) also activates the ORR activity of Rh, suggesting the universality of this strategy. This discovery may provide a new and general way for activation of ORR activity of other precious metal-intercalated nonprecious metal oxide electrocatalysts. [ABSTRACT FROM AUTHOR]

Direct ethanol fuel cells (DEFCs) are considered as the ideal green power suppliers because of high energy density and non-toxicity of ethanol. Here the ball cactus-like gold (Au) particles reduced by hydrogen peroxide solution are coated with sulfhydryl-functionalized carbon dots (SCDs-Au). When the SCDs-Au composite is employed as the anodic electrocatalyst for ethanol oxidation reaction, an anode peak current density of 23.23 mA cm−2 (mass activity of 102.65 mA mg−1) is obtained at 0.19 V (vs. SCE) in 1.0 M KOH and 1.0 M ethanol at a scan rate of 20 mV s−1, which is about 4.4 times than that of Au without modification of SCDs. The higher catalytic activity is attributed to the higher ethanol adsorption capability caused by the shell-like SCDs. According to the adsorption experiment, ethanol adsorption capability of SCDs-Au is calculated as 2.8 times than that of Au without modification. At the same time, the addition of SCDs improves the electrocatalytic stability of Au. Such a surface modification method can be applied in other catalyst design processes. The ball cactus-like gold (Au) particles reduced by hydrogen peroxide solution are coated with sulfhydryl-functionalized carbon dots (SCDs-Au). SCDs-Au shows enhanced anode current density for ethanol oxidation attributed to the higher ethanol adsorption capability caused by CDs shell. [ABSTRACT FROM AUTHOR]

The interfacial engineered Rh-carbon nitride was developed and as advanced electrocatalysts for HER in the acidic and alkaline electrolytes. The interface between Rh nanocrystals and carbon nitride may adjust the electronic structure of Rh, which downshifts their d -band center positions, tuning the adsorption ability for hydrogen and accelerating the HER kinetics. Exploring the highly efficient and durable electrocatalysts for hydrogen evolution reaction (HER) is vitally necessary for sustainable energy conversion and storage system. Herein, we fabricate an interfacial engineered Rh-carbon nitride as advanced electrocatalysts for HER in the acidic and alkaline electrolytes. The interface between Rh nanocrystals and carbon nitride may adjust the electronic structure of Rh, which results in high activity for HER. The optimal Rh-carbon nitride shows low overpotential at current density of −10 mA·cm−2 and small Tafel slope (13 mV and 25.0 mV dec−1 in 0.5 M H 2 SO 4 , 46 mV and 42.0 mV dec−1 in 1.0 M KOH, respectively), which is superior to that of commercial Pt/C (21 mV and 28.5 mV dec−1 in 0.5 M H 2 SO 4 , 55 mV and 44.0 mV dec−1 in 1.0 M KOH, respectively). Importantly, this composite also exhibits long-term stability in 0.5 M H 2 SO 4 and 1.0 M KOH. The excellent HER performances can be attribute to the interface between Rh and carbon nitride, which downshifts their d -band center positions, tuning the adsorption ability for hydrogen and accelerating the HER kinetics. This work may open up an efficient method to design metal/carbon hybrid for electrocatalysis. [ABSTRACT FROM AUTHOR]

The present study aimed to examine the effect of RNA interference targeting cell division cycle-associated protein 4 (CDCA4) on the proliferation and apoptosis of the MCF-7/ADR' human breast cancer cell line. CDCA4 has been shown to have a unique role in regulating cell cycle. In the present study, the expression of CDCA4 was suppressed by CDCA4-specific short hairpin (sh)RNA transfection of the human breast cancer cells, following which changes in the proliferation and apoptosis of the CDCA4-knockdown cells were compared with those of control shRNA-transfected cells. The results confirmed that CDCA4 RNA interference reduced the percentage of human breast cancer cells to <50%. In addition, RNA interference of CDCA4 resulted in a significant increase in the apoptotic rate of cells. Taken together, these results suggested that CDCA4 enhanced proliferation and reduced apoptosis in the MCF-7/ADM human breast cancer cells in vitro. [ABSTRACT FROM AUTHOR]

Pulmonary fibrosis (PF), a lethal lung disease, can lead to structural destruction of the alveoli until death. Sparganii Rhizoma (SR), primarily distributed in East Asia, has been used clinically for hundreds of years against organ fibrosis and inflammation. We intended to verify the effect of SR alleviate PF and further explore mechanisms. Murine model of PF was established by endotracheal infusion of bleomycin. We detected the anti-PF effect of SR through lung coefficient, hydroxyproline content, lung function and pathological staining. Then, we used Western Blot and RT-PCR to verify the mechanism. In vitro experiments, MRC-5 and BEAS-2B were induced to phenotypic transformation by TGF-β1 and then RT-PCR, WB and IF were conducted to verify the effect of SR. SR significantly reduced BLM-induced PF in mice, improved lung function, slowed the degree of lung tissue lesions, and reduced collagen deposition. SR alleviated PF by inhibiting fibroblasts differentiation and epithelial-mesenchymal transition. In vivo studies explored the mechanism and found that it was related to TGF-β1/Smad2/3 pathway. Our research proved SR could effectively treat PF, providing a fresh idea and approach for the treatment of PF with traditional Chinese medicine. [Display omitted] • We reported Sparganii Rhizoma effectively alleviated pulmonary fibrosis. • We verified the anti-PF effect in in vitro and in vivo systems. • Sparganii Rhizoma inhibited fibroblasts differentiation and epithelial-mesenchymal transition. [ABSTRACT FROM AUTHOR]

Poisoning species, such as methanol and air pollutants, degrade the electrocatalytic activity for oxygen reduction reaction (ORR). Here, via taking advantage of the varied electronic property of nano-silicon, a versatile strategy is reported for enhancing the catalytic activity and anti-poisoning ability toward ORR by decorating noble metal catalysts with the size-controlled silicon nanoclusters (DS). Consequently, DS-Pd exhibits the enhanced ORR performance with a large halfwave potential of 0.892 V and an onset potential of 1.010 V. More importantly, it also shows enhanced anti-poisoning performance in methanol, NaNO 2 and NaHSO 3 electrolytes, compared to those of commercial Pt/C and Pd/C catalysts. Mechanism studies reveal that the synergistic effect between Pd and more oxygen-philic and less poison-philic Si nanoclusters largely abbreviate the absorption of poisoning species on the active sites. This strategy also improves the methanol-tolerant performance of Pt based catalysts, providing a versatile strategy for the fabrication of methanol-tolerant ORR catalysts. [Display omitted] • Diluted silicon nanoclusters reduce the d band center of Pd atoms. • A lower d band center of Pd further weakens the adsorption of poisons. • Diluted silicon nanoclusters increase the catalytic activity of Pd or Pt toward ORR. • Diluted silicon nanoclusters enhance the anti-poisoning performance of Pd or Pt. • DS-Pd exhibits improved ORR performance with a halfwave potential of 0.892 V. [ABSTRACT FROM AUTHOR]

ABSTRACT Novel carboxyl- and amino-functionalized copolyesters, based on poly(ε-caprolactone)- block-poly(butylene fumarate)- block-poly(ε-caprolactone), were efficiently synthesized via Michael-type thiol-ene click chemistry. The resulting amphiphilic copolyesters with controllable molecular weights and abundant positively or negatively charged groups could spontaneously form pH-sensitive micelles in aqueous solutions, as confirmed by transmission electron microscopy, dynamic light scattering, fluorescence probing technique, and zeta potential analyses. Importantly, charge-reversal hybrid micelles can be obtained by co-assembly of carboxyl- and amino-functionalized copolyesters. The surface charges of hybrid micelles reversed rapidly from negative to positive at isoelectric point via protonation of surface carboxyl and amino groups. Interestingly, the hybrid micelles showed apparent pH-triggered Nile red-release behavior in acidic condition resembling tumor intracellular environment, which is fairly desirable for drug delivery. Our work indicates that co-assembly is a facile but efficient way to prepare charge-reversal micelles, which have great potential to be used as intelligent drug delivery systems for cancer therapy. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 1259-1267 [ABSTRACT FROM AUTHOR]

Antibacterial and antioxidant monomethyl fumaric acid (MFA) was selected to modify chitosan, using aqueous solution of an ionic liquid as a homogeneous and green reaction media. The chemical structures of resulting polymers were systematically characterized by 1 H NMR, diffusion ordered spectroscopy, solid 13 C NMR and wide-angle X-ray diffraction. The results show that two kinds of MFA modified chitosan materials with totally different chemical structures have been synthesized. One product was a MF-chitosan salt composed of chitosan cation and MFA anion, which was obtained with the mediation of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) and N -hydroxysuccinimide. The other one synthesized with the mediation of EDC was a MF-chitosan amide in which MFA and chitosan are covalently attached. Solubility of chitosan has been improved, and MF-chitosan salt can be readily dissolved in water. The antioxidant activity has been enhanced with the introduction of MFA, irrespective of the chemical structure. [ABSTRACT FROM AUTHOR]