Thermal reflux to synthesise C3N4 nanostructures with high yield and enhanced photocatalytic activity in hydrogen evolution.

Graphitic carbon nitride (g-C3N4) is an attractive photocatalyst and a thermal reflux method was used to significantly increase the yield of g-C3N4 nanostructures and enhance their photocatalytic activity for H2 production. When raw material was placed in an inclined quartz tube with the bottom in the high temperature zone and the top in the low temperature zone, the vapor of the raw material was condensed from the top and refluxed to the bottom to then participate in the reaction again. This method can significantly improve the yield of g-C3N4 with an increase of 28.2%. When used as the photocatalyst in water splitting, these g-C3N4 nanostructures exhibit excellent activity with an H2 production of 2102 µmol h-1 g-1 under visible irradiation, which is 43.2% higher than the sample prepared by a traditional thermal polymerization method. This method is also promising to use for the synthesis of similar two-dimensional nanostructures for effective H2 production.

Mechanism of surface oxygen-containing species promoted electrocatalytic CO2 reduction.

Oxygen-containing species have been demonstrated to play a key role in facilitating electrocatalytic CO2 reduction (CO2RR), particularly in enhancing the selectivity towards multi-carbon (C2+) products. However, the underlying promotion mechanism is still under debate, which greatly limits the rational optimization of the catalytic performance of CO2RR. Herein, taking CO2 and O2 co-electrolysis over Cu as the prototype, we successfully clarified how O2 boosts CO2RR from a new perspective by employing comprehensive theoretical simulations. Our results demonstrated that O2 in feed gas can be rapidly reduced into *OH, leading to the partial oxidation of Cu surface under reduction conditions. Surface *OH accelerates the formation of quasi-specifically adsorbed K+ due to the electrostatic interaction between *OH and K+ ions, which significantly increases the concentration of K+ near the Cu surface. These quasi-specifically adsorbed K+ ions can not only lower the C-C coupling barriers but also promote the hydrogenation of CO2 to improve the CO yield rate, which are responsible for the remarkably enhanced efficiency of C2+ products. During the whole process, O2 co-electrolysis plays an indispensable role in stabilizing surface *OH. This mechanism can be also adopted to understand the effect of high pH of electrolyte and residual O in oxide-derived Cu (OD-Cu) on the catalytic efficiency towards C2+ products. Therefore, our work provides new insights into strategies for improving C2+ products on the Cu-based catalysts, i.e., maintaining partial oxidation of surface under reduction conditions.

Precise synthesis of BN embedded perylene diimide oligomers for fast-charging and long-life potassium-organic batteries.

Replacing the C[double bond, length as m-dash]C bond with an isoelectronic BN unit is an effective strategy to tune the optoelectronic properties of polycyclic aromatic hydrocarbons (PAHs). However, precise control of the BN orientations in large PAH systems is still a synthetic challenge. Herein, we demonstrate a facile approach for the synthesis of BN embedded perylene diimide (PDI) nanoribbons, and the polarization orientations of the BN unit were precisely regulated in the two PDI trimers. These BN doped PDI oligomers show great potential as organic cathodes for potassium-ion batteries (PIBs). In particular, trans-PTCDI3BN exhibits great improvement in voltage potential, reversible capacities (ca. 130 mA h g-1), superior rate performance (19 s to 69% of the maximum capacity) and ultralong cyclic stability (nearly no capacity decay over 30 000 cycles), which are among those of state-of-the-art organic-based cathodes. Our synthetic approach stands as an effective way to access large PAHs with precisely controlled BN orientations, and the BN doping strategy provides useful insight into the development of organic electrode materials for secondary batteries.

SdH Oscillations from the Dirac Surface State in the Fermi-Arc Antiferromagnet NdBi.

The recent progress in CuMnAs and Mn3X (X = Sn, Ge, Pt) shows that antiferromagnets (AFMs) provide a promising platform for advanced spintronics device innovations. Most recently, a switchable Fermi-arc is discovered by the ARPES technique in antiferromagnet NdBi, but the knowledge about electron-transport property and the manipulability of the magnetic structure in NdBi is still vacant to date. In this study, SdH oscillations are successfully verified from the Dirac surface states (SSs) with 2-dimensionality and nonzero Berry phase. Particularly, it is observed that the spin-flop transition only appears when the external magnetical field is applied along [001] direction, and features obvious hysteresis for the first time in NdBi, which provides a powerful handle for adjusting the spin texture in NdBi. Crucially, the DFT shows the Dirac cone and the Fermi arc strongly depend on the high-order magnetic structure of NdBi and further reveals the orbital magnetic moment of Nd plays a crucial role in fostering the peculiar SSs, leading to unveil the mystery of the band-splitting effect and to manipulate the electronic transport, high-effectively, in the thin film works in NdBi. It is believed that this study provides important guidance for the development of new antiferromagnet-based spintronics devices based on cutting-edge rare-earth monopnictides.

A simple descriptor for the nitrogen reduction reaction over single atom catalysts.

The performance of supported catalysts is largely decided by metal-support interactions, which is of great significance for the rational design of catalysts. However, how to quantify the structure-activity relationship of supported catalysts remains a great challenge. In this work, taking MoS2 and WS2 supported single atom catalysts (SACs) as prototypes, a simple descriptor, namely, effective d electron number (labeled as Φ), is constructed to quantitatively describe the effect of metal-support interaction on the nitrogen reduction reaction (NRR) activity. This descriptor merely consists of intrinsic properties of the catalyst (including the number of d electrons, electronegativity of the metal atoms and generalized electronegativity of the substrate atoms) and can accurately predict the limiting potential (UL) for the NRR, with no need for any density functional theory calculations. Moreover, this descriptor possesses superb expansibility that can be applied to other materials, including other metal dichalcogenide (MoSe2, MoTe2, WSe2, WTe2 and NbS2) and even MXene (V2CO2, Ti2CO2 and Nb2CO2)-supported SACs. On this basis, a fast screening of excellent NRR catalysts among these systems is performed and three promising NRR catalysts (i.e. Mo@WTe2, Mo@V2CO2 and Re@NbS2) are successfully selected with UL as low as -0.32, -0.24 and -0.31 V, respectively. This work offers new opportunities for advancing the rapid discovery of high-efficiency NRR catalysts, and the design principle is expected to be widely applicable to other catalytic systems and beyond.

Design of epoxidized natural rubber/poly(lipoic acid) elastomer with fast and efficient self-healing under a mild temperature.

Most of the dynamic covalent bonds (DCBs) for self-healing rubber must be activated at relatively high temperatures due to the requirement of high energy during the exchange of dynamic bonds, which may lead to unexpected degradation or excessive crosslinking of rubber. Herein, we designed and fabricated a highly stretchable, self-healable and reprocessable rubber by introducing dynamic disulfide bonds into the crosslink network of epoxidized natural rubber (ENR). Lipoic acid (LA) was firstly uniformly dispersed into ENR via a latex film formation technique, and then underwent a dynamic covalent ring-opening self-polymerization during hot pressing process, during which the carboxyl group of poly(LA) attacked the epoxy group of ENR to form ß-hydroxyl ester bond crosslinks. As a result, a revisable covalently crosslinked network without rigid steric hindrance groups was constructed, which exhibited a super self-healing efficiency of 99 % after self-healing at 80 °C for only 3 h. The elongation at break of the elastomer could reach 1115 % and the recovery rate of reprocessing was as high as 91 %.

Regiochemically Pure 1,6-Ditriflato-Perylene Diimide: Preparation and Transformation.

Preparation of regioisomerically pure 1,6-disubstituted perylene diimide (PDI) is not a trivial task owing to the lack of facile synthetic and separation methodologies for the precursors. Herein, we present a simple synthesis for 1,6-ditriflato-PDI (1,6-diOTf-PDI) using 1,6,9,10-tetrabromo-perylene monoimide 1 as the starting material. The selective methoxylation of 1 at the 1,6-position is the key step. Based on a four-step sequence of selective methoxylation, domino carbonylative amidation, demethylation, and triflation, 1,6-diOTf-PDI can be obtained in a satisfactory yield. Moreover, as a building block, 1,6-diOTf-PDIa can readily undergo Suzuki and Sonogashira cross-coupling reactions.

Strengthened self-healable natural rubber composites based on carboxylated cellulose nanofibers participated in ionic supramolecular network.

Cellulose, as a green reinforcing agent for rubber, has excellent improvement on the tensile strength but usually accompany with a deterioration of extensibility and self-healing property. Herein, we report an efficient method to prepare robust and self-healable natural rubber/zinc dimethacrylate/carboxylated cellulose nanofibers (NR/ZDMA/CNC) composites which are constructed by a CNC participated ionic supramolecular network. Ionic supramolecular network in NR is generated by the polymerization of ZDMA during a controlled peroxide-initiated vulcanization of NR. Interestingly, NR with massive ion clusters has strong affinity with CNC, which facilitates the uniform dispersion of CNC and the compatibility between CNC and NR. Meanwhile, CNC participates into the supramolecular network via non-covalent interaction with NR chains equipped with ionic crosslinks. This greatly reduces the adverse effect of CNC on the dynamic characteristics of supramolecular network. As a result, the tensile strength of NR/ZDMA composite with 20 phr CNC could reach 4.13 MPa, while its self-healing efficiency still maintains at >80 %. Thus, NR composites with non-covalent interaction between CNC and supramolecular network display improved strength, maintained extensibility, and excellent self-healing capability. This study thus demonstrates a feasible approach to reduce the negative effect of reinforcing fillers on a self-healing rubber based on supramolecular networks.

The positive role of trade openness in industrial green total factor productivity-provincial evidence from China.

The sustainable development of the economy is a key issue of global concern. Green total factor productivity (GTFP) combining economic growth with resources and the environment can evaluate the quality of economic development comprehensively and accurately. In this paper, super slack-based measure (Super-SBM) model and Malmquist-Luenberger (ML) index were used to calculate GTFP. The trend of industrial GTFP in China's 30 provinces from 2006-2015 was analyzed. Furtherly, a dynamic panel model was used to discuss the impact of trade openness on GTFP. The results showed that (1) the growth rate of GTFP rose from 2007 to 2011 and declined significantly from 2011 to 2015, and GTFP only achieved positive growth in 2011; (2) the growth rate of GTFP in the eastern region was higher than that in the central and western regions; (3) the trend of technical progress change (MLTECH) index was highly consistent with that of ML index. That was, technical progress played a major role in the variation of GTFP; (4) trade openness could significantly improve China's GTFP. Every 1% increase in trade openness could increase GTFP by 0.097% on average. It is advisable to implement differentiated economic development and environmental policies in different regions. Meanwhile, relevant measures can be taken to promote import and export trade, such as encouraging companies to increase investment in green technology research and development, optimizing the trade environment.

Perylene Diimide Hexamer Based on Combination of Direct and Indirect Linkage Manners for Non-fullerene Organic Solar Cells.

Perylene diimide (PDI) is one of the most intensively studied building blocks for the construction of non-fullerene acceptors (NFAs). In this contribution, based on combination of the direct and indirect linkage manners of PDI units at the bay position, a propeller-shaped PDI hexamer T-DPDI was designed and synthesized. The singly bonded PDI dimer DPDI and the benzene ring cored PDI trimer TPDI were synthesized for comparison. The photovoltaic performances of these three PDI derivatives were investigated using the commercially available PTB7-Th as electron donor. A best power conversion efficiency (PCE) of 6.58% was obtained for T-DPDI based organic solar cells (OSCs), which is higher than those of DPDI and TPDI based ones. The superior photovoltaic performance of T-DPDI can be ascribed to its stronger absorption and more favorable morphology. This study presents an interesting example of improving the photovoltaic performances of PDI based NFAs by hybridizing the direct and indirect linkage manners.

Molecular Regulation on Carbonyl-Based Organic Cathodes: Toward High-Rate and Long-Lifespan Potassium-Organic Batteries.

Organic redox-active molecules have been identified as promising cathodes for practical usage of potassium-ion batteries (PIBs) but still struggle with serious dissolution problems and sluggish kinetic properties. Herein, we propose a pseudocapacitance-dominated novel insoluble carbonyl-based cathode, [2,6-di[1-(perylene-3,4,9,10-tetracarboxydiimide)]anthraquinone, AQ-diPTCDI], which possesses high reversible capacities of 150 mAh g-1, excellent cycle stability with capacity retention of 88% over 2000 cycles, and fast kinetic properties. The strong intermolecular interactions of AQ-diPTCDI and in situ formed cathode electrolyte interphase films support it against the dissolution problem. The high capacitive-like contribution in capacities and fast potassium-ion diffusion enhance its reaction kinetics. Moreover, a symmetric organic potassium-ion battery (OPIB) based on AQ-diPTCDI electrodes also exhibits outstanding K-storage capability. These results suggest that AQ-diPTCDI is a promising organic cathode for OPIBs and provide a practicable route to realize high-performance K storage.

Identification and validation of a glycolysis-associated multiomics prognostic model for hepatocellular carcinoma.

Increased glycolysis has been reported as a major metabolic hallmark in many cancers, and is closely related to malignant behavior of tumors. However, the potential mechanism of glycolysis in hepatocellular carcinoma (HCC) and its prognostic value are not well understood. To address this, we investigated glycolysis-related gene expression data of patients with HCC from TCGA and ICGC. Patients were categorized into three different glycolysis-associated subgroups: Glycolysis-M, Glycolysis-H, and Glycolysis-L. We found that Glycolysis-H combined with Glycolysis-M (Glycolysis-H+M) subgroup was associated with poor overall survival and distinct cancer stem cell characteristics and immune infiltrate patterns. Additionally, multiomics-based analyses were conducted to evaluate genomic patterns of glycolysis subgroups, including their gene mutations, copy number variations, and RNA-sequencing data. Finally, a glycolysis-associated multiomics prognostic model (GMPM) consisting of 19 glycolysis-associated genes was developed. The capability of GMPM in categorizing patients with HCC into high- and low-risk groups was validated with independent HCC datasets. Finally, GMPM was confirmed as an independent risk factor for the prognosis of patients with HCC. We believe that our findings provide new insights into the mechanism of glycolysis and highlight the potential clinical value of GMPM in predicting the prognosis of patients with HCC.

Synthesis and biological evaluation of biotin-conjugated Portulaca oleracea polysaccharides.

Biotinylated Portulaca oleracea polysaccharide (Bio-POP) conjugates were successfully prepared by the esterification reaction. The biotinylated polysaccharide products were an off-white powder with an average degree of substitution of 42.5%. After grafting biotin onto POP, the thermal stability of Bio-POP conjugates was much higher than that of POP and the surface topography of Bio-POP was a loose and porous cross-linked structure. The cytotoxicity assay in vitro demonstrated that POP, biotin, and Bio-POP conjugates exhibited different cytotoxicity to HeLa, MCF-7, LO-2, and A549, in particular POP inhibited the growth of the A549 cell line more than other cell lines. The nuclear staining method demonstrated that Bio-POP conjugates can interfere with the apoptosis of A549 cells to some extent and the immunofluorescence staining photograph illustrated that Bio-POP conjugates induced A549 cells to exhibit immune activity. Therefore, the combination of biotin and Portulaca oleracea polysaccharides had immune synergistic therapeutic effects on A549 cells and can be applied in the field of anti-tumor conjugate drugs.

π-Extension, Selenium Incorporation, and Trimerization: "Three in One" for Efficient Perylene Diimide Oligomer-Based Organic Solar Cells.

Perylene diimide (PDI) and the vinylene-bridged helical PDI oligomers are versatile building blocks for constructing nonfullerene acceptors (NFAs). In this contribution, a benzene-cored star-shaped NFA, namely, TPDI2-Se, was designed and synthesized for organic solar cells (OSCs). The NFA with smaller π-conjugated blades, namely, TPDI-Se, was synthesized for comparison. Using the commercially available PTB7-Th as the electron donor, the best power conversion efficiency (PCE) of 3.62% was obtained for TPDI-Se-based OSCs. However, a much higher PCE of 8.59% was achieved for TPDI2-Se-based devices owing to the π-extension in the peripheral panels. Moreover, the photovoltaic performance of TPDI2-Se-based OSCs is also superior to those of the parent NFA TPDI2 (PCE of 7.84%)- and the blade moiety PDI2-Se (PCE of 6.61%)- based ones. Additionally, a remarkable short-circuit current (Jsc) value of 17.21 mA/cm2 was obtained for TPDI2-Se-based OSCs, which is among the highest Jsc values reported in PDI-based OSCs. These results argue that the so-called "three in one" molecule design strategy of π-extension, selenium incorporation, and trimerization offers a robust approach to constructing high-performance PDI-based NFAs.

The assembly and antitumor activity of lycium barbarum polysaccharide-platinum-based conjugates.

In this work, the new polysaccharide-platinum conjugates of 5-aminosalicylic acid modified lycium barbarum polysaccharide linking platinum compounds were designed in order to construct an anticancer metal drug delivery system. The multiple analysis methods were used to describe the chemical structure and physical properties of the polysaccharide-metal conjugates. The results showed that 5-aminosalicylic acid successfully acted as linker which was covalently bound between polysaccharide and platinum compound. The morphology and rheological properties of polysaccharide have been changed by the formation of conjugates, which exhibited certain inhibition specificity to A549 (human lung cancer cell line). The agarose gel electrophoresis and fluorescence microscopy results demonstrated that such conjugates promoted the unwinding of DNA and could significantly damage the nucleus of A549 cells. Cell cycle analyzing the Pt complex of conjugates could cause intracellular DNA damage and induced G2 phase arrest. So, polysaccharide-platinum conjugates might find a range of applications, for example in metal anticancer drug delivery.

Isomeric Effect on Optoelectronic Properties and Photovoltaic Performance of Anthraquinone-Core Perylene Diimide (PDI) and Helical PDI dimers.

Isomerism heavily influences the optoelectronic properties and self-assembly behavior of compounds and subsequently affects their device performance. Herein, two pairs of isomeric perylene diimide (PDI) dimers, PDI and PDI2, were designed and synthesized. The electron-deficient 9,10-anthraquinone group was employed as the bridge, and thus, the resultant dimers exhibited an acceptor-acceptor-acceptor (A-A-A) structure. To determine the isomeric effects on the optoelectronic properties and photovoltaic performance of these dimers, their absorptivity, luminescence, and redox behavior were studied. Bulk heterojunction organic solar cells based on these four dimers were fabricated and measured. The two PDI dimers exhibited clear differences in photovoltaic performance, whereas the two PDI2 analogues showed similar power conversion efficiencies (PCEs). The PCEs of the two PDI2 dimers are much higher than those of the PDI dimers. These results illustrate that the isomeric effect of PDI dimers is much larger than that of PDI2 dimers on the device performance, and proper expansion of conjugation could improve the device performance.

High Oxidation Resistance of CVD Graphene-Reinforced Copper Matrix Composites.

Copper-based materials are common industrial products which have been broadly applied to the fields of powder metallurgy, electrical contact, and heat exchangers, etc. However, the ease of surface oxidation limits the durability and effectiveness of copper-based components. Here, we have developed a powder metallurgy process to fabricate graphene/copper composites using copper powders which were first deposited with graphene layers by thermal chemical vapor deposition (CVD). The graphene/copper composites embedded with an interconnected graphene network was then able to be obtained by vacuum hot-pressing. After thermal oxidation (up to 220 °C) in humid air for several hours, we found that the degree of surface oxidation of our samples was much less than that of their pure Cu counterpart and our samples produced a much smaller increase of interfacial contact resistance when used as electrical contact materials. As a result, our graphene/copper composites showed a significant enhancement of oxidation resistance ability (≈5.6 times) compared to their pure Cu counterpart, thus offering potential applications as novel electrical contact materials.

Effect of Epoxy Resin on the Actuating Performance of Piezoelectric Fiber Composites.

Piezoelectric fiber composites (PFC) have shown excellent performance in the areas of vibration control and deformation control. The viscosity and rigidity of the epoxy resin before and after curing, respectively, were very important factors that affected the performance of PFC. In this paper, Aradite 2020, DP 460, and DP 490 epoxy resins, with the viscosities of 0.15, 25.0, and 250.0 Pa·s, respectively, were employed to encapsulate the piezoelectric fiber composite. The PFC that was packaged with Araldite 2020 had the best free strain of 1420 ppm and tip displacement of 17.8 mm. DP 490 caused the lowest performance of PFC, due to the highest viscosity. When the environmental temperature increased from -40 to +80 °C, the free strain of PFC with Aradite 2020 increased at first and then decreased, reaching a maximum value of 1440 ppm at 30 °C, which was mainly related to the mismatch of the resin/ceramic thermal expansion coefficient.

Plant-Based Culture Media for Improved Growth and Sporulation of Cercospora janseana.

Cercospora janseana is the causal agent of narrow brown leaf spot, one of the major diseases of rice in the United States. In vitro studies were conducted to evaluate various plant-based agar media in comparison with potato dextrose agar (PDA) for their effects on radial growth and sporulation of C. janseana. The agar media were evaluated individually with the following plant-extract ingredients: fresh rice leaves, dried rice leaves, dried rice stems, dried rice roots, dried rice hulls, dried rice straw, rice bran, dried sorghum leaves, and dried barnyard grass leaves. Plant-based extracts obtained from 25, 50, 100, or 200 g/liter (plant material/water) were tested either alone or in combination with 10 and 20% clarified V8 juice. PDA served as the control medium. Media with 10 and 20% V8 juice were also included for comparison. Media were inoculated with a disc of 1-week-old actively growing C. janseana at the center of Petri plates and incubated at 28°C with a 12/12-h (light/dark) cycle for 2 weeks. Radial growth was measured at 7 and 14 days after inoculation (DAI), whereas sporulation was measured at 14 DAI. Radial growth and sporulation differed among various media and their amendment concentrations. Media with extracts of fresh rice leaves, dried rice leaves, dried rice stems, dried barnyard grass leaves, and clarified V8 juice enhanced radial growth compared with the PDA control. Of all the agar media evaluated, fresh rice leaf extract amendment at 25 g/liter with no V8 supplementation consistently supported the greatest radial growth, and 10% V8-only medium resulted in greater sporulation of C. janseana than other media evaluated.

Lycium barbarum polysaccharides grafted with doxorubicin: An efficient pH-responsive anticancer drug delivery system.

Lycium barbarum polysaccharide-doxorubicin (LBP-DOX) nanoparticles were synthesized via a one-step Schiff base reaction between oxidized Lycium barbarum polysaccharide (oxidized LBP) and doxorubicin (DOX). The structure of LBP-DOX nanoparticles was characterized by multi-spectral methods, 1H nuclear magnetic resonance (1H NMR), transmission electron microscopy (TEM), and thermo gravimetric analysis (TGA). The rheological properties of LBP-DOX nanoparticles were studied. With the increase of shear rate, the viscosity of LBP and LBP-DOX nanoparticles gradually decreases at 25 °C. Under the same strain, the storage modulus (G') and loss modulus (G″) of LBP-DOX nanoparticles were inferior to LBP. The DOX release from LBP-DOX nanoparticles was pH-dependent and was accelerated by decreasing pH. Cytotoxicity study showed that the LBP-DOX nanoparticles have significantly enhanced cytotoxicity in vitro, especially for human Hepatic cancer cell line HepG2.