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By incorporating a small amount of polymer acceptor (N2200) into an all-small-molecule host system, a novel ternary device is developed which shows an increased PCE of 12.19% with improved stability in comparison with the corresponding binary device.

The water–gas shift reaction (WGSR) plays a pivotal role in many important industrial processes as well as in the elimination of residual CO in feed gas for fuel cells.

Cu-based catalysts are commonly applied in low-temperature water gas shift (WGS) reactions, owing to their low cost and high catalytic activity. The influence of different Cu surfaces on catalytic activity and mechanism over the WGS reaction remains unclear. In this work, the effect of different structures of surfaces on the WGS mechanism is studied using density functional theory (DFT). Three surface terminations (Cu(100), Cu(111), and Cu(211)) of Cu are considered, and the coordination number (CN) of the active Cu site is in the range from 7 to 9. The most stable surface is Cu(211). Then, d-band center values are calculated, which decrease in the following sequence: Cu(211) > Cu(100) > Cu(111). This shows that d-band center values decrease with increasing coordination number. The increase in the centers of the d-band leads to an increase in the adsorption strength of CO and H2O adsorbates, which is in line with the theory of the d-band center. In addition, the further calculated mechanism for WGS reaction over three different Cu surfaces illustrates that the carboxyl path is the most favorable mechanism, and the rate-determining step is H2O dissociation. Cu(211) shows excellent WGS catalytic performance, better than the Cu(100) and Cu(111) surfaces. This work provides theoretical insights into the rational design of highly active Cu-based catalysts toward WGS reaction.

The water gas shift reaction (WGS) process on the NiM(111) bimetallic surfaces (M = Fe, Co, Cu, Zn) are studied by density functional theory method and experimental studies. The NiCo and NiCu exhibit the optimum catalytic activity and CO2 selectivity.

Supplementary data of in vitro cell line experiments, human stomach tumor database/sample analysis and animal experiments.

Dysregulation of Wnt/β-catenin signaling is frequently observed in human gastric cancer. Elucidation of the tumor immune microenvironment is essential for understanding tumorigenesis and for the development of immunotherapeutic strategies. However, it remains unclear how β-catenin signaling regulates the tumor immune microenvironment in the stomach. Here, we identify CCL28 as a direct transcriptional target gene of β-catenin/T-cell factor (TCF). Protein levels of β-catenin and CCL28 positively correlated in human gastric adenocarcinoma. β-Catenin–activated CCL28 recruited regulatory T (Treg) cells in a transwell migration assay. In a clinically relevant mouse gastric cancer model established by Helicobacter (H.) felis infection and N-methyl-N-nitrosourea (MNU) treatment, inhibition of β-catenin/TCF activity by a pharmacologic inhibitor iCRT14 suppressed CCL28 expression and Treg cell infiltration in the stomach. Moreover, an anti-CCL28 antibody attenuated Treg cell infiltration and tumor progression in H. felis/MNU mouse models. Diphtheria toxin–induced Treg cell ablation restrained gastric cancer progression in H. felis/MNU-treated DEREG (Foxp3-DTR) mice, clarifying the tumor-promoting role of Treg cells. Thus, the β-catenin–CCL28–Treg cell axis may serve as an important mechanism for immunosuppression of the stomach tumor microenvironment. Our findings reveal an immunoregulatory role of β-catenin signaling in stomach tumors and highlight the therapeutic potential of CCL28 blockade for the treatment of gastric cancer.Significance:These findings demonstrate an immunosuppressive role of tumor-intrinsic β-catenin signaling and the therapeutic potential of CCL28 blockade in gastric cancer.

Three 12, 8-guaianolide sesquiterpene lactones, including a new compound intybusin F (1), and a new natural product cichoriolide I (2), along with six known 12, 6-guaianolide compounds (4–9) were isolated from the roots of Cichorium intybus L. Their structures were determined by extensive spectroscopic analysis. The absolute configurations of new compounds were elucidated based on analysis of the experimental and calculated electronic circular dichroism spectra. Compounds 1, 2, 4, 7, 8 showed significant effects on facilitating the glucose uptake in oleic acid plus high glucose-stimulated HepG2 cells at 50 μM. In addition, compounds 1, 2, 3, 6, 7 exhibited obvious inhibitory effects against NO production, of them, compounds 1, 2, 7 can significantly decrease the secretion of inflammatory cytokines (TNF-α, IL-6 and COX-2) levels in this hyperglycemic HepG2 cell model.

The H2 production from methanol steam reforming (MSR) reaction is regarded as one promising way to achieve the coupling between hydrogen production and fuel cells. Hitherto, Cu-based catalysts serve as the predominant MSR catalyst, but several fundamental issues still remain ambiguous (e.g., intrinsic active center, catalytic reaction network). Herein, we prepared Cu/Cu(Al)Ox catalysts featured by amorphous alumina-stabilized Cu2O adjoining Cu nanoparticle to provide Cu0-Cu+ sites. The optimized catalyst 4.25Cu/Cu(Al)Ox (Cu/Al molar ratio of 4.25) exhibits extraordinary catalytic performance towards hydrogen generation from MSR reaction, with a CH3OH conversion of 99.5%, a H2 production rate of 110.8 μmol s-1 gcat-1 and prominent durability at 240 ℃(300 h). A combination investigation including in situ FT-IR spectroscopy and mass spectrometry analysis confirms a three-step catalytic reaction pathway: dehydrogenation of methanol to methyl formate (HCOOCH3), hydrolyzation of HCOOCH3 to produce formate (HCOO*), followed by HCOO* decomposition to CO2 and H2. A binary function correlation between CH3OH reaction rate and the surface concentrations of Cu0 and Cu+ is established based on kinetic studies. In addition, in situ XAFS spectroscopy and theoretical calculations reveal the intrinsic active centers: the oxygen-containing intermediates (CH3O* and HCOO*) adsorbed at Cu0-Cu+ sites with a moderate adsorption strength promote electron transfer from catalyst to surface species, which significantly reduces the reaction barrier of rate-determining step (C-H bond cleavage) in CH3O* and HCOO* intermediates. The in-depth understanding of Cu0-Cu+ synergistic catalysis demonstrated in this work is constructive for the development of high-performance heterogeneous catalysts towards hydrogen production.

Maize (Zea mays L.) is a cold-sensitive species that often faces chilling stress, which adversely affects growth and reproduction. However, the genetic basis of low-temperature adaptation in maize remains unclear. Here, we demonstrate that natural variation in the type-A Response Regulator 1 (ZmRR1) gene leads to differences in chilling tolerance among maize inbred lines. Association analysis reveals that InDel-35 of ZmRR1, encoding a protein harboring a mitogen-activated protein kinase (MPK) phosphorylation residue, is strongly associated with chilling tolerance. ZmMPK8, a negative regulator of chilling tolerance, interacts with and phosphorylates ZmRR1 at Ser15. The deletion of a 45-bp region of ZmRR1 harboring Ser15 inhibits its degradation via the 26 S proteasome pathway by preventing its phosphorylation by ZmMPK8. Transcriptome analysis indicates that ZmRR1 positively regulates the expression of ZmDREB1 and Cellulose synthase (CesA) genes to enhance chilling tolerance. Our findings thus provide a potential genetic resource for improving chilling tolerance in maize., The genetic basis of low-temperature tolerance in maize is unclear. Here, the authors show that the type-A Response Regulator 1 (ZmRR1) and mitogen-activated protein kinase (MPK8) are positive and negative regulators of maize chilling tolerance, and ZmRR1 is phosphorylated by ZmMPK8 during cold treatment.

Catalytic conversion of a biomass derivative (levulinic acid, LA) to a high value-added product (γ-valerolactone, GVL) has attracted much attention, in which the control of catalytic selectivity plays an important role. Herein, a stepwise method was developed to prepare Co-MoOx catalysts via topological transformation (calcination reduction) from layered double hydroxide (Mo/CoAl-LDH) precursors. X-ray diffraction, high-resolution transmission electron microscopy, and hydrogen temperature-programmed reduction demonstrate the formation of MoOx-decorated Co structures of Co-MoOx samples. Remarkably, the sample that is reduced at 500 °C is featured with the most abundant interfacial Coδ+ (denoted as Co-MoOx-500), which exhibits an excellent catalytic performance toward the hydrodeoxygenation (HDO) reaction of several biomass-derived platform molecules (furfural, FAL; succinic acid, SA; 5-hydroxymethyl-furfural, HMF; and levulinic acid, LA). Especially, this optimal catalyst displays a high yield (99%) toward the HDO reaction of LA to GVL, which stands at the highest level among non-noble metal catalysts. The combination of in situ FT-IR characterization and theoretical calculation further confirms that interfacial Coδ+ sites in Co-MoOx-500 act as adsorption active sites for the polarization of a C═O bond in an LA molecule, which simultaneously promotes C═O hydrogenation and C-O cleavage. Moreover, the MoOx overlayer suppresses the formation of byproducts by covering the Co0 sites. This work offers a cost-effective and efficient catalyst, which can be potentially applied in catalytic conversion of biomass-derived platform molecules.

GaN-based blue micro-light-emitting diodes (µ-LEDs) with different structures were designed, of which the effect of quantum well (QW) structure on modulation bandwidth was numerically explored. By using trapezoidal QWs, the quantum-confined Stark effect (QCSE) can be reduced, leading to an enhanced electron-hole wave function overlap, thereby increasing the recombination rate and reducing the differential carrier lifetime. In addition, the improved hole transport also creates favorable conditions for shortening the differential carrier lifetime. It is found that the − 3 dB modulation bandwidth of µ-LEDs with trapezoidal QWs was higher than those of ordinary ones. In this work, the − 3 dB modulation bandwidth of µ-LEDs can be raised to 1.13 GHz at 10 kA/cm2.

Background A pathologically confirmed negative margin is required when performing sublobar resection in patients with early stage peripheral lung adenocarcinoma. However, the optimal margin distance to ensure complete tumor resection while preserving healthy lung tissue remains unknown. We aimed to establish a reliable distance range for negative margins. Methods A total of 52 intraoperative para-cancer tissue specimens from patients with peripheral lung adenocarcinoma with pathological tumors ≤2 cm in size were examined. Depending on the distance from the tumor edge (D), the para-cancer tissues were divided into the following five groups: D Results Group V, in which the margin was the farthest from the tumor edge, was the safest. There were significant safety differences in between groups I and V (χ2 = 26.217, P 2 = 9.420, P P = 0.207; P = 0.610). Conclusions We suggest that when performing sublobar resection in patients with early stage peripheral lung adenocarcinoma with pathological tumor sizes ≤2 cm, the resection margin distance should be ≥1 cm to ensure a negative margin.

Both photons and semiconductor quantum-dot (QD) spins are promising candidates for quantum information science and technology. It is of critical significance to realize high-fidelity quantum controlled gates on photon-spin hybrid systems. In this paper, based on the novel balance condition for the interaction between a single input photon and a singly charged QD embedded in an optical single-sided microcavity, we present three schemes for implementing three universal quantum controlled gates, i.e., the two-qubit controlled-NOT (CNOT) gate, the three-qubit Toffoli gate, and the three-qubit Fredkin gate, on composite hybrid quantum systems consisting of flying photons and QD-confined electron spins. By exploiting the balance condition, the noise caused by the unbalanced reflectance of the coupled and uncoupled QD-cavity systems can be efficiently suppressed, so that the fidelity of each quantum gate operation can be raised to unity in principle. The balance condition can be met without the strict requirement of strong coupling, making the high-fidelity quantum gates easier to be demonstrated in experiments. These features can improve the fidelity and feasibility of these schemes, which can be applied to large-scaled quantum computing and quantum information networks.

Hydrodeoxygenation (HDO), one of the effective approaches of C–O bond scission, plays a crucial role in biomass-derived oxygenate conversion to high value-added chemicals and biofuels. Herein, we systematically investigated the HDO reaction of furfural (FAL) to 2-methylfuran (2-MF) over 17 kinds of Ni-based bimetallic catalysts based on periodic density functional theory (DFT) calculations. The Ni-based partner (3d and 4d metals) has an important influence on the catalytic performance toward the FAL HDO reaction, which modifies the Ni electronic environment and induces the bimetal d orbital overlap, giving rise to changes in adsorption configuration and reaction activity. A specific correlation between the oxygen binding energy (OBE) value and energy barrier of C–OH scission/*OH species hydrogenation suggests that OBE serves as the most appropriate descriptor to characterize the activity of bimetallic catalysts. Due to the competitive relationship between C–O scission and *OH species hydrogenation, a trade-off of OBE has been built to promote C–O scission and hydrogenation activity simultaneously, in which Ni–M (M = Fe, Co, Mo, or Ru) bimetallic catalysts show prominent catalytic performance. Besides, we revealed that this descriptor can be extended to other bimetallic catalysts (CoV, CoFe, CuCo). Based on the calculation prediction, we prepared several alloys (NiCu, NiCo and NiZr). A series of characterization techniques (HRTEM, EDS, XPS, H2-TPR) indicated the formation of the alloys, whose catalytic evaluations verify that Ni-based catalysts (e.g., NiCo) with a compromise OBE value (from −4.00 to −2.00 eV) exhibit enhanced catalytic behavior towards FAL HDO to 2-MF, superior to other ones (e.g., NiCu: OBE value > −2.00 eV; NiZr: OBE value < −4.00 eV). This work offers a feasible strategy to design bimetallic catalysts for the HDO reaction based on the electronic environment and chemical nature of doped metals.

Balancing photovoltaic parameters is very challenging to optimize the device performance of nonfullerene small-molecule acceptor (SMA)-based polymer solar cells (PSCs). We herein employed electron-withdrawing fluorinated or chlorinated 1,1-dicyanomethylene-3-indanone (ICF or ICCl) as the terminal acceptor (A) group to develop two acceptor–donor–acceptor (A–D–A) SMAs, DTCFO-ICF and DTCFO-ICCl, with an electron-rich fluorene-fused dithienocyclopentafluorene as the identical central donor (D) core. Compared with the nonhalogenated counterpart (DTCFO-IC), the two halogenated SMAs possessed a red-shifted absorption spectrum, reduced optical bandgap, and increased charge carrier mobility, but these were accompanied by down-shifted HOMO and LUMO levels, especially for the chlorinated molecule (DTCFO-ICCl). Accordingly, with respect to DTCFO-IC, PSCs based on the two halogenated SMAs with polymer PBDB-T as a donor exhibited an improved Jsc, but a dropped Voc, thus leading to a commensurate power conversion efficiency (PCE) of 6.80% for DTCFO-ICF and an increased PCE of 8.55% for DTCFO-ICCl. To further improve the device performance by means of balancing photovoltaic parameters, polymer PBDB-TF with a lower-lying HOMO level relative to PBDB-T was used to replace PBDB-T as the donor. The PCEs of PBDB-TF-based PSCs were further improved mainly due to the significantly enhanced Voc. Importantly, the DTCFO-ICCl-based PSCs achieved a high PCE of up to 11.03% along with an increased Voc (0.93 V), a further increased Jsc (18.80 mA cm−2), and almost retained FF (63.1%). The enhanced device performance could be attributed to better charge transport and collection abilities, less charge recombination and more optimal active layer morphology. These results argue that combining the halogenation on the A group of an A–D–A acceptor and variation of the paired polymer donor could be an effective strategy to enhance the device efficiency by balancing photovoltaic parameters.

Catalytic Transfer Hydrogenation (CTH) of unsaturated functional groups to obtain high value-added products has attracted considerable attention in heterogeneous catalysis. Herein, we report a Ni single atoms (SAs) catalyst anchoring to Mg Al mixed metal oxide (MMO) based on structural topotactic transformation from hydrotalcite precursor, which displays an excellent catalytic behavior toward CTH of cinnamaldehyde (CAL) to cinnamyl alcohol (COL) (conversion: 100%; selectivity: 100%; 2 h). A combination research including AC-STEM, XAFS and in situ CO-IR demonstrates that Ni species anchored by Ni O coordination with different dispersion could be precisely obtained by tuning the reduction temperature: the Ni SAs (only Ni O coordination) were obtained below 450 °C, and the Ni Ni coordination appears and increases gradually with the rise of the reduction temperature. The selective poisoning experiment, kinetic isotope effect (KIE), in situ FT-IR measurement and DFT calculation reveal the synergistic effect between metal Ni SAs and acid–base sites toward CTH of CAL. Specifically, the Ni SAs play a crucial role in dehydrogenation reaction of 2-propanol (2-POL) to supply activated H, the base sites induce α-C H cleavage in 2-POL (the rate-determining step), and the Lewis acid sites serve as the active center for C O adsorption in CAL molecule. This work demonstrates a synergetic effect between Ni SAs and acid–base sites, which would pave the way in the rational design and synthesis of high-performance SAs materials used in CTH reactions.

Summary A “face-on” molecular orientation is essential for photovoltaic materials with efficient vertical carrier transport, but understanding how the molecular structures control their orientations remains challenging. Based on a ladder-type fused-ring core without sp3-hybridized bridging atoms, novel acceptor-donor-acceptor (A-D-A or ADA)-type nonfullerene acceptors (M3 and M32) are developed, and their molecular orientation behaviors are successfully controlled by the neighboring side chains. With linear n-cetyl chains on the nitrogen atoms, the acceptor (M32) tends to adopt an “edge-on” molecular orientation, whereas with bulky branched 2-hexyldecyl chains, the acceptor (M3) has a preferred “face-on” orientation. Blended with a donor polymer of PM6, M3 shows optimal phase separation and dramatically improved electron transport, consequently leading to a much higher device performance than M32. Further optimization of the M3-based devices yields an outstanding efficiency of 16.66%. The strategy of molecular orientation control proposed here will inspire many other innovative designs and syntheses of high-performance nonfullerene acceptors.

Density functional theory (DFT) calculations are carried out to investigate the effect of point defects on acetylene hydrogenation reaction over Ni(111) surface with three different defect concentrations (DC = 0.0500, 0.0625, and 0.0833), compared with the perfect Ni(111) surface. The adsorptions of C2 species and H atoms and the mechanism of acetylene hydrogenation via the ethylene pathway are systematically analyzed. The results indicate that the existence of defects will make C2 species and H atoms more inclined to adsorb near the defects. Introducing an appropriate amount of point defect concentration can enhance the catalytic activity and ethylene selectivity of Ni. In this work, DC = 0.0625 Ni(111) surface has the highest catalytic activity and selectivity of ethylene. This work provides useful theoretical information on the effect of defects on acetylene hydrogenation and is helpful for the design of Ni and related metal catalysts with defects.

Bronchopleural fistula is a serious and fatal complication after lobectomy. Fistula and hydropneumothorax are typical features of the disease. A 27-year-old man underwent right lower lobectomy and was diagnosed with bronchopleural fistula on the 37th day after operation. CT showed massive hydropneumothorax leading to severe atelectasis. He was undergone interventional implantation technique of two thoracic catheters and continuous negative pressure drainage. No complications were found during puncture and drainage. After 1 month of interventional treatment, the hydropneumothorax basically disappeared and the drainage catheters were removed. Herein, we highlight the new technique of thoracic puncture and implantation and continuous negative pressure drainage based on interventional technique is reported for the first time. For bronchopleural fistula complicated with massive hydropneumothorax leading to such serious atelectasis., the interventional technique is a potential economic and effective method.

Major obstacles in immunotherapies include toxicities associated with systemic administration of therapeutic agents, as well as low tumor lymphocyte infiltration that hampers the efficacies. In this study, we report a mesenchymal stem cell (MSC)-based immunotherapeutic strategy in which MSCs specifically deliver T/natural killer (NK) cell-targeting chemokine CXCL9 and immunostimulatory factor OX40 ligand (OX40L)/tumor necrosis factor superfamily member 4 (TNFSF4) to tumor sites in syngeneic subcutaneous and azoxymethane (AOM)/dextran sulfate sodium (DSS)-induced spontaneous colon cancer mouse models. This approach generated potent local antitumor immunity by increasing the ratios of tumor-infiltrating CD8(+) T and NK cells and production of antitumor cytokines and cytolytic proteins in the tumor microenvironment. Moreover, it improved the efficacy of programmed death-1 (PD-1) blockade in a syngeneic mouse model and significantly suppressed the growth of major histocompatibility complex class I (MHC class I)-deficient tumors. Our MSC-based immunotherapeutic strategy simultaneously recruits and activates immune effector cells at the tumor site, thus overcoming the problems with toxicities of systemic therapeutic agents and low lymphocyte infiltration of solid tumors.

Photonic hyperentanglement, which involves photons simultaneously entangled in more than one degree of freedom (DOF), has many important applications in quantum information processing, especially in high-capacity quantum communications. Interestingly, single-photon qubits encoded in the time-bin DOF are robust for long-distance transmissions in noisy channels. In this paper, we present a hyperentangled-Bell-state generation (HBSG) scheme for preparing two-photon six-qubit states which are simultaneously entangled in the polarization, spatial-mode, and time-bin DOFs. Compared with previous HBSG schemes, we construct an error-detected circuit unit with a quantum-dot (QD) spin in a double-sided optical microcavity, with which errors due to imperfect interactions between photons and QD systems can be easily detected, so that the error-detected circuit unit can relax the experimental requirement and improve the fidelity of our scheme largely. Meanwhile, our scheme is used to prepare two-photon hyperentangled states in polarization-spatial-time three DOFs, which is significant for faithful entanglement distribution and quantum repeater. These features make our scheme more feasible and useful in high-capacity and long-distance quantum communications with hyperentanglement.

Nonfullerene acceptors are being investigated for use in polymer solar cells (PSCs), with their advantages of extending the absorption range, reducing the energy loss and therefore enhancing the power conversion efficiency (PCE). However, to further boost the PCE, mobilities of these nonfullerene acceptors should be improved. For nonfullerene acceptors, the π–π stacking distance between cofacially stacked molecules significantly affects their mobility. Here, we demonstrate a strategy to increase the mobility of heteroheptacene-based nonfullerene acceptors by reducing their π–π stacking distances via control over the bulkiness of lateral side chains. Incorporation of 2-butyloctyl substituents into the nonfullerene acceptor (M36) leads to an increased mobility with a reduced π–π stacking distance of 3.45 Å. Consequently, M36 affords an enhanced PCE of 16%, which is the highest among all acceptor-donor-acceptor-type nonfullerene acceptors to date. This strategy of control over the bulkiness of side chains on nonfullerene acceptors should aid the development of more efficient PSCs.

The surface structures at catalytic sites are critical factors for determining catalytic selectivity. Here we use periodic density functional theory and microkinetic modeling to systematically inve...

Dysregulation of Wnt/β-catenin signaling is frequently observed in human gastric cancer. Elucidation of the tumor immune microenvironment is essential for understanding tumorigenesis and for the development of immunotherapeutic strategies. However, it remains unclear how β-catenin signaling regulates the tumor immune microenvironment in the stomach. Here, we identify CCL28 as a direct transcriptional target gene of β-catenin/T-cell factor (TCF). Protein levels of β-catenin and CCL28 positively correlated in human gastric adenocarcinoma. β-Catenin–activated CCL28 recruited regulatory T (Treg) cells in a transwell migration assay. In a clinically relevant mouse gastric cancer model established by Helicobacter (H.) felis infection and N-methyl-N-nitrosourea (MNU) treatment, inhibition of β-catenin/TCF activity by a pharmacologic inhibitor iCRT14 suppressed CCL28 expression and Treg cell infiltration in the stomach. Moreover, an anti-CCL28 antibody attenuated Treg cell infiltration and tumor progression in H. felis/MNU mouse models. Diphtheria toxin–induced Treg cell ablation restrained gastric cancer progression in H. felis/MNU-treated DEREG (Foxp3-DTR) mice, clarifying the tumor-promoting role of Treg cells. Thus, the β-catenin–CCL28–Treg cell axis may serve as an important mechanism for immunosuppression of the stomach tumor microenvironment. Our findings reveal an immunoregulatory role of β-catenin signaling in stomach tumors and highlight the therapeutic potential of CCL28 blockade for the treatment of gastric cancer. Significance: These findings demonstrate an immunosuppressive role of tumor-intrinsic β-catenin signaling and the therapeutic potential of CCL28 blockade in gastric cancer.

The introduction of light elements has received considerable attention to improve the efficiency of Ni-based catalysts toward the water gas shift (WGS) reaction, but an understanding of the role of...