Single-atom catalysts not only maximize metal atom efficiency, they also display properties that are considerably different to their more conventional nanoparticle equivalents, making them a ...promising family of materials to investigate. Herein we developed a general host-guest strategy to fabricate various metal single-atom catalysts on nitrogen-doped carbon (M
/CN, M = Pt, Ir, Pd, Ru, Mo, Ga, Cu, Ni, Mn). The iridium variant Ir
/CN electrocatalyses the formic acid oxidation reaction with a mass activity of 12.9 Formula: see text whereas an Ir/C nanoparticle catalyst is almost inert (~4.8 × 10
Formula: see text). The activity of Ir
/CN is also 16 and 19 times greater than those of Pd/C and Pt/C, respectively. Furthermore, Ir
/CN displays high tolerance to CO poisoning. First-principle density functional theory reveals that the properties of Ir
/CN stem from the spatial isolation of iridium sites and from the modified electronic structure of iridium with respect to a conventional nanoparticle catalyst.
High‐temperature dielectric polymers are in constant demand for the multitude of high‐power electronic devices employed in hybrid vehicles, grid‐connected photovoltaic and wind power generation, to ...name a few. There is still a lack, however, of dielectric polymers that can work at high temperature (> 150 °C). Herein, a series of all‐organic dielectric polymer composites have been fabricated by blending the n‐type molecular semiconductor 1,4,5,8‐naphthalenetetracarboxylic dianhydride (NTCDA) with polyetherimide (PEI). Electron traps are created by the introduction of trace amounts of n‐type small molecule semiconductor NTCDA into PEI, which effectively reduces the leakage current and improves the breakdown strength and energy storage properties of the composite at high temperature. Especially, excellent energy storage performance is achieved in 0.5 vol.% NTCDA/PEI at the high temperatures of 150 and 200 °C, e.g., ultrahigh discharge energy density of 5.1 J cm−3 at 150 °C and 3.2 J cm−3 at 200 °C with high discharge efficiency of 85–90%, which is superior to its state‐of‐the‐art counterparts. This study provides a facile and effective strategy for the design of high‐temperature dielectric polymers for advanced electronic and electrical systems.
This study reports the novel all‐organic dielectric composite films of 1,4,5,8‐naphthalenetetracarboxylic dianhydride (NTCDA)/polyetherimide (PEI) by using a facile solution casting method. By judiciously introducing semiconducting NTCDA into PEI, electron traps are successfully constructed, effectively reducing the leakage current and improving the breakdown strength. Finally, excellent high‐temperature energy storage performance is achieved in 0.5 vol.% NTCDA/PEI at 150 and 200 °C.
Highly enantioselective 3+3 and 3+4 annulations of isatin‐derived enals with ethynylethylene carbonates and ethynyl benzoxazinanones are enabled by NHC/cooper cooperative catalysis, leading to a big ...library of spirooxindole derivatives in high structural diversity and enantioselectivity (up to 99 % ee). Both reactions represent a nicely synergistic integration of NHC and copper catalysis, in which both catalysts activate the substrates and the chiral NHC perfectly controls the stereochemistry.
All together now: A cooperative N‐heterocyclic carbene (NHC)/cooper catalytic system was developed for the diversity‐oriented synthesis of spirooxindole derivatives through enantioselective 3+3 and 3+4 annulation reactions. Highly enantioselective 3+3 and 3+4 annulations of isatin‐derived enals with ethynylethylene carbonates and ethynyl benzoxazinanones were achieved.
Summary Background The value of adding cisplatin, fluorouracil, and docetaxel (TPF) induction chemotherapy to concurrent chemoradiotherapy in locoregionally advanced nasopharyngeal carcinoma is ...unclear. We aimed to compare TPF induction chemotherapy plus concurrent chemoradiotherapy with concurrent chemoradiotherapy alone in a suitably powered trial. Methods We did an open-label, phase 3, multicentre, randomised controlled trial at ten institutions in China. Patients with previously untreated, stage III–IVB (except T3-4N0) nasopharyngeal carcinoma, aged 18–59 years without severe comorbidities were enrolled. Eligible patients were randomly assigned (1:1) to receive induction chemotherapy plus concurrent chemoradiotherapy or concurrent chemoradiotherapy alone (three cycles of 100 mg/m2 cisplatin every 3 weeks, concurrently with intensity-modulated radiotherapy). Induction chemotherapy was three cycles of intravenous docetaxel (60 mg/m2 on day 1), intravenous cisplatin (60 mg/m2 on day 1), and continuous intravenous fluorouracil (600 mg/m2 per day from day 1 to day 5) every 3 weeks before concurrent chemoradiotherapy. Randomisation was by a computer-generated random number code with a block size of four, stratified by treatment centre and disease stage (III or IV). Treatment allocation was not masked. The primary endpoint was failure-free survival calculated from randomisation to locoregional failure, distant failure, or death from any cause; required sample size was 476 patients (238 per group). We did efficacy analyses in our intention-to-treat population. The follow-up is ongoing; in this report, we present the 3-year survival results and acute toxic effects. This trial is registered with ClinicalTrials.gov , number NCT01245959. Findings Between March 1, 2011, and Aug 22, 2013, 241 patients were assigned to induction chemotherapy plus concurrent chemoradiotherapy and 239 to concurrent chemoradiotherapy alone. After a median follow-up of 45 months (IQR 38–49), 3-year failure-free survival was 80% (95% CI 75–85) in the induction chemotherapy plus concurrent chemoradiotherapy group and 72% (66–78) in the concurrent chemoradiotherapy alone group (hazard ratio 0·68, 95% CI 0·48–0·97; p=0·034). The most common grade 3 or 4 adverse events during treatment in the 239 patients in the induction chemotherapy plus concurrent chemoradiotherapy group versus the 238 patients in concurrent chemoradiotherapy alone group were neutropenia (101 42% vs 17 7%), leucopenia (98 41% vs 41 17%), and stomatitis (98 41% vs 84 35%). Interpretation Addition of TPF induction chemotherapy to concurrent chemoradiotherapy significantly improved failure-free survival in locoregionally advanced nasopharyngeal carcinoma with acceptable toxicity. Long-term follow-up is required to determine long-term efficacy and toxicities. Funding Shenzhen Main Luck Pharmaceuticals Inc, Sun Yat-sen University Clinical Research 5010 Program (2007037), National Science and Technology Pillar Program during the Twelfth Five-year Plan Period (2014BAI09B10), Health & Medical Collaborative Innovation Project of Guangzhou City (201400000001), Planned Science and Technology Project of Guangdong Province (2013B020400004), and The National Key Research and Development Program of China (2016YFC0902000).
The flexibility in structural design of organic semiconductors endows organic solar cells (OSCs) not only great function-tunabilities, but also high potential toward practical application. In this ...work, simple non-fused-ring electron acceptors are developed through two-step synthesis from single aromatic units for constructing efficient OSCs. With the assistance of non-covalent interactions, these rotatable non-fused acceptors (in solution) allow transiting into planar and stackable conformation in condensed solid, promoting acceptors not only feasible solution-processability, but also excellent film characteristics. As results, decent power conversion efficiencies of 10.27% and 13.97% can be achieved in single and tandem OSCs consisting of simple solution-cast blends, in which the fully unfused acceptors exhibit exceptionally low synthetic complexity index. In addition, the unfused acceptor and its based OSCs exhibit promising stabilities under continuous illumination. Overall, this work reveals valuable insights on the structural design of simple and effective electron acceptors with great practical perspectives.
Design and development of highly efficient photocatalytic materials are key to employ photocatalytic technology as a sound solution to energy and environment related challenges. This work aims to ...significantly boost photocatalytic activity through rich indium vacancies (VIn) In2S3 with atomic p–n homojunction through a one‐pot preparation strategy. Positron annihilation spectroscopy and electron paramagnetic resonance reveal existence of VIn in the prepared photocatalysts. Mott–Schottky plots and surface photovoltage spectra prove rich VIn In2S3 can form atomic p–n homojunction. It is validated that p–n homojunction can effectively separate carriers combined with photoelectrochemical tests. VIn decreases carrier transport activation energy (CTAE) from 0.64 eV of VIn‐poor In2S3 to 0.44 eV of VIn‐rich In2S3. The special structure endows defective In2S3 with multifunctional photocatalysis properties, i.e., hydrogen production (872.7 µmol g−1 h−1), degradation of methyl orange (20 min, 97%), and reduction in heavy metal ions Cr(VI) (30 min, 98%) under simulated sunlight, which outperforms a variety of existing In2S3 composite catalysts. Therefore, such a compositional strategy and mechanistic study are expected to offer new insights for designing highly efficient photocatalysts through defect engineering.
Rich indium vacancies (VIn) In2S3 are constructed with atomic p–n homojunction for boosting photocatalytic multifunctional properties. The formation of defects and atomic p–n homojunction accelerates carrier separation and migration efficiency. Therefore, such a compositional strategy offers new insights for designing highly efficient atomic p–n homojunction photocatalysts through defect engineering.
To report long‐term results of a randomized controlled trial that compared cisplatin/fluorouracil/docetaxel (TPF) induction chemotherapy (IC) plus concurrent chemoradiotherapy (CCRT) with CCRT alone ...in locoregionally advanced nasopharyngeal carcinoma (NPC). Patients with stage III–IVB (except T3–4 N0) NPC were randomly assigned to receive IC plus CCRT (n = 241) or CCRT alone (n = 239). IC included three cycles of docetaxel (60 mg/m2 d1), cisplatin (60 mg/m2 d1), and fluorouracil (600 mg/m2/d civ d1–5) every 3 weeks. Patients from both groups received intensity‐modulated radiotherapy concurrently with three cycles of 100 mg/m2 cisplatin every 3 weeks. After a median follow‐up of 71.5 months, the IC plus CCRT group showed significantly better 5‐year failure‐free survival (FFS, 77.4% vs. 66.4%, p = 0.019), overall survival (OS, 85.6% vs. 77.7%, p = 0.042), distant failure‐free survival (88% vs. 79.8%, p = 0.030), and locoregional failure‐free survival (90.7% vs. 83.8%, p = 0.044) compared to the CCRT alone group. Post hoc subgroup analyses revealed that beneficial effects on FFS were primarily observed in patients with N1, stage IVA, pretreatment lactate dehydrogenase ≥170 U/l, or pretreatment plasma Epstein–Barr virus DNA ≥6000 copies/mL. Two nomograms were further developed to predict the potential FFS and OS benefit of TPF IC. The incidence of grade 3 or 4 late toxicities was 8.8% (21/239) in the IC plus CCRT group and 9.2% (22/238) in the CCRT alone group. Long‐term follow‐up confirmed that TPF IC plus CCRT significantly improved survival in locoregionally advanced NPC with no marked increase in late toxicities and could be an option of treatment for these patients.
What's new?
Despite advances in the treatment of nasopharyngeal carcinoma, approximately 30% of high‐risk patients experience recurrence after treatment. Here the authors find that combining the conventional chemoradiotherapy with a triple induction chemotherapy (cisplatin/fluorouracil/docetaxel) prolonged survival of patients with locoregionally advanced cancer, even after more than 70 months of follow‐up. The combination treatment increased acute, but not late, toxicities, and the authors propose that it could present a new treatment option for this patient group.
Nasopharyngeal carcinoma (NPC) is a malignant epithelial tumor originating in the nasopharynx and has a high incidence in Southeast Asia and North Africa. To develop these comprehensive guidelines ...for the diagnosis and management of NPC, the Chinese Society of Clinical Oncology (CSCO) arranged a multi‐disciplinary team comprising of experts from all sub‐specialties of NPC to write, discuss, and revise the guidelines. Based on the findings of evidence‐based medicine in China and abroad, domestic experts have iteratively developed these guidelines to provide proper management of NPC. Overall, the guidelines describe the screening, clinical and pathological diagnosis, staging and risk assessment, therapies, and follow‐up of NPC, which aim to improve the management of NPC.
Aberrant mechanical properties and immunosuppression are the two key factors that limit the antitumor efficacy of T cell immune checkpoint blockade inhibitors, e.g., programmed cell death‐1 antibody ...(PD‐1 Ab), against solid tumors in the clinic. This study leverages hyperbaric oxygen (HBO) for the first time to address these two issues and reports the PD‐1‐Ab‐mediated immune responses against various stroma‐rich solid malignancies. The results demonstrate that HBO promoted PD‐1 Ab delivery and T cells infiltration into tumor parenchyma by depleting the extracellular matrix's main components, such as collagen and fibronectin. Furthermore, HBO disrupts hypoxia‐mediated immunosuppression and helps PD‐1 Ab trigger robust cytotoxic T lymphocytes and long‐lasting immunological memory to inhibit tumor relapses. Such enhanced immune responses are effective in solid tumors from rodents and the cancer cells from hepatocellular carcinoma patients. The results illustrate that HBO bolsters antitumor efficacy of PD‐1 Ab, and the HBO–PD‐1 Ab combination is a promising stroma‐rich solid tumors’ treatment in the clinic.
It is revealed that hyperbaric oxygen (HBO) depleted extracellular matrix's major components, including collagen and fibronectin, thereby promoting the delivery of PD‐1 Ab and the infiltration of T cell into tumor parenchyma. Furthermore, HBO disrupted hypoxia‐mediated immunosuppression and helped PD‐1 Ab trigger robust cytotoxic T lymphocytes and long‐lasting immunological memory effect for the inhibition of tumor relapses.
A novel and practical fluoroalkyl radical-initiated cascade reaction was developed to access diverse 2-fluoroalkylbenzothiazoles by reacting various fluoroalkyl radical sources, including ...perfluoroalkyl iodide (IC n F2n+1, n = 3–8, 10), ICF(CF3)2, ICF2COOEt, ICF2CF2Cl, or ICF2CF2Br, tetramethylethane-1,2-diamine (TMEDA), and 2-isocyanoaryl thioethers in tetrahydrofuran under nitrogen atmosphere and blue-light irradiation conditions. Furthermore, this one-pot protocol could well be expanded to access various 2-fluoroalkylbenzoselenazoles starting from (2-isocyanophenyl)(methyl)selane, perfluoroalkyl iodides (IC n F2n+1, n = 3–8) or ICF2COOEt and TMEDA.
PDF
