The synthesis strategy, structural characteristics and stability, proton conducting features and mechanism of COFs in the past five years were fully reviewed. Future design ideas, research priorities ...and application prospects for such promising COFs are highlighted.
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•Proton conductive covalent organic frameworks were reviewed.•COFs are classified and described according to the type of linkages.•Proton conductivity and conducting mechanism were discussed.•The future development trend of such COFs is prospected.
As a new class of promising crystalline solid materials, the preparation and application of covalent organic frameworks (COFs) have aroused great interest in recent years. In this review, we will focus on the recent research achievements of COFs in the field of proton conductivity from the aspects of design strategies, structural characteristics, proton conducting features and mechanism, application research, etc. Finally, we will present a forward-looking view on the future development and challenges of such functional materials as well as preparation techniques and strategies.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
The design on synthesizing a sturdy, low‐cost, clean, and sustainable electrocatalyst, as well as achieving high performance with low overpotential and good durability toward water splitting, is ...fairly vital in environmental and energy‐related subject. Herein, for the first time the growth of sulfur (S) defect engineered self‐supporting array electrode composed of metallic Re and ReS2 nanosheets on carbon cloth (referred as Re/ReS2/CC) via a facile hydrothermal method and the following thermal treatment with H2/N2 flow is reported. It is expected that, for example, the as‐prepared Re/ReS2‐7H/CC for the electrocatalytic hydrogen evolution reaction (HER) under acidic medium affords a quite low overpotential of 42 mV to achieve a current density of 10 mA cm−2 and a very small Tafel slope of 36 mV decade−1, which are comparable to some of the promising HER catalysts. Furthermore, in the two‐electrode system, a small cell voltage of 1.30 V is recorded under alkaline condition. Characterizations and density functional theory results expound that the introduced S defects in Re/ReS2‐7H/CC can offer abundant active sites to advantageously capture electron, enhance the electron transport capacity, and weaken the adsorption free energy of H* at the active sites, being responsible for its superior electrocatalytic performance.
The S‐defect‐rich ReS2/CC electrocatalyst for highly efficient hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is constructed. The as‐prepared Re/ReS2‐7H/CC affords the overpotentials of 44 and 290 mV at 10 mA cm−2 under alkaline condition for HER and OER, respectively, a small cell voltage of 1.30 V in alkaline medium in the two‐electrode system, which are superior to pristine ReS2/CC.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Oxygen‐redox of layer‐structured metal‐oxide cathodes has drawn great attention as an effective approach to break through the bottleneck of their capacity limit. However, reversible oxygen‐redox can ...only be obtained in the high‐voltage region (usually over 3.5 V) in current metal‐oxide cathodes. Here, we realize reversible oxygen‐redox in a wide voltage range of 1.5–4.5 V in a P2‐layered Na0.7Mg0.2Fe0.2Mn0.6□0.2O2 cathode material, where intrinsic vacancies are located in transition‐metal (TM) sites and Mg‐ions are located in Na sites. Mg‐ions in the Na layer serve as “pillars” to stabilize the layered structure during electrochemical cycling, especially in the high‐voltage region. Intrinsic vacancies in the TM layer create the local configurations of “□–O–□”, “Na–O–□” and “Mg–O–□” to trigger oxygen‐redox in the whole voltage range of charge–discharge. Time‐resolved techniques demonstrate that the P2 phase is well maintained in a wide potential window range of 1.5–4.5 V even at 10 C. It is revealed that charge compensation from Mn‐ and O‐ions contributes to the whole voltage range of 1.5–4.5 V, while the redox of Fe‐ions only contributes to the high‐voltage region of 3.0–4.5 V. The orphaned electrons in the nonbonding 2p orbitals of O that point toward TM‐vacancy sites are responsible for reversible oxygen‐redox, and Mg‐ions in Na sites suppress oxygen release effectively.
Na0.7Mg0.2Fe0.2Mn0.6□0.2O2 with native transitional metal (TM) vacancies is designed as a novel cathode material for sodium‐ion batteries. The TM vacancies lead to nonbonding O 2p orbitals in this material, pointing toward these vacancies triggering reversible whole‐voltage‐range oxygen redox during charge and discharge processes. This work provides new ideals for design of cathode materials in anionic redox chemistry.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Herein, we report a method for C3-selective C–H tri- and difluoromethylthiolation of pyridines. The method relies on borane-catalyzed pyridine hydroboration for generation of nucleophilic ...dihydropyridines; these intermediates react with trifluoromethylthio and difluoromethylthio electrophiles to form functionalized dihydropyridines, which then undergo oxidative aromatization. The method can be used for late-stage functionalization of pyridine drugs for the generation of new drug candidates.
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IJS, KILJ, NUK, PNG, UL, UM
Designing highly active and more durable oxygen electrocatalysts for regenerative metal-air batteries and water splitting is of practical significance. Herein, an advanced Co/N–C-800 catalyst ...composed of abundant Co–N x structures and carbon defects derived from cobalt phthalocyanine is synthesized. Remarkably, this catalyst exhibits favorable catalytic performance toward the oxygen evolution reaction (OER) with a receivable overpotential of 274 mV in an alkaline medium achieving a current density of 10 mA cm–2 and a Tafel slope of 43.6 mV decade–1, outperforming the commercial RuO2 catalyst. It further displays a high half-wave potential (0.82 V) for the oxygen reduction reaction in 0.1 M KOH. Theoretical calculations reveal that the Co–N x active sites along with the carbon defects can decrease the adsorption energy of intermediates (OH*, O*, and OOH*) and enhance the electron-transfer ability, thus boosting the OER process.
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IJS, KILJ, NUK, PNG, UL, UM
IMPORTANCE: Among all subtypes of breast cancer, triple-negative breast cancer has a relatively high relapse rate and poor outcome after standard treatment. Effective strategies to reduce the risk of ...relapse and death are needed. OBJECTIVE: To evaluate the efficacy and adverse effects of low-dose capecitabine maintenance after standard adjuvant chemotherapy in early-stage triple-negative breast cancer. DESIGN, SETTING, AND PARTICIPANTS: Randomized clinical trial conducted at 13 academic centers and clinical sites in China from April 2010 to December 2016 and final date of follow-up was April 30, 2020. Patients (n = 443) had early-stage triple-negative breast cancer and had completed standard adjuvant chemotherapy. INTERVENTIONS: Eligible patients were randomized 1:1 to receive capecitabine (n = 222) at a dose of 650 mg/m2 twice a day by mouth for 1 year without interruption or to observation (n = 221) after completion of standard adjuvant chemotherapy. MAIN OUTCOMES AND MEASURES: The primary end point was disease-free survival. Secondary end points included distant disease-free survival, overall survival, locoregional recurrence-free survival, and adverse events. RESULTS: Among 443 women who were randomized, 434 were included in the full analysis set (mean SD age, 46 9.9 years; T1/T2 stage, 93.1%; node-negative, 61.8%) (98.0% completed the trial). After a median follow-up of 61 months (interquartile range, 44-82), 94 events were observed, including 38 events (37 recurrences and 32 deaths) in the capecitabine group and 56 events (56 recurrences and 40 deaths) in the observation group. The estimated 5-year disease-free survival was 82.8% in the capecitabine group and 73.0% in the observation group (hazard ratio HR for risk of recurrence or death, 0.64 95% CI, 0.42-0.95; P = .03). In the capecitabine group vs the observation group, the estimated 5-year distant disease-free survival was 85.8% vs 75.8% (HR for risk of distant metastasis or death, 0.60 95% CI, 0.38-0.92; P = .02), the estimated 5-year overall survival was 85.5% vs 81.3% (HR for risk of death, 0.75 95% CI, 0.47-1.19; P = .22), and the estimated 5-year locoregional recurrence-free survival was 85.0% vs 80.8% (HR for risk of locoregional recurrence or death, 0.72 95% CI, 0.46-1.13; P = .15). The most common capecitabine-related adverse event was hand-foot syndrome (45.2%), with 7.7% of patients experiencing a grade 3 event. CONCLUSIONS AND RELEVANCE: Among women with early-stage triple-negative breast cancer who received standard adjuvant treatment, low-dose capecitabine maintenance therapy for 1 year, compared with observation, resulted in significantly improved 5-year disease-free survival. TRIAL REGISTRATION: ClinicalTrials.gov Identifier: NCT01112826
Rational design hybrid nanostructure photocatalysts with efficient charge separation and transfer, and good solar light harvesting ability have critical significance for achieving high ...solar‐to‐chemical conversion efficiency. Here a highly active and stable composite photocatalyst is reported by integrating ultrathin ZnIn2S4 nanosheets on surface of hollow CdS cube to form the cube‐in‐cube structure. Experimental results combined with density functional theory calculations confirm that the Z‐scheme ZnIn2S4/CdS heterojunction is formed, which highly boosts the charge separation and transfer under the local‐electric‐field at semiconductor/semiconductor interface, and thus prolongs their lifetimes. Moreover, such a structure affords the highly enhanced light‐harvesting property. The optimized ZnIn2S4/CdS nanohybrids exhibit superior H2 generation rate under visible‐light irradiation (λ ≥ 420 nm) with excellent photochemical stability during 20 h continuous operation.
The stable composite photocatalyst integrated by ultrathin ZnIn2S4 nanosheets on surface of hollow CdS exhibits outstanding visible‐light‐driven photocatalytic H2 generation activity, due to that: i) the Z‐scheme charge transfer route facilitates charge separation, prolongs carrier lifetimes, and remains strong electron reduction capacity; ii) the unique cube‐in‐cube structure brings abundant active sites, improves light harvesting ability, shortens charge transfer distance.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Designing an architecture with the ability to temporarily capture one kind of charge carrier has a critical role to play in enhancing the performance of photocatalytic reactions. Here, we report that ...SrTiO3 nanofibers that have been treated with a brief method of H2 calcination in an H2/N2 atmosphere (denoted as STO-NH) form oxygen vacancies (OVs) and achieve significant improvement in performance in photocatalytic H2 production without the presence of cocatalysts. These OVs can trap photogenerated electrons, which inhibits the recombination of electrons and holes in both the surface and the bulk, thus improving the photocatalytic decomposition of water. Moreover, the concentration of surface OVs in STO-NH presents volcanic characteristics: the increase with rise in hydrogenation temperature, with a consequent increase in catalytic activity, indicates well-controlled formation of OVs. The existence and concentration of the OVs in STO-NH photocatalysts are investigated qualitatively through electron paramagnetic resonance, high-resolution transmission electron microscope and photoluminescence emission spectra. A reasonable photocatalytic mechanism is proposed that we expect to be able to provide significant guidance for future study.
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•Integration of S-scheme/Schottky junctions and oxygen vacancies on SrTiO3 is constructed.•Formed junctions enable the transfer of charges with direction.•Designed hybrid dramatically ...improves photocatalytic H2 evolution activity.•Large-scale photocatalytic device (20 cm × 20 cm) is successfully demonstrated.
The interfacial design and defect engineering are of huge interest for achieving efficient photocatalytic H2 evolution using solar energy. In this work, we successfully integrated the Schottky junction and S-scheme heterojunction with oxygen vacancies to achieve the defective Ru/SrTiO3/TiO2 hybrid photocatalyst. As verified by experimental studies, these junctions with defects fully exploit the benefits of interfacial charge separation and transport. It is demonstrated that the designed hybrid exhibits dramatically enhanced photocatalytic H2 evolution rate with respect to pristine SrTiO3, high apparent quantum efficiency at 365 nm irradiation as well as excellent stability. Furthermore, the Ru/SrTiO3/TiO2 based device photocatalyst also displays the excellent H2 evolution activity with easy recycle nature. This finding provides a newfangled thought for developing highly efficient hybrid materials for photocatalytic H2 evolution.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Galectin-10 (Gal-10) forms Charcot-Leyden crystals (CLCs), which play a key role in the symptoms of asthma and allergies and some other diseases. Gal-10 has a carbohydrate-binding site; however, ...neither the Gal-10 dimer nor the CLCs can bind sugars. To investigate the monomer-dimer equilibrium of Gal-10, high-performance size-exclusion chromatography (SEC) was employed to separate serial dilutions of Gal-10 with and without carbohydrates. We found that both the dimerization and crystallization of Gal-10 were promoted by lactose/galactose binding. A peak position shift for the monomer was observed after treatment with either lactose or galactose, implying that the polarity of the monomer was reduced by lactose/galactose binding. Further experiments indicated that alkaline conditions of pH 8.8 mimicked the lactose/galactose-binding environment, and the time interval between monomers and dimers in the chromatogram decreased from 0.8 min to 0.4 min. Subsequently, the electrostatic potential of the Gal-10 monomers was computed. After lactose/galactose binding, the top side of the monomer shifted from negatively charged to electrically neutral, allowing it to interact with the carbohydrate-binding site of the opposing subunit during dimerization. Since lactose/galactose promotes the crystallization of Gal-10, our findings implied that dairy-free diets (free of lactose/galactose) might be beneficial to patients with CLC-related diseases.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
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