Transition metal (TM)‐based bimetallic spinel oxides can efficiently activate peroxymonosulfate (PMS) presumably attributed to enhanced electron transfer between TMs, but the existing model cannot ...fully explain the efficient TM redox cycling. Here, we discover a critical role of TM−O covalency in governing the intrinsic catalytic activity of Co3−xMnxO4 spinel oxides. Experimental and theoretical analysis reveals that the Co sites significantly raises the Mn valence and enlarges Mn−O covalency in octahedral configuration, thereby lowering the charge transfer energy to favor MnOh–PMS interaction. With appropriate MnIV/MnIII ratio to balance PMS adsorption and MnIV reduction, the Co1.1Mn1.9O4 exhibits remarkable catalytic activities for PMS activation and pollutant degradation, outperforming all the reported TM spinel oxides. The improved understandings on the origins of spinel oxides activity for PMS activation may inspire the development of more active and robust metal oxide catalysts.
The Mn−O covalency was enlarged by the Co sites mainly in the octahedral configuration, which results in a decreased charge transfer energy to favor Mn–PMS interaction and enhance MnIV reduction to boost PMS activation activity of Co‐Mn spinel oxides.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Accurately distinguishing between enantiomeric molecules is a fundamental challenge in the field of chemistry. However, there is still significant room for improvement in both the enantiomeric ...selectivity (KR(S)/KS(R)) and binding strength of most reported macrocyclic chiral receptors to meet the demands of practical application scenarios. Herein, we synthesized a water‐soluble conjugated tubular host—namely, corral4BINOL—using a chiral 1,1′‐bi‐2‐naphthol (BINOL) derivative as the repeating unit. The conjugated chiral backbone endows corral4BINOL with good fluorescent emission (QY=34 % ) and circularly polarized luminescence (|glum| up to 1.4×10−3) in water. Notably, corral4BINOL exhibits high recognition affinity up to 8.6×1010 M−1 towards achiral guests in water, and manifested excellent enantioselectivity up to 18.7 towards chiral substrates, both of which represent the highest values observed among chiral macrocycles in aqueous solution. The ultrastrong binding strength, outstanding enantioselectivity, and facile accessibility, together with the superior fluorescent and chiroptical properties, endow corral4BINOL with great potential for a wide range of applications.
A pair of water‐soluble enantiomeric macrocycles was prepared using a chiral 1,1′‐bi‐2‐naphthol derivative as the building unit. The conjugated backbone results in the macrocycles having attractive chiral emissive properties, exceptional recognition affinity (up to 1010 M−1) and excellent enantioselectivity (up to 18.7) in water.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
The exploitation of highly efficient carbon dioxide reduction (CO2RR) electrocatalyst for methane (CH4) electrosynthesis has attracted great attention for the intermittent renewable electricity ...storage but remains challenging. Here, N‐heterocyclic carbene (NHC)‐ligated copper single atom site (Cu SAS) embedded in metal–organic framework is reported (2Bn‐Cu@UiO‐67), which can achieve an outstanding Faradaic efficiency (FE) of 81 % for the CO2 reduction to CH4 at −1.5 V vs. RHE with a current density of 420 mA cm−2. The CH4 FE of our catalyst remains above 70 % within a wide potential range and achieves an unprecedented turnover frequency (TOF) of 16.3 s−1. The σ donation of NHC enriches the surface electron density of Cu SAS and promotes the preferential adsorption of CHO* intermediates. The porosity of the catalyst facilitates the diffusion of CO2 to 2Bn‐Cu, significantly increasing the availability of each catalytic center.
A catalyst with N‐heterocyclic carbene‐ligated Cu SAS as the active site, accompanied by many micro‐nano reactors, synergistically promotes the electrochemical synthesis of methane.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Indoor detection of volatile organic compounds (VOCs) concentration is necessary due to the serious toxicity hazards even at trace level. However, physisorbents usually exhibit weak interactions ...especially in the presence of trace concentrations of VOCs, thus exhibiting poor responsive signal. Herein, we report a new flexible metal–organic framework (MOF) that exhibits interesting pore‐opening behavior after immersing in H2O. The pore‐opening phase shows significant (≈116 folds) and extremely fast (<1 minute) fluorescence enhancement after being exposed to saturated benzene vapor. The limit of detection concentration for benzene vapor can be calculated as 0.133 mg L−1. Thus this material represents the first MOF to achieve visual detection of trace benzene vapor by the naked eyes. Theoretical calculations and single‐crystal structure reveal that the special “bilateral π–π stacking” interactions between the host and guest, which facilitate electron transfer and greatly enhance the intensity of fluorescence.
A new flexible metal–organic framework (MOF) exhibits significant and sensitive fluorescence “turn‐on” behavior for benzene vapor by virtue of unique “bilateral π–π stacking” interactions, enabling visual detection of a trace level of benzene for the first time.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Many protein‐coding oncofetal genes are highly expressed in murine and human fetal liver and silenced in adult liver. The protein products of these hepatic oncofetal genes have been used as clinical ...markers for the recurrence of hepatocellular carcinoma (HCC) and as therapeutic targets for HCC. Herein we examined the expression profiles of long noncoding RNAs (lncRNAs) found in fetal and adult liver in mice. Many fetal hepatic lncRNAs were identified; one of these, lncRNA‐mPvt1, is an oncofetal RNA that was found to promote cell proliferation, cell cycling, and the expression of stem cell‐like properties of murine cells. Interestingly, we found that human lncRNA‐hPVT1 was up‐regulated in HCC tissues and that patients with higher lncRNA‐hPVT1 expression had a poor clinical prognosis. The protumorigenic effects of lncRNA‐hPVT1 on cell proliferation, cell cycling, and stem cell‐like properties of HCC cells were confirmed both in vitro and in vivo by gain‐of‐function and loss‐of‐function experiments. Moreover, mRNA expression profile data showed that lncRNA‐hPVT1 up‐regulated a series of cell cycle genes in SMMC‐7721 cells. By RNA pulldown and mass spectrum experiments, we identified NOP2 as an RNA‐binding protein that binds to lncRNA‐hPVT1. We confirmed that lncRNA‐hPVT1 up‐regulated NOP2 by enhancing the stability of NOP2 proteins and that lncRNA‐hPVT1 function depends on the presence of NOP2. Conclusion: Our study demonstrates that the expression of many lncRNAs is up‐regulated in early liver development and that the fetal liver can be used to search for new diagnostic markers for HCC. LncRNA‐hPVT1 promotes cell proliferation, cell cycling, and the acquisition of stem cell‐like properties in HCC cells by stabilizing NOP2 protein. Regulation of the lncRNA‐hPVT1/NOP2 pathway may have beneficial effects on the treatment of HCC. (Hepatology 2014;60:1278–1290)
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Arranging ionic liquids (ILs) with long‐range order can not only enhance their performance in a desired application, but can also help elucidate the vital between structure and properties. However, ...this is still a challenge and no example has been reported to date. Herein, we report a feasible strategy to achieve a crystalline IL via coordination self‐assembly based reticular chemistry. IL1MOF, was prepared by designing an IL bridging ligand and then connecting them with metal clusters. IL1MOF has a unique structure, where the IL ligands are arranged on a long‐range ordered framework but have a labile ionic center. This structure enables IL1MOF to break through the typical limitation where the solid ILs have lower proton conductivity than their counterpart bulk ILs. IL1MOF shows 2–4 orders of magnitude higher proton conductivity than its counterpart IL monomer across a wide temperature range. Moreover, by confining the IL within ultramicropores (<1 nm), IL1MOF suppresses the liquid–solid phase transition temperatures to lower than −150 °C, allowing it to function with high conductivity in a subzero temperature range.
A reticular chemistry based strategy opens a facile toolbox for designing liquid molecules with long‐rang‐ordered framework of MOF. IL1MOF is the first crystalline ionic liquid (IL) combining a balance of good mechanical properties and high conductivity. It expands the use of IL electrolytes to an low temperature region.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
The laurel family within the Magnoliids has attracted attentions owing to its scents, variable inflorescences, and controversial phylogenetic position. Here, we present a chromosome-level assembly of ...the Litsea cubeba genome, together with low-coverage genomic and transcriptomic data for many other Lauraceae. Phylogenomic analyses show phylogenetic discordance at the position of Magnoliids, suggesting incomplete lineage sorting during the divergence of monocots, eudicots, and Magnoliids. An ancient whole-genome duplication (WGD) event occurred just before the divergence of Laurales and Magnoliales; subsequently, independent WGDs occurred almost simultaneously in the three Lauralean lineages. The phylogenetic relationships within Lauraceae correspond to the divergence of inflorescences, as evidenced by the phylogeny of FUWA, a conserved gene involved in determining panicle architecture in Lauraceae. Monoterpene synthases responsible for production of specific volatile compounds in Lauraceae are functionally verified. Our work sheds light on the evolution of the Lauraceae, the genetic basis for floral evolution and specific scents.
Near‐infrared organic light‐emitting diodes (NIR OLEDs) enable many unique applications ranging from night‐vision displays and photodynamic therapies. However, the development of efficient NIR OLEDs ...with a low efficiency roll‐off is still challenging. Here, a series of new heteroleptic Pt(II) complexes (1–4) flanked by both pyridyl pyrimidinate and functional azolate chelates are synthesized. The reduced ππ* energy gap of the pyridyl pyrimidinate chelate, and strong intermolecular interaction and high crystallinity in vacuum‐deposited thin films engender strong intermolecular charge transfer transition including metal–metal‐to‐ligand charge transfer; thereby, exhibiting efficient photoluminescence within 776–832 nm and short radiative lifetimes of 0.52–0.79 µs. Consequently, nondoped NIR‐emitting OLEDs based on these Pt(II) complexes are fabricated, to which Pt(II) complexes 2 and 4 give record high maximum external quantum efficiency of 10.61% at 794 nm and 9.58% at 803 nm, respectively. Moreover, low efficiency roll‐off is also observed, among which the device efficiencies of 2 and 4 are at least four times higher than that of the best NIR‐emitting OLEDs recorded at current density of 100 mA cm−2.
Nondoped near‐infrared organic light‐emitting diodes based on pyrimidinate‐pyrazolate Pt(II) metal complexes 2 and 4 are fabricated, yielding a record high maximum external quantum efficiency of 10.61% at 794 nm and 9.58% at 803 nm, respectively.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Blockade of the protein–protein interaction between the transmembrane protein programmed cell death protein 1 (PD‐1) and its ligand PD‐L1 has emerged as a promising immunotherapy for treating ...cancers. Using the technology of mirror‐image phage display, we developed the first hydrolysis‐resistant D‐peptide antagonists to target the PD‐1/PD‐L1 pathway. The optimized compound DPPA‐1 could bind PD‐L1 at an affinity of 0.51 μM in vitro. A blockade assay at the cellular level and tumor‐bearing mice experiments indicated that DPPA‐1 could also effectively disrupt the PD‐1/PD‐L1 interaction in vivo. Thus D‐peptide antagonists may provide novel low‐molecular‐weight drug candidates for cancer immunotherapy.
Protein chemical synthesis and mirror‐image phage display were combined to develop a proteolysis‐resistant D‐peptide antagonist (DPPA‐1) which targets the immune checkpoint protein PD‐L1 (the ligand for PD‐1, the programmed cell death protein 1). DPPA‐1 was found to inhibit the PD‐1/PD‐L1 protein–protein interaction at the cellular level. IgV=immunoglobulin‐like variable.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Nasopharyngeal carcinoma (NPC) is an aggressive malignancy with extremely skewed ethnic and geographic distributions. Increasing evidence indicates that targeting the tumor microenvironment (TME) ...represents a promising therapeutic approach in NPC, highlighting an urgent need to deepen the understanding of the complex NPC TME. Here, we generated single-cell transcriptome profiles for 7581 malignant cells and 40,285 immune cells from fifteen primary NPC tumors and one normal sample. We revealed malignant signatures capturing intratumoral transcriptional heterogeneity and predicting aggressiveness of malignant cells. Diverse immune cell subtypes were identified, including novel subtypes such as CLEC9A
dendritic cells (DCs). We further revealed transcriptional regulators underlying immune cell diversity, and cell-cell interaction analyses highlighted promising immunotherapeutic targets in NPC. Moreover, we established the immune subtype-specific signatures, and demonstrated that the signatures of macrophages, plasmacytoid dendritic cells (pDCs), CLEC9A
DCs, natural killer (NK) cells, and plasma cells were significantly associated with improved survival outcomes in NPC. Taken together, our findings represent a unique resource providing in-depth insights into the cellular heterogeneity of NPC TME and highlight potential biomarkers for anticancer treatment and risk stratification, laying a new foundation for precision therapies in NPC.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
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