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Saline–alkaline (SA) stress is characterized by high salinity and high alkalinity (high pH), which severely inhibit plant growth and cause huge losses in crop yields worldwide. Here we show that a moderate elevation of endogenous abscisic acid (ABA) levels by RNAi-mediated suppression of OsABA8ox1 (OsABA8ox1-kd), a key ABA catabolic gene, significantly increased tolerance to SA stress in rice plants. We produced OsABA8ox1-kd lines in two different japonica cultivars, Dongdao 4 and Nipponbare. Compared with non-transgenic control plants (WT), the OsABA8ox1-kd seedlings accumulated 25.9%–55.7% higher levels of endogenous ABA and exhibited reduced plasmalemma injury, ROS accumulation and Na+/K+ ratio, and higher survival rates, under hydroponic alkaline conditions simulated by 10, 15, and 20 mmol L−1 of Na2CO3. In pot trials using SA field soils of different alkali levels (pH 7.59, 8.86, and 9.29), OsABA8ox1–kd plants showed markedly higher seedling survival rates and more vigorous plant growth, resulting in significantly higher yield components including panicle number (85.7%–128.6%), spikelets per panicle (36.9%–61.9%), branches (153.9%–236.7%), 1000–kernel weight (20.0%–28.6%), and percentage of filled spikelets (96.6%–1340.8%) at harvest time. Under severe SA soil conditions (pH = 9.29, EC = 834.4 μS cm−1), OsABA8ox1-kd lines showed an 194.5%–1090.8% increase in grain yield per plant relative to WT plants. These results suggest that suppression of OsABA8ox1 to increase endogenous ABA levels provides a new molecular approach for improving rice yield in SA paddies.

For this study, NiCrBSi–TiN composite coatings were fabricated on Q235 steel substrates by reactive plasma spraying and the coatings were heat treated at 600 °C, 700 °C, 750 °C and 800 °C for 1 hour. The microstructure evolution of these coatings untreated and treated at different temperatures was analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM) combined with energy dispersive spectroscopy (EDS) and transmission electron microscopy (TEM). The hardness of the coatings was characterised using the Weibull distribution while the wear and corrosion resistance were studied using a block-ring tribometer and an electrochemical workstation. The phase composition of coatings after heat treatment changed, the compactness of coatings was increased, and the interlayer bonding was significantly improved. Comprehensive experimental results illustrated that the performance of the NiCrBSi–TiN composite coatings was excellent at the heat treatment temperature of 700 °C.

Here, a simple, economical one-step doping strategy is adopted to prepare N, S co-doped graphene hollow spheres (NSGHS). The NSGHS exhibits remarkable oxygen-reduction-reaction (ORR) activity with a high half-wave potential (E1/2) of 0.847 V vs. RHE and considerable long-term stability. When applied as anode materials for sodium-ion batteries (SIBs), it could deliver a high reversible capacity of 385 mAh g−1 at 500 mA g−1, excellent rate performance of 308 mAh g−1 at even 20 A g−1 and superior cycling performance at 10 A g−1 during 5000 cycles with negligible capacity fade. DFT calculation reveals that the doping of N and S endows the surrounding carbon with high positive charge and spin density, respectively, making them be highly active ORR catalytic sites except for S itself. Despite the possible oxidization of C–S–C active sites, the rest C atoms of NSGHS will still hold a considerably high catalytic activity superior to those of mono-doped or undoped cases. In addition, S doping will improve the binding between Na and graphene substrate to get a high capacity and N doping effectively curbs the rising of oxygen levels and oxidization of S in C–S–C active sites, thus the excellent stability for ORR and SIBs. © 2021 Elsevier Ltd

Amorphous silica nanoparticles (ASiNPs) are generally considered to be biocompatible with limited acute toxicity. These nanoparticles were therefore exploited in diverse nanoproducts (e.g. foods and cosmetics) and may be released into environments in daily life. This has led to substantial concerns on their affects by long-term exposure. Herein, Raw264.7 cells were subjected to long-term exposure of ASiNPs for assessment of the potential cytotoxicity. Two ASiNPs with diameters of 50 ~ 100 nm (ASiNP1) and 450 ~ 500 nm (ASiNP2) were synthesized and comprehensively characterized. The acquired cells were denoted as Raw264.7-NP1 (ASiNP1 treatment) and Raw264.7-NP2 (ASiNP2 treatment) after long-term exposure. Both the small and large ASiNPs showed similar cellular distributions in lysosomes. We therefore examined the impacts of ASiNPs in lysosomal density, size and function by microscopy imaging and proteomics analysis. As a result, Raw264.7-NP1 cells displayed 2.3-fold higher lysosomal density and 149% increments of average lysosomal area than parent cells. Proteomics analysis of lysosomes revealed 25 significantly changed proteins closely relating to 5 cellular effects, including autophagy and lipid metabolism. Confocal imaging and immunoblotting of LC-3 proteins indicated an accumulation of autophagosomes in Raw264.7-NP1 cells. Elevation of cholesterol was also demonstrated in Raw264.7-NP1 cells by visualization and quantification of cellular cholesterols. Notably, the cholesterol elevation in Raw264.7-NP1 cells could be ameliorated by acceleration of autophagic flux (rapamycin treatment) but aggregated by blockage of autolysosome formation (chloroquine treatment), indicating the critical role of autophagic flux in lipid metabolism. Overall, the discovery of these hazard effects raised warnings for the long-term uses of ASiNP-based nanoproducts and may facilitate the decision making on environmental exposure thresholds of ASiNPs.

An effective decontamination method for soils remediation is a long-standing challenge. Herein, hydrogen peroxide (H2O2) was spontaneously produced in thin films generated by evaporating almost all the water. H2O2-sensitive test strips and oxidation of 2-hydroxybenzophenone to 2-hydroxyphenyl benzoate confirmed the generation of H2O2. Experiments in which reaction time and temperature were varied and established dependence of H2O2 production on the long-lasting thin films. H2O2 production was independence of irradiation and oxygen from air or dissolved oxygen. Spin-trapping probe experiments suggested that electric fields at the thin interfacial films enabled OH- to hydroxyl radicals and further recombination to H2O2. As a proof-of-principle experiment, perfluorooctanoic acid (PFOA) was effectively degraded on the thin films without catalysts and UV irradiation could further facilitate the degradation. A degradation mechanism was proposed involving the PFOA radicals on thin interfacial films and the subsequent decomposition of the radicals with successive loss of CF2. These findings have important implications for the development of decontamination method for soils remediation based on thin films, because thin film formats are ubiquitous at the surface of soils and when aerosols falling onto a substrate.

[Image: see text] CDK8 and its paralog CDK19 are cyclin-dependent kinases that are core components of the so-called Mediator complex that has essential roles as a positive and negative regulator of gene expression. Several efforts to develop inhibitors have yielded natural and synthetic ATP-competitive compounds including cortistatin A, Sel120, BCD-115, CCT251921 (1), and MSC2530818 (2). Here, we used a hybridization approach starting from CCT251921 and MSC2530818 to derive new inhibitors with the aim of developing highly potent and selective inhibitors of CDK8/19. Initial compounds suffered from rapid aldehyde oxidase-mediated metabolism. This liability was overcome by utilizing a pyrazolopyridine hinge binder with a chlorine at the C-3 position. These efforts resulted in JH-XVI-178 (compound 15), a highly potent and selective inhibitor of CDK8/19 that displays low clearance and moderate oral pharmacokinetic properties.

Drug development has a high failure rate, with safety properties constituting a considerable challenge. To reduce risk, in silico tools, including various machine learning methods, have been applied for toxicity prediction. However, these approaches often confront a serious problem: the training data sets are usually biased (imbalanced positive and negative samples), which would result in model training difficulty and unsatisfactory prediction accuracy. Multitask networks obtained significantly better predictive accuracies than single-task methods, and capsule neural networks showed excellent performance in sparse data sets in previous studies. In this study, we developed a new multitask framework based on a capsule neural network (multitask CapsNet) to measure 12 different toxic effects simultaneously. We found that multitask CapsNet excelled in toxicity prediction and outperformed many other computational approaches using the multitask strategy. Only after training on biased data sets did multitask CapsNet achieve significantly improved prediction accuracy on the Tox21 Data Challenge, which gave the largest ratio of highest accuracy (8/12) among compared models. Our model gave a prediction accuracy of 96.6% for the target NR.PPAR.gamma, whose ratio of negative to positive samples was up to 36:1. These results suggested that multitask CapsNet could overcome the bias problems and would provide a novel, accurate, and efficient approach for predicting the toxicities of compounds.

The aim of the current study was to investigate the anti-lung cancer effects of astragalin. Studies were also undertaken to evaluate its effects on apoptosis induction, ROS production, cellular migration and invasion and JAK/STAT3 signalling pathway. MTT assay was used to evaluate cell viability in NSCLC A549 cells after exposure to astragalin molecule. Apoptosis was investigated using AO/EB staining, comet assay and western blotting assay. Fluorescence microscopy was implemented to estimate ROS production. Cell migration and invasion were measured using transwell chambers assay. Effects of astragalin on JAK/STAT pathway were investigated using western blotting assay. Results showed astragalin molecule induced inhibition of proliferation in A549 cells in a dose-dependent fashion. Further, the antiproliferative effects were found to mediate via apoptosis as suggested by AO/EB staining and western blotting assay. Astragalin modulated the expressions of caspase-3, caspase-9, Bax, Bak, Cyt-c Bcl-2, XIAP and Bcl-xL. Astragalin induced DNA damage in A549 cells which too indicated apoptotic cell death. Astragalin molecule enhanced the production of ROS by A549 cells. It inhibited both cell migration and invasion of A549 cells in a concentration-dependent manner. Finally, astragalin drug was observed with remarkable potential of targeting JAK/STAT pathway in A549 NSCLC cells. These results indicated that astragalin drug could prove helpful in lung cancer treatment and research provided more in-vivo studies are performed.

The ionotropic γ-aminobutyric acid (iGABA) receptor is commonly considered as a fast inhibitory channel and is an important insecticide target. Since 1990, RDL, LCCH3, and GRD have been successively isolated and found to be potential subunits of the insect iGABA receptor. More recently, one orphan gene named 8916 was found and considered to be another potential iGABA receptor subunit according to its amino acid sequence. However, little information about 8916 has been reported. Here, the 8916 subunit from Chilo suppressalis was studied to determine whether it can form part of a functional iGABA receptor by co-expressing this subunit with CsRDL1 or CsLCCH3 in the Xenopus oocyte system. Cs8916 or CsLCCH3 did not form functional ion channels when expressed alone. However, Cs8916 was able to form heteromeric ion channels when expressed with either CsLCCH3 or CsRDL1. The recombinant heteromeric Cs8916/LCCH3 channel was a cation-selective channel, which was sensitive to GABA or β-alanine. The current of the Cs8916/LCCH3 channel was inhibited by dieldrin, endosulfan, fipronil, or ethiprole. In contrast, fluralaner, broflanilide, and avermectin showed little effect on the Cs8916/LCCH3 channel (IC50s > 10 000 nM). The Cs8916/RDL1 channel was sensitive to GABA, but was significantly different in EC50 and Imax for GABA to those of homomeric CsRDL1. Fluralaner, fipronil, or dieldrin showed antagonistic actions on Cs8916/RDL1. In conclusion, Cs8916 is a potential iGABA receptor subunit, which can interact with CsLCCH3 to generate a cation-selective channel that is sensitive to several insecticides. Also, as Cs8916/RDL1 has a higher EC50 than homomeric CsRDL1, Cs8916 may affect the physiological functions of CsRDL1 and therefore play a role in fine-tuning GABAergic signaling.

Polo-like kinase 4 (PLK4) is one of the key regulators of centrosomal replication. However, its role and mechanism in spinal cord injury (SCI) are still unclear. The SCI model on rats was constructed and the expression and localization of PLK4 in the spinal cord are analyzed with Western blot and immunofluorescence, respectively. Then the specific siRNAs were encapsulated in nanoparticles for the inhibition of PLK4 expression. Afterward, the role of PLK4 on astrocytes was investigated by knocking down its expression in the primary astrocytes. Moreover, siRNA-loaded nanoparticles were injected into the injured spinal cord of rats, and the motor function recovery of rats after SCI was assessed using the Basso, Beattie, and Bresnahan (BBB) locomotor scale method. Notably, the siRNA-loaded nanoparticles effectively transfect primary astrocytes and significantly inhibit PLK4 expression, together with the expression of PCNA with significance. After treatment, restoration of the motor function following SCI was significantly improved in the PLK4 knockdown group compared with the control group. Therefore, we speculate that inhibition of Plk4 may inhibit the proliferation of astrocytes and decrease the inflammatory response mediated by astrocytes, so as to promote the functional recovery of SCI. In conclusion, inhibition of PLK4 expression via siRNA-loaded nanoparticles may be a potential treatment for SCI.

The perovskite oxides La0.7Sr0.3Fe0.8B0.2O3 (B = Ti, Mn, Co, Ni and Cu) synthesized by sol–gel method were used as cathodes and tested in asymmetric electrocarboxylation of aromatic ketones. The study showed the La0.7Sr0.3Fe0.8Ni0.2O3 (La7Sr3Fe8Ni2) catalyst is more active for asymmetric electrocarboxylation of acetophenone with 95% enantiomeric excess and 85% yield. The high electrocatalytic activity is attributed mainly to several factors, including the increased amount of lattice oxygen and Fe4+ species on the surface of La7Sr3Fe8Ni2, enhanced electrochemically active surface area and faster electron transfer. Furthermore, La7Sr3Fe8Ni2 also exhibited remarkable stability and reusability.

The mitogen-activated protein kinase (MAPK) cascades play important roles in various signaling transduction networks of biotic and abiotic stress responses. However, MAPK signaling pathways in cold-active yeast Rhodotorula mucilaginosa have not been reported comprehensively. In the present study, MAPK gene ( RmMAPK ) was first cloned and characterized from Antarctic sea ice yeast R. mucilaginosa AN5. The full length of the RmMAPK gene is 1086 bp and encodes a 361 amino acids protein with a predicted molecular mass of 40.9 kDa and a pI of 5.25. The RmMAPK contains 11 MAPK conserved subdomains and the phosphorylation motif TGY located in the activation loop of the kinase. Quantitative real-time PCR assay revealed that the expression of RmMAPK up-regulated rapidly and significantly when yeast cells were subjected to low temperature (4 °C), high salinity (120‰ NaCl) and heavy metal (2 mmol/L CuCl 2 ), which suggested that the RmMAPK might act as a key function in response to extreme stresses, such as low temperature, high salinity and heavy metal.

Aberrant activation of FGFR signaling occurs in many cancers, and ATP-competitive FGFR inhibitors have received regulatory approval. Despite demonstrating clinical efficacy, these inhibitors exhibit dose-limiting toxicity, potentially due to a lack of selectivity amongst the FGFR family and are poorly tolerated. Here, we report the discovery and characterization of DGY-09-192, a bivalent degrader that couples the pan-FGFR inhibitor BGJ398 to a CRL2(VHL) E3 ligase recruiting ligand, which preferentially induces FGFR1&2 degradation while largely sparing FGFR3&4. DGY-09-192 exhibited two-digit nanomolar DC(50)s for both wildtype FGFR2 and several FGFR2-fusions, resulting in degradation-dependent antiproliferative activity in representative gastric cancer and cholangiocarcinoma cells. Importantly, DGY-09-192 induced degradation of a clinically relevant FGFR2 fusion protein in a xenograft model. Taken together, we demonstrate that DGY-09-192 has potential as a prototype FGFR degrader.

Ligustrazine, an alkaloid extracted from the traditional Chinese herbal medicine Ligusticum Chuanxiong Hort, has been clinically applied to treat the cerebrovascular diseases. Hyperhomocysteinemia (Hhcy) is an independent risk factor for Alzheimer's disease (AD). Memory deficits can be caused by Hhcy via pathologies of AD-like tau and amyloid-β (Aβ) in the hippocampus. Here, we investigated whether homocysteine (Hcy) can induce AD-like pathologies and the effects of ligustrazine on these pathologies. The Hcy rat model was constructed by 14-day Hcy injection via vena caudalis, and rats were treated with daily intragastric administration of ligustrazine at the same time. We found that the pathologies of tau and Aβ were induced by Hcy in the hippocampus, while the Hcy-induced tau hyperphosphorylation and Aβ accumulation could be markedly attenuated by simultaneous ligustrazine treatment. Our data demonstrate that ligustrazine may be used as a promising neuroprotective agent to treat the Hcy-induced AD-like pathologies.

Tubular In2O3 was fabricated by the annealing of In-MIL-68 and further treated by Ar plasma to yield oxygen vacancies (Ov) followed by the growth of In2S3 nanoflowers. Unexpectedly, the resulting porous In2S3@In2O3 composites were discovered to display a broad visible-light response and especially enhanced capacities for efficient photocatalytic production of H2O2 in pure water, with a rate of 4.59 μmol·g-1·min-1. An apparent quantum yield of 28.9% at 420 nm can also be expected without the use of noble metals or organic scavengers. Herein, the high light utilization might be profited from their porous tubular heterostructure for powerful "light captivity". Moreover, the Ar plasma-derived Ov sites on the composites might tune the H2O2 generation route from the single-electron reduction to the two-electron one toward the significantly enhanced photocatalysis, as validated by the Koutecky-Levich plots. This work demonstrates a new perspective of designing porous heterostructures with the advantages of high light harvest and plasma-derived Ov active sites. Importantly, it may provide a promising defect-induced strategy of two-electron reduction triggered by the plasma treatment for the efficient photocatalytic H2O2 production under visible light.

Progesterone resistance can significantly restrict the efficacy of conservative treatment for patients with endometrial cancer who wish to preserve their fertility or those who suffer from advanced and recurrent cancer. SREBP1 is known to be involved in the occurrence and progression of endometrial cancer, although the precise mechanism involved remains unclear. In the present study, we carried out microarray analysis in progesterone-sensitive and progesterone-resistant cell lines and demonstrated that SREBP1 is related to progesterone resistance. Furthermore, we verified that SREBP1 is over-expressed in both drug-resistant tissues and cells. Functional studies further demonstrated that the inhibition of SREBP1 restored the sensitivity of endometrial cancer to progesterone both in vitro and in vivo, and that the over-expression of SREBP1 promoted resistance to progesterone. With regards to the mechanism involved, we found that SREBP1 promoted the proliferation of endometrial cancer cells and inhibited their apoptosis by activating the NF-κB pathway. To solve the problem of clinical application, we found that Fatostatin, an inhibitor of SREBP1, could increase the sensitivity of endometrial cancer to progesterone and reverse progesterone resistance by inhibiting SREBP1 both in vitro and in vivo. Our results highlight the important role of SREBP1 in progesterone resistance and suggest that the use of Fatostatin to target SREBP1 may represent a new method to solve progesterone resistance in patients with endometrial cancer.

Background Hepatocellular carcinoma (HCC) cells-secreted exosomes (exo) could stimulate M2 macrophage polarization and promote HCC progression, but the related mechanism of long non-coding RNA distal-less homeobox 6 antisense 1 (DLX6-AS1) with HCC-exo-mediated M2 macrophage polarization is largely ambiguous. Thereafter, this research was started to unearth the role of DLX6-AS1 in HCC-exo in HCC through M2 macrophage polarization and microRNA (miR)-15a-5p/C-X-C motif chemokine ligand 17 (CXCL17) axis. Methods DLX6-AS1, miR-15a-5p and CXCL17 expression in HCC tissues and cells were tested. Exosomes were isolated from HCC cells with overexpressed DLX6-AS1 and co-cultured with M2 macrophages. MiR-15a-5p/CXCL17 down-regulation assays were performed in macrophages. The treated M2 macrophages were co-cultured with HCC cells, after which cell migration, invasion and epithelial mesenchymal transition were examined. The targeting relationships between DLX6-AS1 and miR-15a-5p, and between miR-15a-5p and CXCL17 were explored. In vivo experiment was conducted to detect the effect of exosomal DLX6-AS1-induced M2 macrophage polarization on HCC metastasis. Results Promoted DLX6-AS1 and CXCL17 and reduced miR-15a-5p exhibited in HCC. HCC-exo induced M2 macrophage polarization to accelerate migration, invasion and epithelial mesenchymal transition in HCC, which was further enhanced by up-regulated DLX6-AS1 but impaired by silenced DLX6-AS1. Inhibition of miR-15a-5p promoted M2 macrophage polarization to stimulate the invasion and metastasis of HCC while that of CXCL17 had the opposite effects. DLX6-AS1 mediated miR-15a-5p to target CXCL17. DLX6-AS1 from HCC-exo promoted metastasis in the lung by inducing M2 macrophage polarization in vivo. Conclusion DLX6-AS1 from HCC-exo regulates CXCL17 by competitively binding to miR-15a-5p to induce M2 macrophage polarization, thus promoting HCC migration, invasion and EMT.

Large-scale distributed thermal storage requires high-energy-density and low-cost thermal storage materials. Here, a concocted composite composed of Al2(SO4)3·18H2O and FeSO4·7H2O salts, as well as...

An approach, i.e., atmospheric-pressure nonequilibrium oxygen plasma jet technology, has been reported for the first time to in situ prepare ultrathin nonstoichiometric nickel oxide layers with mix...

Porphyromonas gingivalis is a bacterial species known to be involved in the pathogenesis of chronic periodontitis, that more recently has been as well associated with Alzheimer’s disease. P. gingivalis expresses a glutaminyl cyclase (PgQC) whose human ortholog is known to participate in the beta amyloid peptide metabolism. We have elucidated the crystal structure of PgQC at 1.95 Å resolution in unbound and in inhibitor-complexed forms. The structural characterization of PgQC confirmed that PgQC displays a mammalian fold rather than a bacterial fold. Our biochemical characterization indicates that PgQC uses a mammalian-like catalytic mechanism enabled by the residues Asp149, Glu182, Asp183, Asp218, Asp267 and His299. In addition, we could observe that a non-conserved Trp193 may drive differences in the binding affinity of ligands which might be useful for drug development. With a screening of a small molecule library, we have identified a benzimidazole derivative rendering PgQC inhibition in the low micromolar range that might be amenable for further medicinal chemistry development.

Puromycin-hydrolizing peptidases have been described as members of the prolyl oligopeptidase peptidase family. These enzymes are present across all domains of life but still little is known of the homologs found in the pathogenic bacterium Mycobacterium tuberculosis. The crystal structure of a M. tuberculosis puromycin hydrolase peptidase has been determined at 3 Angstrom resolution, revealing a conserved prolyl oligopeptidase fold, defined by α/β-hydrolase and β-propeller domains with two distinctive loops that occlude access of large substrates to the active site. The enzyme displayed amino peptidase activity with a substrate specificity preference for hydrophobic residues in the decreasing order of phenylalanine, leucine, alanine and proline. The enzyme's active site is lined by residues Glu564 for the coordination of the substrates amino terminal moiety and His561, Val608, Tyr78, Trp306, Phe563 and Ty567 for the accommodation of hydrophobic substrates. The availability of a crystal structure for puromycin hydrolase of M. tuberculosis shall facilitate the development of inhibitors with therapeutic applications.

The chiral deformation of a conventional helical actuator is unidirectional in each activation (stimuli-on) process and in each recovery (stimuli-off) process, which means that the twisting direction remains the same regardless of the nature of deformation (either winding or unwinding or helix-inversion). In these cases, a complete stimuli-switching cycle is necessary for the realization of a bidirectional helical deformation process that comprises a reversal of twisting direction. Here, we achieved bidirectional and even multi-directional helical shape evolution in each stimuli-on (or off) process. The strategy relies on, on one hand, asymmetrically crosslinking and/or elongating the two sides of a photocrosslinkable liquid crystal polymer (LCP) monolith, and on the other hand, tailoring the uniaxially aligned polymer strip to form an off-axis mesogen orientation. We obtained a wide variety of helical actuators capable of reversing their twisting directions by only cooling (or heating). The mechanisms of these various chiral deformation-reversal behaviours and the two observed reversals of the twisting direction during cooling have been elucidated.

Structural features are important factors determining the performance of electrode materials for alkaline metal (Li, Na, and K) storage. In this work, we report a fascinating Kirkendall-effect-based method for the synthesis of a spindle-like FeP@C composite with a hierarchical structure comprising carbon-coated hollow FeP sub-nanoparticles (S-HFeP@C). In such a unique structure, the interconnected carbon network and intimate C/FeP contact allow for the ready transfer of charge during redox reactions. The hollow structure of the FeP nanoparticles and their thin walls allow for easy ion diffusion and satisfactory alleviation of the overall strain of FeP, endowing S-HFeP@C with fast reaction kinetics, satisfactory utilization of active material, and excellent structural robustness upon redox reaction. Enhanced performance was observed for Li, Na, and K storage by S-HFeP@C, consisting of a high specific capacity, excellent rate capabilities, and satisfactory cycling stability.

We describe a catalytic asymmetric iminium ion cyclization reaction of simple 2-alkenylbenzaldimines using a BINOL-derived chiral N-triflyl phosphoramide. The corresponding 1-aminoindenes and tetracyclic 1-aminoindanes are formed in good yields and high enantioselectivities. Further, the chemical utility of the obtained enantiopure 1-aminoindene is demonstrated for the asymmetric synthesis of (S)-rasagiline.

It is generally believed that metals which are unalloyable with Li are not active for Li storage. This work, however, demonstrates that transition metals with unoccupied 3d orbitals are usable as anode materials for Li storage although they are unalloyable with Li. Specifically, we synthesize spindle-shaped Fe@C (S-Fe@C) by the calcination of an Fe based metal–organic framework, which comprises carbon coated Fe subnanoparticles with an interconnected carbon network. When used in LIBs, S-Fe@C can exhibit a stable reversible capacity of 967.3 ± 16.2 mA h g−1 at 100 mA g−1. More interestingly, when S-Fe@C with smaller Fe nanoparticles and more spacing between the Fe nanoparticles and carbon shell is used as the anode for LIBs, the stable reversible capacity can reach up to 1091.9 ± 17.6 mA h g−1 at 100 mA g−1 after 100 cycles. The in operando XRD patterns exclude the contribution of capacities from the alloying between Fe and Li. DFT calculations indicate that the unoccupied 3d orbitals of Fe atoms can accept electrons from Li, which makes the surface of Fe nanoparticles highly active for Li adsorption. The Li adsorption can be multi-layered. Our findings can well explain why some transition metal oxides can exhibit extra capacities beyond their theoretical capacities.