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The responses of Al/PTFE reactive materials (RMs) under shock compression were investigated by a single-stage gas gun. A 3D mesoscale-model was established based on micro-computed tomography (micro-CT) slice images and confirmed with experimental results. In the high-pressure stage, the composites reacted partially, whereas there were no deviations between the partially reacted Hugoniot and the inert simulation results. The simulation reveals that the Teflon matrix melting on the high shock pressure. Melts and decomposition of the PTFE accelerated the diffusion of the atoms. Thus, the reactions of the Al/PTFE composites are more like a combustion rather than a detonation.

To elucidate the response of oxidative metabolism, triggered by elevated ammonium (NH4+) concentrations, on root growth of wheat seedlings, Yumai 49 (NH4+-tolerant) and Lumai 15 (NH4+-sensitive) cultivars were supplied with either 5.0 mmol L−1 NH4+-N (EAC) or 5.0 mmol L−1 NO3–-N (CON) under hydroponic conditions. Root growth in both cultivars was significantly reduced under EAC, and the negative effect was greater in Lumai 15. EAC enhanced the activities of monodehydroascorbate reductase and dehydroascorbate reductase in the roots of both cultivars, while it decreased ascorbic acid (ASA) content and GDP-mannose pyrophosphorylase (GMPase) activity at the 12th day after treatment in Lumai 15 by 62.0 and 71.4%; and in Yumai 49 by 38.8 and 62.2%, respectively, indicating that the regeneration of ASA was increased, but the biosynthesis of ASA was reduced under EAC treatment. Moreover, EAC increased DHA/ASA, reactive oxygen species (ROS), and malondialdehyde contents, as well as antioxidant enzyme activities in the roots of both cultivars. Relatively greater increases in ROS and soluble sugar, and lower antioxidant enzyme activities in Lumai 15 indicate severe disruption of oxidative metabolism when compared to Yumai 49. Results reveal that the reduction of ASA biosynthesis via decreased GMPase activity under the EAC condition probably acts as a trigger for accumulated ROS and imbalanced redox status, resulting in root growth inhibition during wheat seedling growth stage. Yumai 49, being an NH4+ -tolerant cultivar, had the stronger capacity to protect itself from oxidative stress, which allowed it to retain a lower DHA to ASA ratio by maintaining a better redox homeostasis than could be maintained in the NH4+ -sensitive cultivar Lumai 15.

All-hydrocarbon stapling strategy has been widely applied for enhancing the proteolytic stability of peptides. However, two major technical hurdles to some extent limit the development of stapled peptides for therapeutic usage: rational selection of the stapling sites and the corresponding deletion of the native side chains. Previously we described the development of the olefin-terminated amino acids with the retention of native side chains and successfully applied them in the synthesis of hydrocarbon stapled peptides with single side-chain retention. Here, we explored the feasibility and effectiveness of hydrocarbon stapling strategy characterized as double side-chains retention. Modeled after a lengthy human immunodeficiency virus-1 (HIV-1) fusion inhibitor SC34EK, Leui, Seri+4 and Lysi, Leui+4 stapled peptides with the retention of double side-chains were effectively obtained. Our complementary study provided a convenient alternative to address where to install the staple in sequence for conventional all-hydrocarbon peptide stapling. Furthermore, this method not only conferred conformational reinforcement for SC34EK with high α-helicity and protease resistance, but also preserved the structural characteristic (key peripheral residues, charge and solubility) of the linear peptide to the maximum, which are crucial for anti-HIV-1 activity.

The desulfurization of 2-phenylcyclohexanethiol (2-PCHT) was studied over sulfided Mo/γ-Al2O3, Ni-Mo/γ-Al2O3, and Co-Mo/γ-Al2O3 catalysts under 5.0 MPa H2 or Ar at 240 °C. Under H2, the desulfurization of 2-PCHT proceeded mainly through the hydrogenolysis and β-elimination pathways. The former was faster than the latter over Mo/γ-Al2O3. Ni and Co accelerated the β-elimination pathway but hardly affected the hydrogenolysis pathway. The activity of Mo/γ-Al2O3 was enhanced by Ni, whereas Co did not show any promoting effect. Under Ar, the desulfurization of 2-PCHT occurred mainly through the β-elimination and dehydrogenation pathways. The β-elimination pathway was faster than the dehydrogenation pathway. Both pathways were enhanced by Ni and Co. Ni and Co promoted the dehydrogenation pathway mainly by promoting the dehydrogenation-ring closure reaction. The inhibiting effects of piperidine depended on the reaction and catalyst. Under Ar, Ni-Mo/γ-Al2O3 was more sensitive to piperidine inhibition.

Brain-specific loss of a microtubule-binding protein collapsin response mediator protein-2 (CRMP2) in the mouse recapitulates many schizophrenia-like behaviors of human patients, possibly resulting from associated developmental deficits in neuronal differentiation, path-finding, and synapse formation. However, it is still unclear how the Crmp2 loss affects neuronal circuit function and plasticity. By conducting in vivo and ex vivo electrophysiological recording in the mouse primary visual cortex (V1), we reveal that CRMP2 exerts a key regulation on the timing of postnatal critical period (CP) for experience-dependent circuit plasticity of sensory cortex. In the developing V1, the Crmp2 deficiency induces not only a delayed maturation of visual tuning functions but also a precocious CP for visual input-induced ocular dominance plasticity and its induction activity – coincident binocular inputs right after eye-opening. Mechanistically, the Crmp2 deficiency accelerates the maturation process of cortical inhibitory transmission and subsequently promotes an early emergence of balanced excitatory-inhibitory cortical circuits during the postnatal development. Moreover, the precocious CP plasticity results in deteriorated binocular depth perception in adulthood. Thus, these findings suggest that the Crmp2 deficiency dysregulates the timing of CP for experience-dependent refinement of circuit connections and further leads to impaired sensory perception in later life.

Designing and developing composites with excellent mechanical, friction, and durability properties at low cost has long been highly desirable for the applications of friction materials. Herein, we employed a cost-effective method to obtain bio-based silica (RHC-SiO2) from gasified rice husk carbon (RHC). Subsequently, inspired by the characteristics of RHC-SiO2 and its hardening process, we report a simple and efficient so-called “hybrid pressing and sintering molding” method for manufacturing copper-based friction materials (CFMs). The CFM-R4 (CFM with 4% RHC-SiO2) possesses a unique combination of high hardness (55.50 H V), low density (0.62 g/cm3), low wear rate (0.081%), suitable friction coefficient (0.26), and good durability. Based on the cost-effective method, the increased and decreased stages of RHC-SiO2 yield were determined mainly by reaction rate and compatibility, respectively. Compared with CFM-0 (CFM without SiO2), the CFM with RHC-SiO2 possesses better mechanical and friction properties. In view of high-performance and eco-friendly, such CFM with RHC-SiO2 would hold a promising application in friction fields such as transmission, differential, and synchronizer.

One of the hottest topics in industrial and engineering applications of applied mathematics is the advances in nanotechnology particularly in nanofluids, hybrid nanofluids which consist of a typical base fluid saturated with nano-size metallic particles with enhanced thermophysical properties. In this regard, current study reports an entropy nature of steady, laminar, relative contributions of thermal and solutal Marangoni convections on passage in Casson A l 2 O 3 − Cu − H 2 O hybrid nanofluid stream past over a disk under the impact of nonlinear heat source/sink, viscous dissipation, radiation, and nonlinear convection. Suitable similarity transformation is apt to reduce the governing partial differential equations to a series of ordinary differential equations. The obtained nonlinear ODE set is then solved numerically by using bvp4c method. The impact of various pertinent flow parameters on the velocity, thermal, concentration, entropy production, rate of heat and mass transfer fields are discussed in detail through graphs. The results reveal that, boost up values of Marangoni number and radiation parameter inclines the heat transfer of the fluid flow system. The upsurge in Exponential heat source/ sink parameter and thermal source/sink parameter inclines the thermal profile. Further, increase in value of volume fraction inclines the rate of mass transfer.

Gold nanostar (AuNS) particles, characterized by pointed tips emerging from a central core, exhibit localized surface plasmon resonance (LSPR) with strongly amplified electric field upon illumination. Compared to Au nanospheres and nanorods, the absorbance is enhanced with the absorption band extending from 500 to above 1000 nm. However, they are easily reshaped by Ostwald ripening and therefore difficult to use in any application. This study shows that the AuNS particles can be effectively stabilized by encapsulation with TiO2 using a low temperature method. The synthesis parameters and capping solution were optimized to form nanostars. The encapsulated Au nanoparticles promoted the aerobic oxidation of benzyl alcohol to benzaldehyde at ambient temperature under visible light irradiation. AuNS@TiO2 showed significantly higher photocatalytic activity than Au nanospheres, Au nanorods or bulk TiO2 due to its enhanced LSPR. Encapsulation of the colloidal nanoparticles with TiO2 confers robustness to the resulting heterogeneous catalyst with retention of the metal particle size, morphology and associated LSPR properties.

Polymer stimuli-responsive microgels find their use in various applications. The knowledge of its internal structure is of importance for further improvement and expanding the scope. Interpenetrating network (IPN) microgels may possess a remarkable feature of strongly non-uniform inner architecture, even microphase separation, in conditions of a selective solvent. In this research, we, for the first time, use a combination of static light scattering (SLS) and small-angle X-ray scattering (SAXS) techniques to collect the structure factors of aqueous dispersions of poly(N-isopropylacrylamide)-polyacrylic acid IPN microgels on the broad scale ofqvalues. We study the influence of solvent quality on microgel conformations and show that in a selective solvent, such a system undergoes microphase separation: the sub-network in a poor solvent conditions forms dense small aggregates inside the large swollen sub-network in a good solvent. We propose the microstructured sphere model for the IPN microgel structure factor interpretation and perform additional analysis and verification through coarse-grained molecular dynamics computer simulations.

The joint signatures of binary-state and multi-state (semi-coherent or mixed) systems with i.i.d. (independent and identically distributed) binary-state components are considered in this work. For the comparison of pairs of binary-state systems of different sizes, transformation formulas of their joint signatures are derived by using the concept of equivalent systems and a generalized triangle rule for order statistics. Similarly, for facilitating the comparison of pairs of multi-state systems of different sizes, transformation formulas of their multi-state joint signatures are also derived. Some examples are finally presented to illustrate and to verify the theoretical results established here.

The increasing demand of cooling in internal combustion engine (ICE) may require the shift of heat removal method from traditional single phase liquid convection to subcooled flow boiling in order to fulfill the desired functional temperature. Thus, the characteristics of subcooled flow boiling heat transfer should be studied exclusively considering the practical conditions in ICEs. Accordingly, in this article, subcooled flow boiling experiments were conducted in a rectangular channel using 50/50 volume mixture of ethylene glycol and water coolant (EG/W) as working fluid. Aluminum and cast iron surfaces were selected as the heated surfaces to simulate the material of cylinder head in gasoline and diesel engines, respectively. Experimental results showed a trend that the aluminum surface had a better performance than the cast iron surface in terms of heat transfer coefficient in the boiling region. The difference between these two surfaces was concluded as results of different surface thermophysical properties. A modified wall heat flux model was proposed based on the power-type addition method. The proposed model modified the nucleation boiling contribution by introducing a new parameter which accounts for the influence of thermophysical properties of heated surface on the boiling process. Thus, one such modified model could be useful for practical engine cooling applications.

The electro-catalytic methanol oxidation reaction (MOR) has received considerable research attention due to its importance in the development of direct methanol fuel cells. In this study, the dehydrogenation step in MOR was investigated using low levels of platinum (Pt) which supported on carbon nanotubes as a catalyst. The concentration of H+ had a significant effect on the MOR activity of Pt catalysts supported by carbon nanotubes (Pt/CNTs), indicating that the dehydrogenation process was a critical step in MOR for Pt/CNTs with low Pt loading. Furthermore, the effects of Pt particle size and the distance between the Pt particles were investigated. We suggested a hypothesis: for the Pt catalyst with large particle size, only a few particles were needed for dehydrogenation to proceed; for the Pt catalyst with small particle size, many Pt particles were needed to form a network for the dehydrogenation reaction, but when the Pt particles were close enough, only a few Pt particles were needed. Our study provided insight into the electro-catalytic activity of Pt/CNTs from a mechanistic perspective.

Embedded noble metal nanostructures and surface anti-reflection (AR) layers affect the optical properties of methylammonium lead iodide (CH3NH3PbI3) perovskite solar cells significantly. Herein, by employing a combined finite element method and genetic algorithm approach, we report five different types of CH3NH3PbI3 perovskite solar cells by introducing embedded Ag nanoparticles within the CH3NH3PbI3 layer and/or top ITO cylinder grating as an AR layer. The maximum photocurrent was optimized to reach 23.56 mA/cm2, which was 1.09/1.17 times higher than Tran’s report/ flat cases. It is also comparable with values (23.6 mA/cm2) reported in the literature. The calculations of the electric field and charge carrier generation rate of the optimized solar cell further confirms this improvement than flat cases. It attributes to the synergistic effect of the embedded Ag nanoparticles and ITO AR layer. The results obtained herein hold great promise for future boosting the optical efficiency of perovskite solar cells.

Polymer membranes typically possess a broad pore-size distribution that leads to much lower selectivity in ion separation when compared to membranes made of crystalline porous materials; however, they are highly desirable because of their easy processability and low cost. Herein, we demonstrate the fabrication of ion-sieving membranes based on a polycarbazole-type conjugated microporous polymer using an easy to scale-up electropolymerization strategy. The membranes exhibited high uniform sub-nanometer pores and a precisely tunable membrane thickness, yielding a high ion-sieving performance with a sub-1 Å size precision. Both experimental results and molecular simulations suggested that the impressive ion-sieving performance of the CMP membranes originates from their uniform and narrow pore-size distribution.

A novel three-component reaction of α-ketoaldehydes, 1,3-dicarbonyl compounds, and organic boronic acids catalyzed by CuO in water has been developed to give a wide range of products containing 1,3/1,4-diketones. The method has some advantages such as the use of readily available starting materials, wide substrate scopes, excellent yields, gram-scale synthesis, and mild reaction conditions.

Mammalian cell cycle is a central process for tissue growth and maintenance. Protein O-linked β-N-acetylglucosamine (O-GlcNAc) modification has been found to occur on several important cell cycle regulators. However, the O-GlcNAcylated proteome has not been extensively profiled during cell cycle progression. Herein, we report a quantitative profiling of protein O-GlcNAcylation sites in cell proliferation, by using an O-GlcNAc chemoproteomic strategy. In HeLa cells, a total of 902, 439, and 872 high-confidence O-GlcNAcylation sites distributed on 414, 265, and 425 proteins are identified in the interphase, early mitosis, and mitotic exit stages, respectively. The identified O-GlcNAcylation events occur on a variety of important regulators, which are involved in the processes of cell division, DNA repair, and cell death. Furthermore, we show that O-GlcNAcylation is dynamically regulated in a cell cycle stage-dependent manner. Our results provide a valuable resource for investigating the functional roles of O-GlcNAc in the mammalian cell cycle.

A visible-light-induced decarboxylation reaction was developed for the synthesis of alkylated benzimidazo[2,1-a]isoquinoline-6(5H)-ones and indolo[2,1-a]isoquinolin-6(5H)-ones under metal-free conditions. Impressively, metal catalysts and traditionally volatile organic solvents could be effectively avoided.

High ionic conductivity, good mechanical strength, strong electrode adhesion, and low volatilization are highly desired properties for flexible solid electrolytes. However, it is difficult to realize all these properties simultaneously, which needs a rational synergy of different electrolyte constituents. Here, we present the use of polyoxometalates as versatile enhancers to fabricate nonvolatile flexible hybrid polymer electrolytes with improved conductive, stretchable, and adhesive properties. These electrolytes are based on the molecular hybridization of a polyacrylate elastomer, phosphoric acid, and a commercial polyoxometalate H3PW12O40 (PW). PW can serve as a nanosized plasticizer to favor the chain relaxation of polyacrylate and improve stretchability. Meanwhile, PW as a solid acid can increase the proton concentration and form a hybrid hydrogen-bonding network to facilitate proton conduction. Besides, the strong adsorption ability of PW on solid surfaces enables the electrolytes with enhanced adhesion. The hybrid electrolyte with 30 wt % PW shows a break stress of 0.28 MPa, a break elongation of 990%, and a conductivity of 0.01 S cm-1 at 298 K, which are 1.8, 1.8, and 2.5 times higher compared to the case without PW, respectively. Moreover, PW enhances the adhesive strength of hybrid electrolytes on polypropylene, steel, and glass substrates. The flexible supercapacitors based on the hybrid electrolytes and polyaniline electrodes hold a stable electrode-electrolyte interface and exhibit a high specific capacitance of 592 mF cm-2 and an excellent capacitance retention of 84% after 6000 charge-discharge cycles. These results demonstrate great potential of polyoxometalates as multifunctional enhancers to design hybrid electrolyte materials for energy and electronic applications.

Equipped with a fully lithiated cathode with a bare anode current collector, the anode-free lithium cell architecture presents remarkable advantages in terms of both energy density and safety compared with conventional lithium-ion cells. However, it is challenging to realize high Li reversibility, especially considering the limited Li reservoir (typically zero lithium excess) in the cell configuration. In this study we have introduced Li2O as a preloaded sacrificial agent on a LiNi0.8Co0.1Mn0.1O2 cathode, providing an additional Li source to offset the irreversible loss of Li during long-term cycling in an initial-anode-free cell. We show that O2− species, released through Li2O oxidation, are synergistically neutralized by a fluorinated ether additive. This leads to the construction of a LiF-based layer at the cathode/electrolyte interface, which passivates the cathode surface and restrains the detrimental oxidative decomposition of ether solvents. We have achieved a long-life 2.46 Ah initial-anode-free pouch cell with a gravimetric energy density of 320 Wh kg–1, maintaining 80% capacity after 300 cycles. Anode-free batteries offer high-energy prospects but suffer from poor cycling stability due to limited lithium sources. Here, the authors preload lithium oxide onto a high-energy cathode in initial-anode-free cells, which substantially improves the cyclability while maintaining high energy density.

The construction of nanostructured ion-transport channels is highly desirable in the design of advanced electrolyte materials, as it can enhance ion conductivity by offering short ion-transport pathways. In this work, we present a supramolecular strategy to fabricate a nanocomposite electrolyte containing highly ordered lamellar proton-conducting nanochannels, by the electrostatic self-assembly of a polyoxometalate H3PW12O40 (PW) and a comb copolymer poly(4-methlstyrene)-graft-poly(N-vinyl pyrrolidone). PW can effectively regulate the self-assembling order of polymer moieties to form a large-range lamellar structure, meanwhile, introducing protons into the nanoscale lamellar domains to build proton transport channels. Moreover, the rigid PW clusters contribute a remarkable mechanical reinforcement to the nanocomposites. The lamellar nanocomposite exhibits a conductivity of 4.3 × 10−4 S/cm and a storage modulus of 1.1 × 107 Pa at room temperature. This study provides a new strategy to construct nanostructured ion-conductive pathways in electrolyte materials.

Creep deformation can be classified as homogeneous flow and inhomogeneous flow in bulk metallic glass (BMG). In order to understand the conversion conditions of the two types of creep deformation, the effect of loading rate on the creep behavior of a Ti40Zr10Cu47Sn3 (at.%) BMG at ambient temperature was investigated using nanoindentation and molecular dynamic simulation. Results indicate that at low loading rates, many serrations appear in loading stage, leading to inhomogeneous serrated flow in the creep stage. When the loading rate is high enough, the creep deformation tends to be homogeneous. The related mechanism responsible for the rate-dependent creep behavior is attributed to the number of pre-existing major shear bands which is influenced significantly by the loading rate.

Houttuynia cordata has been used as a traditional medicine for more than 1500 years. It has aroused wide public concern about its safety in the past few years, for it contains various aristolactams. However, the safety of H. cordata extract remains unclear. In the present study, single dose (2000 mg/kg) and subacute (250, 500, and 1000 mg/kg/day for 28 days) oral toxicity studies of the 95% ethanol extract of H. cordata (HCE) were performed in both male and female Sprague-Dawley (SD) rats. Hematological, biochemical, histopathological parameters, and plasma metabolic profiling were assessed. The single-dose toxicity of HCE was more than 2000 mg/kg. The subacute toxicity results showed that no significant adverse effect of HCE was observed at 250 mg/kg/day. However, five rats died in 500 and 1000 mg/kg/day groups and exhibited toxicities to liver and kidney. Plasma metabolic profiling analysis suggested that a number of metabolic disturbances were induced by oral administration of HCE, focusing on energy metabolism, amino acid metabolism, and lipids metabolism. Moreover, it appeared that male rats were more susceptible to the toxic effects of HCE than female rats. Therefore, in this preliminary study, oral administration of HCE 250 mg/kg/day can be regarded as the no observed adverse effect level in rats over 28 days. However, long-term use of HCE with large doses exhibited some hepatotoxicity and nephrotoxicity in rats.

A novel Pd(II)-catalyzed enantioselective oxycarbonyl-ation of alkenes has been established herein. The ligand with an ethyl group at the C-6 position of Pyox plays a significant role in the intermolecular oxypalladation process, leading to high reactivity and excellent enantioselective control. Compared to the conventional methods, the reaction itself features alkenes as easily prepared starting materials, mild and operationally simple reaction conditions, and insensitivities to air and water. Moreover, this method allows for broad alkene substrate scope, excellent regio- and enantio-selectivities, scalabilities and a wide array of applications, and provides a useful route for the convenient and straightforward synthesis of chiral s -hydroxy alkylcarboxylic acids/esters.

High temperature (HT) severely limits rice production, but effective measures can reduce the adverse effects of HT. A 2-year experiment was conducted involving five sowing dates to investigate the effects of potassium dihydrogen phosphate (KH2PO4), salicylic acid (SA), and the sowing date on the physiological characteristics, yield and quality of rice subjected to HT. Under ambient HT conditions (daily average temperature ≥ 30 °C for ≥ 3 days or maximum temperature ≥ 35 °C for ≥ 3 days), KH2PO4 (KP1-KP2: 22.05 and 36.75 mmol L−1), SA (SA1-SA2: 0.5 and 1.5 mmol L−1), and their combinations were applied to leaves from the late-booting stage to the flowering stage, with deionized water as a control (CK). Compared with CK, KP1, KP2, SA1, KP1 + SA1, and KP2 + SA1 alleviated the adverse effects of HT on the number of grains per panicle, seed set, and yield, among which SA1, KP2 + SA1, and KP1 were the best. The antioxidant enzyme (superoxide dismutase, peroxidase, and catalase) activities, levels of osmotic protective substances (soluble sugars, soluble proteins, and proline), and chlorophyll content were increased and the malonaldehyde content and leaf temperature were decreased in the SA1, KP2 + SA1, and KP1 treatments. Compared with those sown on April 25 and May 5, plants sown on May 15, May 25, and June 5 had suitable temperature conditions and presented increased grain yield and quality. Therefore, the application of SA1, KP2 + SA1, and KP1 and the use of an optimal sowing date (from May 15 to June 5) increased the rice yield and quality under HT.

SummarySeawater injection is widely used to improve oil recovery in offshore oil reservoirs. However, injecting seawater into reservoirs can cause many flow-assurance issues, such as scaling and reservoir souring, which are strongly related to the percentage of seawater breakthrough. Thermodynamic models have been developed to evaluate the effects of barite deposition on oil production, but the reservoir stripping effect has not been fully considered. In this study, a new model that incorporates both chemical reaction (barium and sulfate reaction) and physical reactions (ion adsorption/desorption) is developed to investigate the in-situ barite-deposition process. To the best of our knowledge, for the first time, ion adsorption/desorption is integrated by coupling the adsorption/desorption isotherm to the reservoir simulator. The barium and sulfate chemical reaction is modeled by incorporating the solubility product constant into the model. The model accuracy is verified through convergence rate tests and comparison with the coreflood experimental results. The simulation results of both barium and sulfate concentration profiles are greatly improved by integrating the ion adsorption/desorption process. The new physicochemical model is further used to investigate barite deposition under various scenarios. Simulation results indicate that most barite deposits are in the deep reservoir for the areal model. Barite that deposits in the reservoir before seawater breakthrough accounts for 45% of total barite deposition and the barite deposited during the seawater-breakthrough period makes up 54%, while the deposition during the tailing period, where the seawater fraction is larger than 95%, is negligible. For a homogeneous reservoir, the barite-deposition period at the near-wellbore area of the producer is between 30% and 65% of the seawater-breakthrough percentage, and heterogeneity leads to a broader deposition period. For vertical heterogeneous reservoirs, a considerable amount of barite forms in the wellbore, which accounts for 17% of total barite deposition. Based on the accurate simulation of barium and sulfate transport in the reservoir, barium and sulfate concentration profiles can be used to determine the seawater-breakthrough percentage and help optimize production operations that aim to mitigate flow assurance issues.

A Cd(ΙI)-based luminescent coordination polymer, namely [Cd(L)2(H2O)2]n (1), has been synthesized by 1-(tetrazo-5-yl)-4-(triazo-1-yl)benzene ligand (HL) and structurally characterized. The selectiv...

A major QTL for seed weight was fine-mapped in rapeseed, and a 24,482-bp deletion likely mediates the effect through multiple pathways. Exploration of the genes controlling seed weight is critical to the improvement of crop yield and elucidation of the mechanisms underlying seed formation in rapeseed (Brassica napus L.). We previously identified the quantitative trait locus (QTL) qSW.C9 for the thousand-seed weight (TSW) in a double haploid population constructed from F1 hybrids between the parental accessions HZ396 and Y106. Here, we confirmed the phenotypic effects associated with qSW.C9 in BC3F2 populations and fine-mapped the candidate causal locus to a 266-kb interval. Sequence and expression analyses revealed that a 24,482-bp deletion in HZ396 containing six predicted genes most likely underlies qSW.C9. Differential gene expression analysis and cytological observations suggested that qSW.C9 affects both cell proliferation and cell expansion through multiple signaling pathways. After genotyping of a rapeseed diversity panel to define the haplotype structure, it could be concluded that the selection of germplasm with two specific markers may be effective in improving the seed weight of rapeseed. This study provides a solid foundation for the identification of the causal gene of qSW.C9 and offers a promising target for the breeding of higher-yielding rapeseed.

Line scanning thermography (LST) is a fast non-destructive inspection (NDI) method for large-scale components. However, the current reconstruction algorithms for LST require the match between the frame rate and the scanning velocity. Moreover, these algorithms bring in spatial distortions. This paper proposes a non-orthogonal reconstructed space for LST. In such a space, the excitation motion in the line scanning process is described as a function of time delay, the moving velocity is estimated by the derived position map, and the reconstruction is achieved by image registration. The LST data are registered spatially by allowing the temporal misalignment among the pixels within the same reconstructed frame. The effectiveness of the proposed reconstruction algorithm is validated by both numerical simulations and experiments. The reconstruction results of experimental data indicate that the velocity is finely estimated so that the temporal alignment error is controlled within one pixel. Besides, no spatial distortions occur no matter how the frame rate and scanning velocity change. Furthermore, the Fourier phase image of the reconstructed LST reaches the diameter-to-depth ratio of 1.25 when inspecting a planar specimen with flat-bottom holes.

The oriental armyworm Mythimna separata (Walker) (Lepidoptera: Noctuidae) is a major migratory pest of cereal crops in East Asia, South Asia and Australia. To comprehensively understand the ecological tolerance of M. separata, we collected life table data of individuals from four consecutive generations reared under outdoor natural fluctuating temperatures from 15 April to 17 October 2018 in Yangling, Shaanxi, China. The results showed that the immature stage in early summer and summer were shorter than in spring and autumn. High mortality in late larval instar and pupal stages was observed in the summer generation. The adult pre-oviposition period in autumn was longer than the other seasons. The population in the earlier two seasons had heavier pupae and higher fecundity than the population in the latter two seasons. The intrinsic rate of increase and the finite rate of increase was the highest in early summer (r = 0.1292 day−1, λ = 1.1391 day−1), followed by spring (r = 0.1102 day−1, λ = 1.1165 day−1), and was the lowest in summer (r = 0.0281 day−1, λ = 1.0293 day−1). The results of this study would be useful to predict the population dynamics of M. separata and deepen our standing of the adaptiveness of this migratory pest in natural fluctuating ambient environments.

Purpose The purpose of this paper is to quickly manufacture full Cu3Sn-microporous copper composite joints for high-temperature power electronics applications and study the microstructure evolution and the shear strength of Cu3Sn at different bonding times. Design/methodology/approach In this paper, a novel structure of Cu/composite solder sheet/Cu was designed. The composite solder sheet was made of microporous copper filled with Sn. The composite joint was bonded by thermo-compression bonding under pressure of 0.6 MPa at 300°C. The microstructure evolution and the growth behavior of Cu3Sn at different bonding times were observed by electron microscope and metallographic microscope. The shear strength of the joint was measured by shear machine. Findings At initial bonding stage the copper atoms in the substrate and the copper atoms in the microporous copper dissolved into the liquid Sn. Then the scallop-liked Cu6Sn5 phases formed at the interface of liquid Sn/microporous copper and liquid Sn/Cu substrates. During the liquid Sn changing to Cu6Sn5 phases, Cu3Sn phases formed and grew at the interface of Cu6Sn5/Cu substrates and Cu6Sn5/microporous copper. After that the Cu3Sn phases continued to grow and the Cu3Sn-microporous copper composite joint with a thickness of 100 µm was successfully obtained. The growth rule of Cu3Sn was parabolic growth. The shear strength of the composite joints was about 155 MPa. Originality/value This paper presents a novel full Cu3Sn-microporous copper composite joint with high shear strength for high-temperature applications based on transient liquid phase bonding. The microstructure evolution and the growth behavior of Cu3Sn in the composite joints were studied. The shear strength and the fracture mechanism of the composite joints were studied.

Lead ion(Pb2+) is one of the most hazardous heavy metal ions in aquatic environments. Carbon materials and manganese dioxide(MnO2) have been shown to be prospective adsorbents to cope with the lead pollution. In this study, a novel hollow carbon@MnO2 composite nanofiber adsorbent was prepared by the combination of electrospinning and carbonization. The PAN nanofiber membrane is subjected to a pre-oxidation and carbonization process, and then the obtained carbon nanofibers react with KMnO4 solution during the hydrothermal process to develop the hollow carbon@MnO2 nanofibers. The hollow carbon@MnO2 nanofibers displayed a higher adsorption capacity of Pb2+ than carbon and MnO2/PDA/PAN nanofibers. The maximum adsorption capacity toward Pb2+ by hollow carbon@MnO2 nanofibers was 460.83 mg/g. After 5 adsorption-desorption cycles, the carbon@MnO2 nanofibers had a good recyclability and the removal efficiency remained 81.47%. Moreover, the removal efficiency of the hollow composite nanofibers for Pb2+ from real wastewater could reach 94.37%. This work shows a strategy for synthetics of the hollow carbon@MnO2 nanofibers, which exhibits a promising potential in actual wastewater treatment.

Reactive oxygen species (ROS)-induced nanosystems represent one of the most essential, efficient, and encouraging nanobactericides for eliminating bacterial infection concerning the increasing resistance threats of existing antibiotics. Among them, Fenton-type metal peroxide nanoparticles are exciting nanomaterials with intriguing physiochemical properties, yet the study of this antimicrobial agent is still in its infancy. Herein, a robust pH-responsive Fenton nanosystem is constructed by the assembly of copper peroxide nanodots in pomegranate-like mesoporous silica nanoshells (CuO2@SiO2) that are capable of self-supplying H2O2 and sustainably generating O2. The enhanced antimicrobial performance is attributed to the pH responsiveness and excellent Fenton catalytic activity through either the Cu2+-catalyzed conversion of H2O2 to detrimental ROS under acid treatment or in situ O2 evolution in neutral media. Moreover, in vitro and in vivo investigations demonstrate that this nanocomposite can exhibit boosted antimicrobial capabilities and can significantly accelerate skin wound closure, while retaining outstanding cytocompatibility and hemocompatibility. Given its excellent physicochemical and antimicrobial properties, the broad application of this nanocomposite in bacteria-associated wound management is anticipated.

Long-term exposure to excessive fluorine could cause damage to various tissues and organs in human and animals. However, there is no effective antidote to prevent and cure fluorosis except for avoiding fluoride intake. As an essential nutrient, riboflavin (VB2) has been identified to relieve oxidative stress and inflammation in animal tissues caused by other toxic substances, whether it can alleviate the damage caused by fluoride is unknown. For this, 32 ICR male mice were allocated to four groups of eight each. They were treated with 0 (distilled water), 100 mg/L sodium fluoride (NaF), 40 mg/L VB2, and their combination (100 mg/L NaF plus 40 mg/L VB2) via the drinking water for 90 consecutive days, respectively. The content of bone fluoride and the histomorphology of the main organs including liver, kidney, cerebral cortex, epididymis, small intestine, and colon were evaluated and pathologically scored. The results found that fluoride caused the pathological changes in liver, kidney, cerebral cortex, epididymis, small intestine, and colon at varying degrees, while riboflavin supplementation reduced significantly the accumulation of fluoride in bone, alleviated the morphological damage to cerebral cortex, epididymis, ileum, and colon. This study provides new clues for deeply exploring the mechanism of riboflavin intervention in fluorosis.

Renal ischemia-reperfusion injury (RI/R) is one of the main causes of acute renal injury and a common clinical disease with high morbidity and mortality. It is of great significance to deliver microRNAs (miRNAs) to cells and in vivo to realize gene regulation and treatment of related diseases. In this study, we reported that the nanocomplex FMN-17 could realize both therapeutic and functional monitoring simultaneously in vivo and in vitro. The nanocomplex comprised a cationic cell-penetrating peptide nona-arginine, a targeting ligand folic acid, a caspase-3 responsive moiety, and a Cy imaging moiety. The nanocomplex FMN-17 has been shown to deliver miR-17-5p efficiently and selectively into HK-2 cells and tissues. Treatment of HK-2 cells with the nanocomplex significantly increased the miR-17-5p level and inhibited apoptosis, as evident by reducing the expression of active caspase-3 and reactive oxygen species. Uptake of FMN-17 in vivo alleviated renal tissue injury by histological assessment. In summary, we designed and synthesized a new miRNA delivery system with high transfection efficiency, good therapeutic effect, and near-infrared imaging in renal ischemia/reperfusion injury.

s In this work, the creep behaviors of the graphitic and graphite-TiB2 composite as cathode materials have been investigated at high temperature aluminum electrolysis for discussing the role of TiB2 particles in creep resistance and mechanical properties connected with the microstructural evolution involving electrolyte penetration and cracking. The graphite-TiB2 composite has superior creep resistance over the graphitic sample. The corresponding creep strain can be as low as ~0.2% after the high temperature electrolysis. The addition of TiB2 particles greatly densifies the prepared composite with low porosity, resulting in the reduction of penetrating channels. The well-wetted TiB2 particles by liquid Al generate a protective dense Al layer on the surface of composite, greatly blocking the electrolyte penetration. In turn, liquid Al may slowly penetrate into the composite via the cracks formed channels. The fracture strength of the graphite-TiB2 composite increases from 41.6 MPa to 48.9 MPa after creep test at high temperature loading. Such improved properties should be attributed to the combined mechanism with reduced micro-cracks, decreased penetrating channels and the reinforcement due to addition of TiB2 particles.

Ni-rich materials, as one type of cathode materials for next-generation lithium-ion batteries, suffer from poor cycling stability due to severe structural degradation and surface deterioration. Lattice doping is an effective method to stabilize crystal structures, yet it has little effect on inhibiting surface side reactions. Herein, we demonstrate a strategy that can tailor the distribution of doping element Al in the entire secondary sphere in a controllable way to simultaneously stabilize the crystal structure and surface of the cathode material. The strategy takes advantage of the interdiffusion of elements at the solid-solid interface formed by aluminum-containing species that uniformly cover the surface of the Ni0.8Co0.1Mn0.1(OH)2 precursor at a high temperature. The extent of Al doping in the materials can be properly regulated by the amount of aluminum-containing species to generate uniform doping, gradient doping, and gradient doping with a thin Al coating layer. As a result, the Al gradient-doped cathode material exhibits excellent capacity retention of 81.9% after 500 cycles at 2C, which is much higher than the capacity retention of 54.3% for the pristine counterpart.

Li-metal batteries (LMBs) have attracted increasing attention because of the high energy density and low reduction potential of lithium metal. However, lithium dendrites generated by the uneven Li deposition during cycling seriously threaten the safety of the battery and limit its commercial application. Herein, we propose a novel and facile strategy by adding Cu(NO3)2 additive in carbonate electrolyte, which effectively inhibits the growth of lithium dendrites and prolongs the lifespan of LMBs based on LiMn2O4 as 4 V class cathode. Due to the contribution of Cu(NO3)2, the solid electrolyte interphase (SEI) is rapidly and stably formed attaching on lithium metal without evident lithium dendrites. Moreover, Cu ions can also participate in the formation of cathode electrolyte interphase (CEI), effectively suppressing the decomposition of electrolyte and dissolution of Mn in LiMn2O4. The Li|LiMn2O4 cell with additive maintains the capacity retention of 87.26% and an average coulombic efficiency of 99.40% when approching 1000 cycles at ~1.2 mA cm−2. Our findings shed light on understanding the role of transiton metal nitrate additive for stabilizing LMBs with long lifespan.

Magnetoelectric (ME) materials have been attracting extensive attention due to their potential applications. It is important to realize strong ME effect in one single material at sufficiently high temperature, and thus substantial efforts in searching for ME materials with strong ME coupling together and a comprehensive understanding of the underlying mechanism is necessary. Herein we focus on the Mn-doped linear ME material Co4-xMnxNb2O9, in which a large electric polarization driven by magnetic field emerges below its Neel temperature TN, by presenting the detailed characterizations on the structure, magnetism, and ME effect. It is revealed that an increasing Mn substitution x allows largely enhanced TN and gradually suppressed ME coefficient αME. This ME coupling suppression is attributed to the weak spin-orbit interaction of Mn2+ with respect to Co2+. It is indicated that the Dzyaloshinskii-Moriya (DM) interaction plays an important role in the ME coupling. The measured largest αME is found in For Co0.8Mn3.2Nb2O9, reaching up to 9.9 ps/m at 10 K while the TN reaches up to 102 K, exceeding most of the linear ME materials that have been reported.

The outbreak of COVID-19, caused by SARS-CoV-2 has spread across many countries globally. Greatly limited study concerned the effect of airborne pollutants on COVID-19 infection, while exposure to airborne pollutants may harm human health. This paper aimed to examine the associations of acute exposure to ambient atmospheric pollutants to daily newly COVID-19 confirmed cases in 41 Chinese cities. Using a generalized additive model with Poisson distribution controlling for temperature and relative humidity, we evaluated the association between pollutant concentrations and daily COVID-19 confirmation at single-city level and multi-city level. We observed a 10 μg/m3 rise in levels of PM2.5 (lag 0−14), O3 (lag 0−1), SO2 (lag 0) and NO2 (lag 0−14) were positively associated with relative risks of 1.050 (95% CI: 1.028, 1.073), 1.011 (1.007, 1.015), 1.052 (1.022, 1.083) and 1.094 (1.028, 1.164) of daily newly confirmed cases, respectively. Further adjustment for other pollutants did not change the associations materially (excepting in the model for SO2). Our results indicated that COVID-19 incidence may be susceptible to airborne pollutants such as PM2.5, O3, SO2 and NO2, and mitigation strategies of environmental factors are required to prevent spreading.

Background The widespread pandemic of novel coronavirus disease 2019 (COVID-19) poses an unprecedented global health crisis. In the United States (US), different state governments have adopted various combinations of non-pharmaceutical public health interventions (NPIs), such as non-essential business closures and gathering bans, to mitigate the epidemic from February to April, 2020. Quantitative assessment on the effectiveness of NPIs is greatly needed to assist in guiding individualized decision making for adjustment of interventions in the US and around the world. However, the impacts of these approaches remain uncertain. Methods Based on the reported cases, the effective reproduction number (Rt) of COVID-19 epidemic for 50 states in the US was estimated. Measurements on the effectiveness of nine different NPIs were conducted by assessing risk ratios (RRs) between Rt and NPIs through a generalized linear model (GLM). Results Different NPIs were found to have led to different levels of reduction in Rt. Stay-at-home contributed approximately 51% (95% CI 46–57%), wearing (face) masks 29% (15–42%), gathering ban (more than 10 people) 19% (14–24%), non-essential business closure 16% (10–21%), declaration of emergency 13% (8–17%), interstate travel restriction 11% (5–16%), school closure 10% (7–14%), initial business closure 10% (6–14%), and gathering ban (more than 50 people) 7% (2–11%). Conclusions This retrospective assessment of NPIs on Rt has shown that NPIs played critical roles on epidemic control in the US in the past several months. The quantitative results could guide individualized decision making for future adjustment of NPIs in the US and other countries for COVID-19 and other similar infectious diseases.

Large-size and -scale bismuth germanate (Bi4Ge3O12, BGO) crystals were grown in an oxidizing atmosphere using the modified Bridgman method. Although the growth condition has been optimized, we found a few reddish crystals, resulting in poor performance. In this work, the red-color-induced characteristic absorption bands corresponding to 506, 389, and 332 nm were studied by measuring the optical transmission and absorption spectra. A modified oxygen-annealing was applied to eliminate the reddish in BGO single crystal. Based on the comparison of the optical performance, the absorption band in the visible range of the reddish crystals disappeared after annealing. This phenomenon greatly improved the light output and energy resolution. The effects of annealing in reducing atmosphere were studied. The formation mechanism of crystal coloration was also discussed.

In this paper, we consider multi-state coherent systems that can be regarded as a series/parallel/recurrent connection of multi-state modules with binary/multi-state components. The multi-state (survival) signatures of such systems are presented in terms of multi-state (survival) signatures of related modules based on the structures. For a recurrent structure, the multi-state survival signature of the structure is also needed. The results established here are finally illustrated with a number of examples.

Two-dimensional (2D) transition metal oxides (TMOs) have attracted much attention for various applications, owing to the abundance of active sites, rapid ion transmission speed, and short carrier migration distance. However, the current preparation strategies are usually limited to producing intrinsically layered compounds or sacrificing template. Here, we report a universal strategy for preparing ultrathin porous 2D TMO nanosheets by chemical topological transformation of the corresponding transition metal selenides. We observed that the as-prepared 2D TMO nanosheets not only perfectly inherit the transition metal selenides’ 2D topological structure, but also possess numerous pore structures formed as a way to release the structural stress associated with lattice growth. As a proof of concept, ultrathin porous WO3, MoO3, and Co3O4 nanosheets were successfully prepared based on the in-situ oxidation of the corresponding ultrathin WSe2, MoSe2, and Co0.85Se, respectively. The outstanding sensing properties and photodetector performance displayed by the as-prepared porous 2D WO3 nanosheets further indicate the promising prospects of topology transformation for the preparation of porous 2D TMO nanosheets.

Treatment resistance of the tumors to photodynamic therapy (PDT) owing to O2 deficiency largely compromised the therapeutic efficacy, which could be addressed via modulating oxygen levels by using O2 self-enriched nanosystems. Here, we report on augmenting the O2-evolving strategy based on a biomimetic, catalytic nanovehicle (named as N/P@MCC), constructed by the catalase-immobilized hollow mesoporous nanospheres by enveloping a cancer cell membrane (CCM), which acts as an efficient nanocontainer to accommodate nitrogen-doped graphene quantum dots (N-GQDs) and protoporphyrin IX (PpIX). Inheriting the virtues of biomimetic CCM cloaking, the CCM-derived shell conferred N/P@MCC nanovehicles with highly specific self-recognition and homotypic targeting toward cancerous cells, ensuring tumor-specific accumulation and superior circulation durations. N-GQDs, for the first time, have been evidenced as a new dual-functional nanoagents with PTT and PDT capacities, enabling the generation of 1O2 for PDT and inducing local low-temperature hyperthermia for thermally ablating cancer cells and infrared thermal imaging (IRT). Leveraging the intrinsic catalytic features of catalase, such N/P@MCC nanovehicles effectively scavenged the excessive H2O2 to sustainably evolve oxygen for a synchronous O2 self-supply and hypoxia alleviation, with an additional benefit because the resulting O2 bubbles could function as an echo amplifier, leading to the sufficient echogenic reflectivity for ultrasound imaging. Concurrently, the elevated O2 reacted with N-GQDs and PpIX to elicit a maximally increased 1O2 output for augmented PDT. Significantly, the ultrasound imaging coupled with fluorescence imaging, IRT, performs a tumor-modulated trimodal bioimaging effect. Overall, this offers a paradigm to rationally explore O2 self-supply strategies focused on versatile nanotheranostics for hypoxic tumor elimination.

Surface-related-multiple wavefields constitute redundant information in conventional migration and can often be difficult to attenuate. However, when used for migration, multiple wavefields can improve subsurface illumination. Unfortunately, the process of imaging using multiples involves the management of crosstalk, which largely restricts its application. Crosstalk causes phantom images formed by spurious correlation of unrelated events in a migration process. These events can be unrelated orders of multiples in the source and receiver wavefields; they can also be one event associated with a reflector in the source wavefield and another event generated by a different reflector in the receiver wavefield. We have first examined crosstalk by explicitly investigating its generation mechanisms in a migration process and classifying it into different categories based on causality. Following this analysis, crosstalk can be predicted in a migration process and subtracted in the image domain; however, this method is usually difficult to apply due to the complexity of wavefield separation and adaptive subtraction. Furthermore, we develop different algorithms to attenuate the crosstalk, including a deconvolution imaging condition, a least-squares migration (LSM) method, and an advanced algorithm combining LSM with a deconvolution imaging condition. We evaluate these different strategies with synthetic examples. A deconvolution imaging condition can attenuate some crosstalk, but it is less effective at suppressing strong coherent crosstalk events. However, the LSM method can fundamentally address the crosstalk issue, and this approach is further optimized when combined with a deconvolution imaging condition.

Supercontinents signify self-organization in plate tectonics. Over the past ~2 billion years, three major supercontinents have been identified, with increasing age: Pangaea, Rodinia and Columbia. In a prototypal form, a cyclic pattern of continental assembly and breakup likely extends back to ~3 billion years ago, albeit on the smaller scale of Archaean supercratons, which, unlike global supercontinents, were tectonically segregated. In this Review, we discuss how the emergence of supercontinents provides a minimum age for the onset of the modern global plate tectonic network, whereas Archaean supercratons might reflect an earlier geodynamic and nascent tectonic regime. The assembly and breakup of Pangaea attests that the supercontinent cycle is intimately linked with whole-mantle convection. The supercontinent cycle is, consequently, interpreted as both an effect and a cause of mantle convection, emphasizing the importance of both top-down and bottom-up geodynamics, and the coupling between them. However, the nature of this coupling and how it has evolved remains controversial, resulting in contrasting models of supercontinent formation, which can be tested by quantitative geodynamic modelling and geochemical proxies. Specifically, which oceans close to create a supercontinent, and how such predictions are linked to mantle convection, are directions for future research. Repeated amalgamation and dispersal of continents over Earth history is known as the supercontinent cycle; however, the geodynamic processes driving this cyclicity remain debated. This Review synthesizes observations, plate reconstructions and geodynamic models of supercontinent, and older Archaean supercraton, cycles.

Oxide-derived Cu (OD-Cu) has been viewed as a highly active form for catalyzing the multielectron transfer of electrochemical CO2 reduction, but the underlying catalytic mechanism is still controversial. In the current study, the crystalline and valency factors that influence the CO2R activities of OD-Cu are revisited by employing single crystal Cu(111) foils that exclude convolutions from initial morphological and crystallographic heterogeneity. We observe that the overall CO2R performance, especially the C2H4 selectivity, correlates well with the initial oxidation level of the Cu(111) foil, of which the surface oxide layer is reduced into small fragments comprising rich grain boundaries and diversely orientated facets. Nonetheless, we find that the polycrystallinity and grain boundaries of OD-Cu, in this circumstance, are not the major causes of the observed activity enhancement. Instead, a transition state between the initial oxide and the finally reduced copper phases, as well as its longevity, dictates the catalytic property of OD-Cu in electrochemical CO2 reduction. Consequently, this work furnishes further evidence and in-depth understanding to help clarify the catalytic mechanism of OD-Cu in CO2R.

Gels are soft-elastic materials consisting of a three-dimensional crosslinked polymer network and liquid filling the space between this network. Numerous gels with unique physical properties have been synthesized and are widely used in our daily lives. However, all of these gels contain a substantial level of structural defects, as detected by scattering measurements. Despite the tremendous efforts made in recent decades to remove imperfections from gels, discernible signs of spatial defects have been persistently observed in gels. Researchers believe that gels are inherently heterogeneous. In this focus review, I briefly introduce a recent finding from our research group’s efforts to fabricate polymer gels free of spatial heterogeneities. The commonly observed scattering profiles for the spatial defects disappeared in the homogeneous gels. The newly observed scattering profiles are a benchmark for gel structures. Despite the tremendous efforts made in recent decades to remove imperfections from gels, discernible signs of spatial defects have been persistently observed in gels. Researchers believe that gels are inherently heterogeneous. In this focus review, I briefly introduce a recent finding from our research group’s efforts to fabricate polymer gels free of spatial heterogeneities via “bond percolation”. The commonly observed scattering profiles for the spatial defects disappeared in the homogeneous gels. The newly observed scattering profiles are a benchmark for gel structures.

Chiral phosphoric acid-catalyzed Pictet-Spengler reactions of 2-(1H-indolyl)aniline derivatives and isatins by the condensation/cyclization process have been realized. A series of enantioenriched 5',11'-dihydrospiro[indoline-3,6'-indolo[3,2-c]quinolin]-2-ones bearing quaternary stereogenic centers were obtained with excellent yields and up to >99% ee. This protocol was suitable for the Pictet-Spengler reactions of 2-(1-benzyl-5-methyl-1H-pyrrol-2-yl)aniline, and a variety of 1',5'-dihydro-spiro[indoline-3,4'-pyrrolo[3,2-c]quinolin]-2-ones could also be obtained in good yields and up to 88% ee.

Temperature-programmed reduction of transition-metal phosphate precursors is the most commonly used method for the preparation of transition-metal phosphides (a new class of versatile metal catalysts), but the reduction processes are still not clear. Here we describe the construction of a temperature-programmed reduction-infrared spectroscopy apparatus (TPR-IR) to analyze the gas flows during the reduction of nickel, molybdenum, and tungsten phosphates. PH3 and Pn+ species already appeared in the gas flows at low temperature (ca. 200 °C), and PH3 was involved in the formation of phosphides. The emission of PH3 and Pn+ during the reduction of the molybdenum and tungsten phosphates was smaller than that of the nickel phosphate. Ni2 P drastically accelerated the formation of the PH3 and Pn+ . These results explain why excess phosphorus is needed for the preparation of Ni2 P, and also demonstrate that the TPR-IR technique is an efficient method to understand the complex processes of catalyst preparation.