Theoretical study of the nonlinear magnon-phonon coupling in CoF2.

The coupling and interplay between magnon and phonon are important topics for spintronics and magnonics. In this work we studied the nonlinear magnon-phonon coupling in CoF2. First-principles calculations demonstrate that the antiferromagnetic resonance magnon drives a phonon with B1gcharacter; the oscillating driving force has a frequency twice of that of the magnon. Comparing with similar materials indicates a strong correlation between the strength of nonlinear magnon-phonon coupling and the orbital magnetic moment of the magnetic ion. This work pave the way for theoretical study of nonlinear magnon-phonon coupling.

Geographical provenance variation of growth and wood properties of 18-year-old Schima superba.

We analyzed the variation patterns of growth and wood properties of 24 different provenances of 18-year-old Schima superba in Jian'ou, Fujian Province. A total of 11 growth and wood indices were measured, including tree height, diameter at breast height, wood basic density and anatomical structure. We analyzed the geographical variation patterns of growth and wood properties, and the provenance areas were divided. Further, the excellent timber provenances were selected according to different uses. The results showed that the variation of growth traits, which was 17.6%-27.3% with mean value of 22.4%, was larger than that of wood properties (7.0%-21.0%, mean 12.7%). Growth properties and some wood properties (fiber length, fiber lumen diameter and fiber cell wall thickness) had significant differences among provenances. Growth traits were not correlated with fiber traits, and they could be selected independently without emphasis on other traits. There was significant correlation between the longitudinal and radial growth indicators of wood properties, but they were not correlated with the wood basic density, which could be selected independently. In addition, the growth and wood properties were significantly influenced by temperature and precipitation, which showed a latitudinal variation pattern. According to Q-type clustering analysis, 24 provenances could be divided into four categories, of which southern provenances from distribution area of S. superba had vigorous growth and supper wood properties. They had smaller microfibril angle, higher maturity, longer fiber length, and thicker fiber cell wall. Finally, five excellent provenances were selected according to pulpwood and building use.

Theoretical Study on the Raman Effect Due to Magnons in Two-Dimensional Magnets.

Raman spectroscopy is one of the most useful experimental tools for studying elementary excitations in two-dimensional (2D) materials. The Raman scattering due to phonons was widely employed for detecting structural evolutions, especially those caused by magnetic phase transitions in 2D magnets. A first-principles theory of the Raman scattering effect caused by magnons is still lacking. We theoretically study the magnon Raman effect in 2D magnet CrI3. We propose a first-principles method and have calculated the intensity of circularly polarized Raman signals due to different magnon modes in the CrI3 monolayer and bilayers. The calculated Raman intensities due to magnons in the CrI3 monolayer and the rhombohedral bilayer are consistent with the selection rule deduced from the magnon pseudoangular moment and the parity of magnon modes. We also find that the selection rule is violated in the symmetry-broken monoclinic bilayer due to interlayer coupling.

Total Syntheses of Polycyclic Diterpenes Phomopsene, Methyl Phomopsenonate, and iso-Phomopsene via Reorganization of C-C Single Bonds.

The first total syntheses of polycyclic diterpenes phomopsene (1), methyl phomopsenonate (2), and iso-phomopsene (3) have been accomplished through the unusual cascade reorganization of C-C single bonds. This approach features: (i) a synergistic Nazarov cyclization/double ring expansions in one-step, developed by authors, to rapid and stereospecific construction of the 5/5/5/5 tetraquinane scaffold bearing contiguous quaternary centers and (ii) a one-pot strategic ring expansion through Beckmann fragmentation/recombination to efficiently assemble the requisite 5/5/6/5 tetracyclic skeleton of the target molecules 1-3. This work enables us to determine that the correct structure of iso-phomopsene is, in fact, the C7 epimer of the originally assigned structure. Finally, the absolute configurations of three target molecules were confirmed through enantioselective synthesis.

Revealing 3D Ripple Structure and Its Dynamics in Freestanding Monolayer MoSe2 by Single-Frame 2D Atomic Image Reconstruction.

An atomic-scale ripple structure has been revealed by electron tomography based on sequential projected atomic-resolution images, but it requires harsh imaging conditions with negligible structure evolution of the imaged samples. Here, we demonstrate that the ripple structure in monolayer MoSe2 can be facilely reconstructed from a single-frame scanning transmission electron microscopy (STEM) image collected at designated collection angles. The intensity and shape of each Se2 atomic column in the single-frame projected STEM image are synergistically combined to precisely map the slight misalignments of two Se atoms induced by rippling, which is then converted to three-dimensional (3D) ripple distortions. The dynamics of 3D ripple deformation can thus be directly visualized at the atomic scale by sequential STEM imaging. In addition, the reconstructed images provide the first opportunity for directly testing the validity of the classical theory of thermal fluctuations. Our method paves the way for a 3D reconstruction of a dynamical process in two-dimensional materials with a reasonable temporal resolution.

Different photoprotective strategies for white leaves between two co-occurring Actinidia species.

At the outer canopy, the white leaves of Actinidia kolomikta can turn pink but they stay white in A. polygama. We hypothesized that the different leaf colors in the two Actinidia species may represent different photoprotection strategies. To test the hypothesis, leaf optical spectra, anatomy, chlorophyll a fluorescence, superoxide (O2 ˙- ) concentration, photosystem II photo-susceptibility, and expression of anthocyanin-related genes were investigated. On the adaxial side, light reflectance was the highest for white leaves of A. kolomikta, followed by its pink leaves and white leaves of A. polygama, and the absorptance for white leaves of A. kolomikta was the lowest. Chlorophyll and carotenoid content of white and pink leaves in A. kolomikta were significantly lower than those of A. polygama, while the relative anthocyanin content of pink leaves was the highest. Chloroplasts of palisade cells of white leaves in A. kolomikta were not well developed with a lower maximum quantum efficiency of PSII than the other types of leaves (pink leaves of A. kolomikta and white leaves of A. Polygama at the inner/outer canopy). After high light treatment from the abaxial surface, Fv /Fm decreased to a larger extent for white leaves of A. kolomikta than pink leaf and white leaves of A. polygama, and its non-photochemical quenching was also the lowest. White leaves of A. kolomikta showed higher O2 ˙- concentration compared to pink leaves under the same strong irradiance. The expression levels of anthocyanin biosynthetic genes in pink leaves were higher than in white leaves. These results indicate that white leaves of A. kolomikta apply a reflection strategy for photoprotection, while pink leaves resist photoinhibition via anthocyanin accumulation.

Heterogeneous Structural Color Conductive Photonic Organohydrogel Fibers with Alternating Single and Dual Networks.

Intelligent interactive electronic devices can dynamically respond to and visualize various stimuli, promoting the rapid development of flexible electronics. In this paper, an alternating single- and dual-network design strategy was developed for ingeniously constructing an interactive electronic fiber sensor with heterogeneous structural color (HSCEF sensor). The resulting sensor can rapidly output the synchronous electrical and optical dual signals under strain by adjusting the transport distance of conductive ions and the lattice spacing of the photonic crystal (∼200 ms). Meanwhile, the addition of low-freezing-point glycerol endowed the HSCEF sensor with excellent low-temperature tolerance (-25 °C) and cyclic stability. Notably, benefiting from the alternating single- and dual-network structure, the HSCEF sensor exhibits attractive heterogeneous structural color, which achieves colorimetric changes in the full visible light region with high mechanochromic sensitivity (2.25 nm %-1) and large wavelength shift (Δλ ∼ 225 nm). An intelligent wearable interactive sensor is finally used for real-time dynamic detection of joint movements, realizing precise resolution of different amplitudes. This work provides a general strategy to transform conventional photonic gels into heterogeneous structural color ones, and the developed new interactive sensor with rich optical information could be further used for visual health and exercise monitoring, intelligent soft robotics, wearable sensors, etc.

Structure of Amorphous Two-Dimensional Materials: Elemental Monolayer Amorphous Carbon versus Binary Monolayer Amorphous Boron Nitride.

The structure of amorphous materials has been debated since the 1930s as a binary question: amorphous materials are either Zachariasen continuous random networks (Z-CRNs) or Z-CRNs containing crystallites. It was recently demonstrated, however, that amorphous diamond can be synthesized in either form. Here we address the question of the structure of single-atom-thick amorphous monolayers. We reanalyze the results of prior simulations for amorphous graphene and report kinetic Monte Carlo simulations based on alternative algorithms. We find that crystallite-containing Z-CRN is the favored structure of elemental amorphous graphene, as recently fabricated, whereas the most likely structure of binary monolayer amorphous BN is altogether different than either of the two long-debated options: it is a compositionally disordered "pseudo-CRN" comprising a mix of B-N and noncanonical B-B and N-N bonds and containing "pseudocrystallites", namely, honeycomb regions made of noncanonical hexagons. Implications for other nonelemental 2D and bulk amorphous materials are discussed.

Engineering the Crack Structure and Fracture Behavior in Monolayer MoS2 By Selective Creation of Point Defects.

Monolayer transition-metal dichalcogenides, e.g., MoS2 , typically have high intrinsic strength and Young's modulus, but low fracture toughness. Under high stress, brittle fracture occurs followed by cleavage along a preferential lattice direction, leading to catastrophic failure. Defects have been reported to modulate the fracture behavior, but pertinent atomic mechanism still remains elusive. Here, sulfur (S) and MoSn point defects are selectively created in monolayer MoS2 using helium- and gallium-ion-beam lithography, both of which reduce the stiffness of the monolayer, but enhance its fracture toughness. By monitoring the atomic structure of the cracks before and after the loading fracture, distinct atomic structures of the cracks and fracture behaviors are found in the two types of defect-containing monolayer MoS2 . Combined with molecular dynamics simulations, the key role of individual S and MoSn point defects is identified in the fracture process and the origin of the enhanced fracture toughness is elucidated. It is a synergistic effect of defect-induced deflection and bifurcation of cracks that enhance the energy release rate, and the formation of widen crack tip when fusing with point defects that prevents the crack propagation. The findings of this study provide insights into defect engineering and flexible device applications of monolayer MoS2 .

A novel tool for predicting the risk of central lymph node metastasis in patients with papillary thyroid microcarcinoma: a retrospective cohort study.

INTRODUCTION: Central lymph node status in papillary thyroid microcarcinoma (PTMC) plays an important role in treatment decision-making clinically, however, it is not easy to predict central lymph node metastasis (CLNM). The present work focused on finding the more rational alternative for evaluating central lymph node status while identifying influencing factors to construct a model to predict CLNM incidence. METHODS: In this study, we retrospectively analyzed the typical sonographic and clinicopathologic features of 546 PTMC patients who underwent surgery, among which, the data of 382 patients were recruited in the training cohort and that of 164 patients in the validation cohort. Based on the outcome of the training cohort, significant influencing factors were further identified through univariate analysis and were considered as independent variables in multivariable logistic regression analysis and incorporated in and presented with a nomogram. RESULTS: In total, six independent predictors, including the age, sex, tumor size, multifocality, capsular invasion, Hashimotos thyroiditis were entered into the nomogram. Both internal validation and external validation revealed the favorable discrimination of our as-constructed nomogram. Calibration curves exhibited high consistency. As suggested by decision-curve analyses, the as-constructed nomogram might be applied in clinic. Besides, the model also distinguished patients according to risk stratification. CONCLUSIONS: The novel nomogram containing remarkable influencing factors for CLNM cases was established in the present work. The nomogram can assist clinicians in clinical decision-making.

An efficient approach to angular tricyclic molecular architecture via Nazarov-like cyclization and double ring-expansion cascade.

A modular and efficient method for constructing angular tri-carbocyclic architectures containing quaternary carbon center(s) from 1,3-dicycloalkylidenyl ketones is established, which involves an unconventional synergistic cascade of a Nazarov cyclization and two ring expansions. It features high selectivity, mild conditions and convenient operation, wide scope and easy availability of substrate. Substitution with R1 and R2 at the 4πe-system with electron-donating group favors this reaction, while that with electron-withdrawing group or proton disfavors. The electron-donating group as R1 directs the initial ring expansion at its own site, while the p-π- or n-π- associated substituent as R2 favors selectively the later ring expansion near its location because of the beneficial maintenance of an original conjugated system. The stereoselectivity has proved to be governed by either the steric effect of R3 and R4 at the expanded rings, or the migration ability of the migrating atom. Density Functional Theory calculation suggests the initial Nazarov cyclization would be the rate-determining step. A racemic total synthesis of the natural (±)-waihoensene is realized in 18 steps by use of this methodology.

Synergetic stability enhancement with magnesium and calcium ion substitution for Ni/Mn-based P2-type sodium-ion battery cathodes.

The conventional P2-type cathode material Na0.67Ni0.33Mn0.67O2 suffers from an irreversible P2-O2 phase transition and serious capacity fading during cycling. Here, we successfully carry out magnesium and calcium ion doping into the transition-metal layers (TM layers) and the alkali-metal layers (AM layers), respectively, of Na0.67Ni0.33Mn0.67O2. Both Mg and Ca doping can reduce O-type stacking in the high-voltage region, leading to enhanced cycling endurance, however, this is associated with a decrease in capacity. The results of density functional theory (DFT) studies reveal that the introduction of Mg2+ and Ca2+ make high-voltage reactions (oxygen redox and Ni4+/Ni3+ redox reactions) less accessible. Thanks to the synergetic effect of co-doping with Mg2+ and Ca2+ ions, the adverse effects on high-voltage reactions involving Ni-O bonding are limited, and the structural stability is further enhanced. The finally obtained P2-type Na0.62Ca0.025Ni0.28Mg0.05Mn0.67O2 exhibits a satisfactory initial energy density of 468.2 W h kg-1 and good capacity retention of 83% after 100 cycles at 50 mA g-1 within the voltage range of 2.2-4.35 V. This work deepens our understanding of the specific effects of Mg2+ and Ca2+ dopants and provides a stability-enhancing strategy utilizing abundant alkaline earth elements.

Engineering Dual Single-Atom Sites on 2D Ultrathin N-doped Carbon Nanosheets Attaining Ultra-Low-Temperature Zinc-Air Battery.

Herein, a novel dual single-atom catalyst comprising adjacent Fe-N4 and Mn-N4 sites on 2D ultrathin N-doped carbon nanosheets with porous structure (FeMn-DSAC) was constructed as the cathode for a flexible low-temperature Zn-air battery (ZAB). FeMn-DSAC exhibits remarkable bifunctional activities for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Control experiments and density functional theory calculations reveal that the catalytic activity arises from the cooperative effect of the Fe/Mn dual-sites aiding *OOH dissociation as well as the porous 2D nanosheet structure promoting active sits exposure and mass transfer during the reaction process. The excellent bifunctional activity of FeMn-DSAC enables the ZAB to operate efficiently at ultra-low temperature of -40 °C, delivering 30 mW cm-2 peak power density and retaining up to 86 % specific capacity from the room temperature counterpart.

The magnetic proximity effect at the MoS2/CrI3interface.

The vicinity to a two-dimensional magnetic material provides a simple and effective way to break the valley degeneracy of transition-metal dichalcogenides because of the magnetic proximity effect. Based on first-principles calculations, we study the band structure of a MoS2/CrI3van der Waals heterostructure and its manipulation by vertical electric fields. A huge valley splitting of about 19.60 meV, equivalent to an external magnetic fields of about 89.0 T can be generated by an electric field of 0.115 V Å-1. The electric field causes discontinuous changes in the valley splitting. The electric field drives the bands of MoS2across those of CrI3. At the critical electric fields, the interlayer orbital hybridization leads to the energy level repulsion and an abrupt exchange of the band index. We also study the effect of interlayer distance on the valley splitting and observe a more significant electric field modulation. This work deepens our understanding on the interfacial magnetic proximity effect as a result of the orbital hybridization across the van der Waals gap.

Effects of pressure and strain on physical properties of VI3.

The van der Waals ferromagnetic material VI3is a magnetic Mott insulator. In this work, we investigate the effects of isotropic and anisotropic pressure on the atomic structure and the electronic structure of VI3using the first-principles method. The in-plane strain induces structural distortion and breaks the three-fold rotational symmetry of the lattice. Both the in-plane and out-of-plane strain widen the conduction and the valence bands, reduce the energy band gap and drive VI3from a semiconductor to a three-dimensional metal. The structural distortion is not the cause of insulator-to-metal transition. Calculations of the magnetocrystalline anisotropy energy indicate an easy-axis to easy-plane transition when the pressure is higher than 2 GPa. The ferromagnetic Curie temperature falls from 63 K at 0 GPa to 25 K at 6 GPa.

Straw biochar enhanced removal of heavy metal by ferrate.

This study demonstrated that As(III) was appreciably removed by ferrate in the presence of straw biochar. Removal efficiency of As in ferrate/biochar system was over 91%, increased by 34% compared with ferrate alone ([biochar]0 = 10 mg/L, [ferrate]0 = 6 mg/L, [As(III)]0 = 200 µg/L). In the reaction process, As(III) was oxidized to As(V) mainly by ferrate, while ferrate was reduced into ferric (hydr)oxides and coated on the biochar. Biochar was oxidized in the reaction and its surface area, pore volume and the amount of Lewis acid functional groups were substantially improved, which provided interaction sites for As adsorption. Analysis of hydrodynamic diameter and zeta potential revealed that biochar interacted with the ferrate resulted ferric oxides and enlarged the Fe-C-As particle/floc, which promoted their settlement and thus the liquid-solid separation of As. As(V) was adsorbed on the surface of biochar and ferric (hydr)oxides through hydrogen bond, electrostatic attraction and As-(OFe) bond. Ferrate/biochar was not only effective for As removal, but removed 73.31% of As, 50.38% of Cd, and 75.27% of Tl when these hazardous species synchronously existed in polluted water (initial content: As, 100 µg/L; Cd, 50 µg/L; Tl, 1 µg/L). The combination of ferrate with biochar has potential for the remediation of hazardous species polluted water.

Upregulated PD-L1 delays human neutrophil apoptosis and promotes lung injury in an experimental mouse model of sepsis.

PD-L1 is a ligand for PD-1, and its expression has been shown to be upregulated in neutrophils harvested from septic patients. However, the effect of PD-L1 on neutrophil survival and sepsis-induced lung injury remains largely unknown. In this study, PD-L1 expression correlated negatively with rates of apoptosis in human neutrophils harvested from patients with sepsis. Coimmunoprecipitation assays on control neutrophils challenged with interferon-γ and LPS showed that PD-L1 complexes with the p85 subunit of phosphatidyl 3-kinase (PI3K) to activate AKT-dependent survival signaling. Conditional CRE/LoxP deletion of neutrophil PD-L1 in vivo further protected against lung injury and reduced neutrophil lung infiltration in a cecal ligation and puncture (CLP) experimental sepsis animal model. Compared with wild-type animals, PD-L1-deficient animals presented lower levels of plasma tumor necrosis factor-α and interleukin-6 (IL-6) and higher levels of IL-10 after CLP, and reduced 7-day mortality in CLP PD-L1-knockout animals. Taken together, our data suggest that increased PD-L1 expression on human neutrophils delays cellular apoptosis by triggering PI3K-dependent AKT phosphorylation to drive lung injury and increase mortality during clinical and experimental sepsis.

Transcriptome and Biochemical Analysis Jointly Reveal the Effects of Bacillus cereus AR156 on Postharvest Strawberry Gray Mold and Fruit Quality.

Postharvest strawberry is susceptible to gray mold disease caused by Botrytis cinerea, which seriously damage the storage capacity of fruits. Biological control has been implicated as an effective and safe method to suppress plant disease. The aim of this study is to evaluate the postharvest disease control ability of Bacillus cereus AR156 and explore the response of strawberry fruit to this biocontrol microorganism. Bacillus cereus AR156 treatment significantly suppressed gray mold disease and postponed the strawberry senescence during storage. The bacterium pretreatment remarkably enhanced the reactive oxygen-scavenging and defense-related activities of enzymes. The promotion on the expression of the encoding-genes was confirmed by quantitative real-time PCR (qRT-PCR) that significantly increased the expression of the marker genes of salicylic acid (SA) signaling pathway, such as PR1, PR2, and PR5, instead of that of the jasmonic acid (JA)/ethylene (ET) pathway, which was also shown. Moreover, through transcriptome profiling, about 6,781 differentially expressed genes (DEGS) in strawberry upon AR156 treatment were identified. The gene ontology (GO) classification and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway enrichment indicated that AR156 altered the transcription of numerous transcription factors and genes involved in the SA-related plant disease resistance, metabolism, and biosynthesis of benzoxazinoids and flavonoids. This study offered a non-antagonistic Bacillus as a method for postharvest strawberry storage and disease control, and further revealed that the biocontrol effects were arisen from the induction of host responses on the transcription level and subsequent resistance-related substance accumulation.