Core-Hole Excitation Spectra of the Oxides and Hydrates of Fullerene C60 and Azafullerene C59N.

The interaction of fullerenes and their derivatives with environmental molecules such as oxygen or water was crucial for the rational design of low-dimensional materials and devices. In this paper, the near-edge X-ray absorption fine structure (NEXAFS), X-ray emission spectroscopy (XES) and X-ray photoelectron spectroscopy (XPS) shake-up satellites were employed to distinguish the oxides and hydrates of the fullerene C60 and azafullerene C59N families. The study includes various isomers, such as the open [5,6] and closed [6,6] isomers of C60O, C60H(OH), C60-O-C60, C60H-O-C60H, C59N(OH) and C59N-O-C59N, based on density functional theory. These soft X-ray spectra offered comprehensive insights into the molecular orbitals of these azafullerene molecular groups. The oxygen K-edge NEXAFS, carbon and oxygen K-edge XPS shake-up satellite spectra provided valuable tools for distinguishing oxides or hydrates of fullerene C60 and azafullerene C59N. Our findings could significantly benefit the development of fullerene functional molecular materials and expand the application scope of soft X-ray spectroscopy as a molecular fingerprinting tool for the fullerene family.

Exploring the effect of LncRNA DANCR to regulate the Keap1-Nrf2/ARE pathway on oxidative stress in rheumatoid arthritis.

INTRODUCTION: Aberrant expression of long noncoding RNAs (LncRNAs) can regulate oxidative stress in rheumatoid arthritis (RA). This study focused on investigating the effects of LncRNA differentiation antagonizing nonprotein coding RNA (DANCR) regulation of Keap1-Nrf2/ARE pathway on inflammation and oxidative stress in RA. METHODS: The levels of LncRNA DANCR/miR-486-3p/Keap1 in peripheral blood of 30 RA groups and 30 normal subjects were examined, and the association of LncRNA DANCR with inflammatory indicators of RA was investigated. We stimulated fibroblast-like synoviocytes (FLS) from RA patients with tumor necrosis factor α and subsequently performed in vitro cellular assays to construct overexpression plasmids and small interfering RNAs of LncRNA DANCR to investigate the relationship between LncRNA DANCR and FLSs viability and migration in RA, as well as the effects on cellular oxidative stress factors and Keap1-Nrf2/ARE pathway; molecular biology analysis was used to predict microRNAs that can bind LncRNA DANCR, and luciferase verified the binding sites of LncRNA DANCR with Keap1 and miR-486-3p; to further refine the gene and protein expression results, we used reverse transcription-quantitative polymerase chain reaction and immunoblotting assays. RESULTS: In both groups of peripheral blood mononuclear cells, the expression levels of LncRNA DANCR and Keap1 messenger RNA were higher in the RA group than in the normal control group, and the opposite was true for miR-486-3p; LncRNA DANCR was positively correlated with total antioxidant capacity (TAOC), IL6, IL17, malondialdehyde (MDA), but not with IL11, rheumatoid factor, cyclic citrullinated peptide, superoxide dismutase (SOD), with 28-joint disease activity score, reactive oxygen species, C-reactive protein, and erythrocyte sedimentation rate were negatively correlated; overexpression of LncRNA DANCR stimulated the Keap1-Nrf2/ARE pathway, decreased the expression of IL10, SOD, TAOC, and increased the expression levels of MDA, IL11, IL-17, PD-L1, and silencing of LncRNA DANCR was the opposite, but knockdown of miR-486-3p or overexpression of keap1 reversed the expression of the above-mentioned inflammatory and oxidative factors. In addition, pcDNA-DANCR clearly showed stronger cell invasion and migration ability and exacerbated its inflammatory response, which may be related to the regulatory role of miR-486-3p and Keap1-Nrf2/ARE signaling pathway, and we verified their targeting relationship using dual luciferase, showing that DANCR could regulate Keap1-Nrf2/ARE through miR-486-3p modulates the Keap1-Nrf2/ARE pathway and affects inflammatory and oxidative responses in RA patients. CONCLUSION: The low-expressed LncRNA DANCR may regulate the Keap1-Nrf2/ARE pathway and suppress the inflammatory and oxidative responses in RA patients.

A velocity-guided Harris hawks optimizer for function optimization and fault diagnosis of wind turbine.

Harris hawks optimizer (HHO) is a relatively novel meta-heuristic approach that mimics the behavior of Harris hawk over the process of predating the rabbits. The simplicity and easy implementation of HHO have attracted extensive attention of many researchers. However, owing to its capability to balance between exploration and exploitation is weak, HHO suffers from low precision and premature convergence. To tackle these disadvantages, an improved HHO called VGHHO is proposed by embedding three modifications. Firstly, a novel modified position search equation in exploitation phase is designed by introducing velocity operator and inertia weight to guide the search process. Then, a nonlinear escaping energy parameter E based on cosine function is presented to achieve a good transition from exploration phase to exploitation phase. Thereafter, a refraction-opposition-based learning mechanism is introduced to generate the promising solutions and helps the swarm to flee from the local optimal solution. The performance of VGHHO is evaluated on 18 classic benchmarks, 30 latest benchmark tests from CEC2017, 21 benchmark feature selection problems, fault diagnosis problem of wind turbine and PV model parameter estimation problem, respectively. The simulation results indicate that VHHO has higher solution quality and faster convergence speed than basic HHO and some well-known algorithms in the literature on most of the benchmark and real-world problems.

New Reactions for the Formation of Organic Nitrate in the Atmosphere.

Organic nitrates make an important contribution to the formation of secondary organic aerosols, but the formation mechanisms of organic nitrates are not fully understood at the molecular level. In the present work, we explore a new route for the formation of organic nitrates in the reaction of formaldehyde (HCHO) with nitric acid (HNO3) catalyzed by water (H2O), ammonia (NH3), and dimethylamine ((CH3)2NH) using theoretical methods. The present results using CCSD(T)-F12a/cc-pVTZ-F12//M06-2X/MG3S unravel that dimethylamine has a stronger catalytic ability in the reaction of HCHO with HNO3, reducing the barrier by 21.97 kcal/mol, while water and ammonia only decrease the energy barrier by 7.35 and 13.56 kcal/mol, respectively. In addition, the calculated kinetics combined with the corresponding concentrations of these species show that the HCHO + HNO3 + (CH3)2NH reaction can compete well with the naked HCHO + HNO3 reaction at 200-240 K, which may make certain contributions to the formation of organic nitrates under some atmospheric conditions.

Two-dimensional ZrC2 as a novel anode material with high capacity for sodium ion battery.

Rational design of high-performance anode materials is of paramount importance for developing rechargeable lithium ion batteries (LIBs) and sodium ion batteries (SIBs). In this work, a ZrC2 monolayer is predicted by performing the particle swarm optimization (PSO) algorithm. The high energetic, dynamic, and thermal stabilities of the ZrC2 monolayer are confirmed by cohesive energy, phonon dispersion, and molecular dynamics simulations, respectively. Unexpectedly, we find that the theoretical specific capacity for Na on the ZrC2 monolayer reaches as high as 932 mA h g-1, which is even higher than that of Li. Meanwhile, the diffusion energy barrier of Na on the ZrC2 monolayer is only 0.02 eV, ensuring the ultrafast charge/discharge rate. Additionally, the calculated open-circuit voltage (OCV) suggests that the change of Na intercalation voltage is steady. Therefore, our results consistently demonstrate that the ZrC2 monolayer can be an ideal anode material for SIBs.

Two-dimensional ScN with high carrier mobility and unexpected mechanical properties.

Two-dimensional (2D) semiconductors with desirable bandgaps and high carrier mobility have great potential in electronic and optoelectronic applications. In the present work, 2D M-ScN, H-ScN, and O-ScN are predicted by the swarm-intelligent global structure search method. The low formation energies and high dynamical and thermal stabilities indicate the high feasibility of experimental synthesis of these ScN monolayers. The electronic structure calculations reveal that M-ScN and O-ScN are both direct bandgap semiconductors with the bandgaps of 1.39 and 2.14 eV, respectively, while H-ScN has a large indirect bandgap of 3.21 eV. In addition, both M-ScN and H-ScN exhibit ultra-high electron mobilities (3.09 × 104 cm2 V-1 s-1 and 1.22 × 104 cm2 V-1 s-1, respectively). More notably, O-ScN is found to be a promising 2D auxetic and ferroelastic material. The values of negative Possion's ratios and reversible strain of this monolayer are predicted to be -0.27% and 15%, respectively.

Sc/C codoping effect on the electronic and optical properties of the TiO2 (101) surface: a first-principles study.

Extension of the light absorption range and a reduction of the possibility of the photo-generated electron-hole pair recombination are the main tasks to break the bottleneck of the photocatalytic application of TiO2. In this paper, we systematically investigate the electronic and optical properties of Sc-doped, C-doped, and Sc/C-codoped TiO2 (101) surfaces using spin-polarized DFT+U calculations. The absorption coefficient of the Sc/C-codoped TiO2 (101) surfaces were enhanced the most compared with the other two doped systems in the high energy region of visible light, which can be attributed to the shallow impurity states. Furthermore, we studied the optical absorption properties with the change of the impurity concentration. The Sc/C-codoped TiO2 (101) surface with 5.56% impurity concentration exhibited optimal photocatalytic performance in the visible region. These results may be helpful for designing the high-performance of the photocatalysts by doping.

Atom-Pair Catalysts Supported by N-Doped Graphene for the Nitrogen Reduction Reaction: d-Band Center-Based Descriptor.

Achieving an effective nitrogen reduction reaction (NRR) under mild conditions is a great challenge for industrial ammonia synthesis. NRR is often accompanied by a competing hydrogen evolution reaction (HER), which causes an extremely low Faraday efficiency. We systematically investigated the NRR reactivity of atom-pair catalysts (APCs) formed by 20 transition metal (TM) elements supported by N-doped graphene via three reaction pathways. By analyzing the correlation among the limiting potential, Gibbs free energy, and d-band center, we evaluated the activity trends of the TM APCs. Our computations revealed that the enzymatic pathway is the most suitable reaction pathway for the TM APCs, and the intrinsic activity trend of these APCs can be determined by the d-band center-based descriptor, which has a simple linear correlation with the bonding/antibonding orbital population. In addition, the NRR APCs with excellent performance have been screened out through selective analysis of the competing HER in the electrocatalytic NRR process.

Dynamics of an SEIR model with infectivity in incubation period and homestead-isolation on the susceptible.

In this paper, we present an SEIR epidemic model with infectivity in incubation period and homestead-isolation on the susceptible. We prove that the infection-free equilibrium point is locally and globally asymptotically stable with condition R 0 < 1 . We also prove that the positive equilibrium point is locally and globally asymptotically stable with condition R 0 > 1 . Numerical simulations are employed to illustrate our results. In the absence of vaccines or antiviral drugs for the virus, our results suggest that the governments should strictly implement the isolation system to make every effort to curb propagation of disease during the epidemic.

Single Pt atoms stabilized on Mo2TiC2O2 for hydrogen evolution: A first-principles investigation.

Single-atom catalysis offers an effective way to reduce the amount of used noble metals and maximizes their catalytic activity. We systematically explore electrocatalytic performances of Pt doped Mo2TiC2O2 monolayer by the first principles calculations. Our results show that the presence of donor defects in Mo2TiC2O2 can always increase the reaction free energy of hydrogen adsorption and further promotes the performance in hydrogen evolution reaction (HER). More interestingly, the substitution of Pt for O in the Mo2TiC2 can modify the free energy to an ideal value and is responsible for the significantly enhanced catalytic activity. Furthermore, the large value of diffusion barrier indicates that single Pt atoms can be stabilized onto the O vacancy sites, which can effectively prevent them to aggregate into nanoparticles. Our works are useful for understanding the recent experimental observations and pave the way for further experimental improvements of catalytic activity for the HER.

Interface Schottky barrier in Hf2NT2/MSSe (T = F, O, OH; M = Mo, W) heterostructures.

The Schottky barrier height (SBH) is a critical parameter that determines the carrier transfer at metal/semiconductor interfaces. In this work, the interfacial properties of Hf2NT2/MSSe (T = F, O, OH; M = Mo, W) heterostructures are systematically investigated using first-principles calculations. It is found that, for MoSSe and WSSe, the use of S or Se atomic layers in contact with Hf2NT2 can give significantly different SBHs. In addition, SB-free contact for electron injection can be realized for F-S interfaces in Hf2NF2/MoSSe and Hf2NF2/WSSe heterostructures. Furthermore, the SBHs of the heterostructures can be tuned by applying compressive strain and p-type ohmic contact can be obtained for O-Se interfaces in Hf2NO2/MoSSe and Hf2NO2/WSSe heterostructures. This work proposes a feasible strategy to regulate the SBHs of interfaces.

Impulsive vaccination and dispersal on dynamics of an SIR epidemic model with restricting infected individuals boarding transports.

To understand the effect of impulsive vaccination and restricting infected individuals boarding transports on disease spread, we establish an SIR model with impulsive vaccination, impulsive dispersal and restricting infected individuals boarding transports. This SIR epidemic model for two regions, which are connected by transportation of non-infected individuals, portrays the evolvement of diseases. We prove that all solutions of the investigated system are uniformly ultimately bounded. We also prove that there exists globally asymptotically stable infection-free boundary periodic solution. The condition for permanence is discussed. It is concluded that the approach of impulsive vaccination and restricting infected individuals boarding transports provides reliable tactic basis for preventing disease spread.

Exciton Seebeck effect in molecular systems.

We investigate the exciton dynamics under temperature difference with the hierarchical equations of motion. Through a nonperturbative simulation of the transient absorption of a heterogeneous trimer model, we show that the temperature difference causes exciton population redistribution and affects the exciton transfer time. It is found that one can reproduce not only the exciton population redistribution but also the change of the exciton transfer time induced by the temperature difference with a proper tuning of the site energies of the aggregate. In this sense, there exists a site energy shift equivalence for any temperature difference in a broad range. This phenomenon is similar to the Seebeck effect as well as spin Seebeck effect and can be named as exciton Seebeck effect.

Nitrogen contents of rice panicle and paddy by hyperspectral remote sensing.

The nitrogen content or crude protein content in rice grains is one of the important indices to evaluate the nutrition and taste quality of rice. Normal determination of their contents by chemical methods is highly expensive and time consuming. The hyperspectral reflectances of the canopy, flag leaf and panicle of 5 rice varieties are measured by a ASD FieldSpec Pro FR in field under 3 nitrogen support levels in maturing process. The nitrogen contents of stems, leaves, flag leaves, panicles and rice paddy and their crude protein contents are determined. The correlation among them is analyzed. The panicles nitrogen contents (%) are very significantly correlate not only to that of stems, leaves and flag leaves and chlorophyll contents (mg g(-1)) of flag leaves at milking and maturing stages, but also to the spectral reflectance rho(lambda), the first derivative spectra D(lambda) and RVI of canopy, flag leaf and panicle itself. The nitrogen contents (%) of rice paddy are very significantly correlative to that of stems and leaves and the spectral reflectance rho(lambda), the first derivative spectra D(lambda) and RVI of canopy at some wave bands at booting, milking and maturing stages. For the squared multiple correlation coefficients (R2) of estimating the nitrogen contents of panicle and paddy by canopies spectra, we find R2 > 0.80 at milking stage, R2 > 0.75 at maturing stage, but for the estimation of panicle by the spectra of flag leaf and panicle itself, we have R2 > 0.65. It indicates that it can be feasible for estimating the contents of nitrogen and crude protein in rice grains by hyperspectral remote sensing. It provide basis for monitoring rice quality by remote sensing.