Detailed information on the H/D isotope effects for adsorption on the surface and absorption in the bulk is important for understanding the nuclear quantum effect. To achieve this purpose, we developed a new theoretical approach, namely, the combined plane wave and localized basis set (CPLB) method. By using the multi-component quantum chemical method, which takes into account the quantum effect of proton or deuteron, with localized part in CPLB method, direct analysis of H/D isotope effect about adsorption and absorption is achieved. In this study, we performed a theoretical investigation of the H/D isotope effects for adsorption on a Pd(111) surface and absorption in bulk Pd. We clearly showed H/D isotope effect on geometry during adsorption and absorption. Our developed CPLB approach is a powerful tool for analyzing the quantum nature of H/D in surface, bulk, and inhomogeneous systems.

GridMol is a “one-stop” platform for molecular modeling, scientific computing and molecular visualization aided by High Performance Computing Environment. GridMol version 2.0 emphatically introduces two unique features, the first is fragment-based linear scaling quantum chemistry methods, such as molecular fractionation with conjugate caps and fragment molecular orbital methods; the second is visualization of computational processes, such as structural optimization and intrinsic reaction coordinate calculation. Compared with version 1.0, fragment-based linear scaling quantum chemistry methods implemented in GridMol version 2.0 can be used as a useful tool for performing quantum calculations for large molecular systems to explore the mechanisms involved in protein–ligand or targeted-drug interactions.

Hydraulic properties control plant responses to climate and are likely to be under strong selective pressure, but their macro-evolutionary history remains poorly characterized. To fill this gap, we compiled a global dataset of hydraulic traits describing xylem conductivity (Ks), xylem resistance to embolism (P50), sapwood allocation relative to leaf area (Hv) and drought exposure (ψmin), and matched it with global seed plant phylogenies. Individually, these traits present medium to high levels of phylogenetic signal, partly related to environmental selective pressures shaping lineage evolution. Most of these traits evolved independently of each other, being co-selected by the same environmental pressures. However, the evolutionary correlations between P50 and ψmin and between Ks and Hv show signs of deeper evolutionary integration because of functional, developmental or genetic constraints, conforming to evolutionary modules. We do not detect evolutionary integration between conductivity and resistance to embolism, rejecting a hardwired trade-off for this pair of traits.

Background: Pulmonary sarcoidosis is characterized by an exaggerated CD4+ T-cell response and formation of non-necrotizing granulomas. Tumour necrosis factor α (TNF-α) is regarded as crucial for granuloma formation and TNF-α inhibitors offer a 3rd line treatment option for patients not responding to conventional treatment. However, not all patients benefit from treatment, and an optimal dose and treatment duration have not been established. Insight into the influence of TNF-α inhibitors on lung immune cells may provide clues to what drives inflammation in sarcoidosis and improve our understanding of treatment outcomes. Objectives: To evaluate effects of treatment with the TNF- α inhibitor infliximab on lung immune cells and clinical features of the patients. Methods: Thirteen patients with sarcoidosis refractory to conventional treatment were assessed with bronchoalveolar lavage (BAL), spirometry and CT scan in close adjacent to start of infliximab treatment. These investigations were repeated after six months of treatment. Results: Treatment with TNF- α inhibitor infliximab was well tolerated with no adverse events, except for one patient who developed a probable adverse event with liver toxicity. Ten patients were classified as responders, having a reduced CD4/CD8 ratio, a decreased percentage of CD4+ T-cells expressing the activation marker CD69 and number of mast cells (p<0.05 for all). The percentage of T regulatory cells (Tregs), defined as FoxP3+ CD4+ T-cells decreased in most patients. Conclusions: Six months of infliximab treatment in patients with sarcoidosis led to signs of decreased CD4+ T-cell alveolitis and decreased mastocytosis in the lungs of responders.

The Sanjiang Plain is the biggest freshwater wetland locating within northeastern China. Due to climate change and human activities, that wetland has degraded to a successional gradient from the original flooded wetland to dry shrub vegetation and a forest area with lower ground water level, resulting in changes in soil microbiologic structure and functions. The present study investigated the microbial diversity and community structure in relation to soil properties along this gradient. The soil physic-chemical properties changed significantly with degradation. The Shannon variety of soil fungi as well as bacteria varied significantly with successional stage (both P < 0.05). The community structures of soil bacteria and fungi in the early successional stages (i.e., the wetland) were significantly structured via total phosphorus, available nitrogen and total nitrogen concentrations in soils, while those in the later successional stages (i.e., forests) were significantly structured by soil organic carbon, soil pH and available phosphorus concentrations. Our results indicated that variations in the soil environment affected soil microbial communities along a successional gradient from wetland to forests are mainly. These outcomes indicate that above ground plant composition is a forceful determinant of the structure as well as functions of bacterial and fungal communities, might finally causing substantial alterations in ecosystem activity.

Synthesis of adipic acid (AA) through the oxidation of cyclohexanol and cyclohexanone (K/A oil) with nitric acid was conducted in a capillary microreactor system. Effects of the temperature, the nitric acid concentration, the volumetric flow rate ratio of nitric acid to K/A oil, and the capillary length on the selectivity and the product yield were investigated systematically to achieve optimal reaction conditions. Notably, a high yield of adipic acid (i.e., 90%) was achieved just in 6 seconds at 85℃ with the use of 55 wt% nitric acid. Gas components produced in this oxidation process and its total volumetric flow rate were determined under various operating conditions, which was beneficial for reaction mechanism characterization and process optimization. Finally, a kinetic model was established, which was of crucial theoretical significance and practical value for optimizing the reactor design and better understanding such fast and highly exothermic multiphase processes with abundant gas production.

In this letter, two time delay dynamic models, TDD-NCP model and Fudan-CCDC model, are introduced to track the data of COVID-19. The TDD-NCP model is developed recently by Cheng's group group in Fudan and SUFE. The TDD-NCP model introduced the time delay process into the differential equations to describe the latent period of the epidemic. The Fudan-CDCC model is established when Wenbin Chen suggested to determine the kernel functions in the TDD-NCP model by the public data from CDCC. By the public data of the cumulative confirmed cases in different regions in China and different countries, these models can clearly illustrate that the containment of the epidemic highly depends on early and effective isolations.

The páramos, a neotropical alpine grassland-peatland dominated biome of the northern Andes and Central America, play an essential role in regional and global cycles of water, carbon, and nutrients. They act as water towers, delivering water and ecosystem services mainly from the continental water divide at the Andean highland down to the Pacific and Amazon regions. The anthropogenic influence in form of the climate crisis exerts enormous pressures on these identified “hotspot” ecosystems and increases the vulnerability of nearby populations undermining the socio-economic and human development. Further, increasing pressures reduce the resilience to face climate shocks, and dramatically alters the hydro-climatic regime and shifts the páramos from long-term carbon sinks towards carbon sources. Despite their importance and vulnerability, only three decades ago, páramos, were globally among the least studied ecosystems. However, researchers have since identified them as ideal targets for solving water scarcity issues and to offset carbon emissions. Increasing awareness of the need for hydrological evidence to guide sustainable management of the páramos prompted action for generating data and to fill long-standing knowledge gaps. This has led to a remarkably successful community-research-policy effort to generate this knowledge. The combination of well-established and innovative approaches was used to data collection, processing and knowledge extraction. In this review, we provide a short overview of the state of knowledge of the hydrometeorology, flux dynamics, anthropogenic and the influence of extreme events in the regional páramos. Then, we present emerging technologies for hydrology and water resources research and management applied to páramos. Lastly, we discuss how converging science and policy efforts have leveraged traditional and new observational techniques to generate an evidence base that can support the sustainable management of the páramos. We conclude that this co-evolution of science policy was able to cover different spatial and temporal scales. Finally, we outline future research directions to showcase how sustainable long-term data collection can be sustained for the responsible development of páramo water towers.

Phenotypic diversity, or disparity, can be explained by simple genetic drift or, if functional constraints are strong, by selection for ecologically relevant phenotypes. We here studied phenotypic disparity in head shape in aquatic snakes. We investigated whether conflicting selective pressures related to different functions have driven shape diversity and explore whether similar phenotypes may give rise to the same functional output (i.e. many-to-one mapping of form to function). We focused on the head shape of aquatically foraging snakes as they fulfil several fitness-relevant functions and show a large amount of morphological variability. We used 3D surface scanning and 3D geometric-morphometrics to compare the head shape of 62 species in a phylogenetic context. We first tested whether diet specialization and size are drivers of head shape diversification. Next, we tested for many-to-one mapping by comparing the hydrodynamic efficiency of head shapes characteristic of the main axis of variation in the dataset. We 3D printed these shapes and measured the forces at play during a frontal strike. Our results show that diet and size explain only a small amount of shape variation. Shapes did not functionally converge as more specialized aquatic species evolved a more efficient head shape than others. The shape disparity observed could thus reflect a process of niche specialization under a stabilizing selective regime.

Many eusocial insects, including ants, show complex colony structures, distributions, and reproductive strategies. In the ant Vollenhovia emeryi Wheeler (Hymenoptera: Myrmicinae), queens and males are produced clonally, while sterile workers arise sexually, unlike other ant species and Hymenopteran insects in general. Furthermore, there is a wing length polymorphism in the queen caste. Despite its ecological and evolutionary importance, little is known about the population dynamics and structure of this ant species, which may provide insight into its unique reproductive mode and polymorphic traits. We performed in-depth analyses of ant populations from Korea, Japan, and North America using three mitochondrial genes (COI, COII, and Cytb). The long-winged (L) morph is predominant in Korean populations, and the short-winged (S) morph is very rare. Interestingly, all L morphs were infected with Wolbachia, while all Korean S morphs lacked Wolbachia, demonstrating a novel association between a symbiont and a phenotypic trait. A phylogenetic analysis revealed that the S morph is derived from the L morph. We propose that the S morph is associated with potential resistance to Wolbachia infection, and that Wolbachia infection does not influence clonal reproduction.

The photocatalytic yield of the g-C3N4 for CO2 reduction was modified by phosphorus doping. The possible reaction pathways for CO2 reduction on the P-doped g-C3N4 (PCN) surface were investigated by DFT calculations for the first time. The experimental results showed that P doping improves the production of CH4 through the increase in the driving force of the electrons. The partial density of states of the PCN showed that the VBM and CBM are composed of px, py and s orbitals of the N atoms and pz states of carbon, nitrogen, and phosphorus, respectively and therefore, the P-doping increase carriers lifetime. Mechanism studies confirm that formic acid, formaldehyde, methanol and methane are the most probable products. The methane having positive adsorption energy can be easily desorbed from the PCN surface and the Gibbs activation energy of the final step is 1.98 eV. The formation of H2COOH is the rate-determining step.

The field of molecular magnetism has benefited from the fluid synergy between experimentalists and theoreticians for decades This has led to fundamental understanding of the processes that govern Single Molecule Magnets, allowing for the establishment of clear design criteria to control properties and the development of new synthetic methodologies, sophisticated magnetic measurements and innovative computational techniques. Herein we give an overview on the experimental and theoretical collaborative work we carried out as part of the synthesis group led by David Mills and the computational/theoretical team led by Nicholas Chilton at the University of Manchester. Together with this, we provide a perspective on collaborative work in molecular magnetism and how such collaborations are essential for advancing the field further.

We studied the ring opening of propylene oxide (PO) by salen-M coordinated OH- group [M = Al(Ⅲ), Sc(Ⅲ), Cr(Ⅲ), Mn(Ⅲ), Fe(Ⅲ), Co(Ⅱ), Co(Ⅲ), Ni(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Ru(Ⅲ) and Rh(Ⅲ)]. The results show that the ring opening energy barriers for M(II) complexes are much lower than those with M(III) complexes in the gas phase, and the barriers correlate linearly with the negative charges on the OH- group, the Fukui function condensed on the OH- group. The nucleophilicity ordering in gas phase can be rationalized by the ratio of formal positive charges/radius of M cations. Solvent effect greatly increases the barriers of M(II) complexes, but slightly changes the results of M(III) ones, making the barriers similar. Analysis indicates that the reaction heats are linearly proportional to the reverse reaction barriers. The relationships established here can be used to estimate the ring opening barriers and to screen epoxide ring opening catalysts.

In this work, we study a weakly singular Volterra integro differential equation with Caputo type fractional derivative. First, we derive a sufficient condition for the existence and uniqueness of the solution of this problem based on the maximum norm. It is observed that the condition depends on the domain of definition of the problem. Thereafter, we show that this condition will be independent of the domain of definition based on an equivalent weighted maximum norm. In addition, we have also provided a procedure to extend the existence and uniqueness of the solution in its domain of definition by partitioning it. We also derive a sufficient condition under which the model problem will provide an analytic solution. Next, we introduce a operator based parameterized method to generate an approximate solution of this problem. Convergence analysis of this approach is established here. Next, we have optimized this solution based on least square method. For this, residual minimization is used to obtain the optimal values of the auxiliary parameter. In addition, we have also provided an error bound based on this technique. Several numerical examples are produced to clarify the effective behavior of the convergence of the present method. Comparison of the standard method and optimized method based on residual minimization signify the better accuracy of modified one. In addition, we also consider an equivalent form of weakly singular integro differential equation of a Heat transfer problem to show the effectiveness of the present approach.

In this paper, a class of nonautonomous SEIRS epidemic models with vaccination and nonlinear incidence is investigated. Under some quite weak assumptions, a couple of new threshold values in the form of integral, i.e., $R_1$, $R^*_1$, $R_2$ and $R^*_2$ on the extinction and permanence of disease for the model are established. As special cases of our model, the autonomous, periodic and almost periodic circumstances are discussed respectively. The nearly necessary and sufficient criteria of threshold on the extinction and permanence of disease for above cases are obtained as well. Numerical examples and simulations are presented to illustrate the analytic results.

A mixed boundary value problem for the L\’ame equation in a thin layer $\Omega^h:\cC\times[-h,h]$ around a surface $\cC$ with the Lipshitz boundary is investigated. The main goal is to find out what happens when the thickness of the layer tends to zero $h\to0$. To this end we reformulate BVP into an equivalent variational problem and prove that the energy functional has the $\Gamma$-limit being the energy functional on the mid-surface $\cC$. The corresponding BVP on $\cC$, considered as the $\Gamma$-limit of the initial BVP, is written in terms of G\”unter’s tangential derivatives on $\cC$ and represents a new form of the shell equation. It is shown that the Neumann boundary condition from the initial BVP on the upper and lower surfaces transforms into a right-hand side term of the basic equation of the limit BVP.

The identification of the mechanisms underlying co-occurrence patterns of species is a way to identify which processes (niche, neutral or both) structure metacommunities. In this paper, our goals are to identify patterns of co-occurrence in neotropical stream fish and determine which processes structure the metacommunity and the gradients that underlie this structure. Our results pointed out that the metacommunity formed by the total pool of species is structured by a nested pattern (Hyperdispersed Species Loss) of co-occurrence and the mass effect mechanism. On the other hand, a set of core species displays a Clementisian pattern and is structured by the species sorting mechanism. Both, hyperdispersed species loss and the Clementisian patterns point to a discrete set of communities in the metacommunity. These communities could be isolated by physicochemical conditions, or physical barriers, like dams or waterfalls.

In this study, the viscosity of MgO-Water nanofluid in a different volume fraction of nanoparticles, temperatures, and shear rates has been predicted by Artificial Neural Networks (ANNs) and surface methods. In the ANN method, an algorithm is proposed to select the best neuron number for the hidden layer. In the fitting method, a surface is proposed for each volume fraction of nanoparticles, and finally, the results of ANN and surface fitting method have been compared. It can be observed that, increasing the volume fraction from 0.07% to 1.25% at temperatures of 25, 30, 40, 50, and 60 °C resulted in about two-fold increase in viscosity. Also, the best network has 24 neurons in the hidden layer. It can be seen that for a network with 24 neurons in the hidden layer has the best overall correlation, and this coefficient is 0.999035. The mean absolute value of errors in ANN and fitting method are 0.0118 and 0.0206, respectively.