Whole-soil warming leads to substantial soil carbon emission in an alpine grassland.

The sensitivity of soil organic carbon (SOC) decomposition in seasonally frozen soils, such as alpine ecosystems, to climate warming is a major uncertainty in global carbon cycling. Here we measure soil CO2 emission during four years (2018-2021) from the whole-soil warming experiment (4 °C for the top 1 m) in an alpine grassland ecosystem. We find that whole-soil warming stimulates total and SOC-derived CO2 efflux by 26% and 37%, respectively, but has a minor effect on root-derived CO2 efflux. Moreover, experimental warming only promotes total soil CO2 efflux by 7-8% on average in the meta-analysis across all grasslands or alpine grasslands globally (none of these experiments were whole-soil warming). We show that whole-soil warming has a much stronger effect on soil carbon emission in the alpine grassland ecosystem than what was reported in previous warming experiments, most of which only heat surface soils.

Selective Formation of Homochiral Dimers by Intermolecular Charge Transfer on a hBN Nanomesh.

In this study, a comprehensive characterization was conducted on a chiral starburst molecule (C57H48N4, SBM) using scanning tunneling microscopy. When adsorbed onto the hBN/Rh(111) nanomesh, these molecules demonstrate homochiral recognition, leading to a selective formation of homochiral dimers. Further tip manipulation experiments reveal that the chiral dimers are stable and primarily controlled by strong intermolecular interactions. Density functional theory (DFT) calculations supported that the chiral recognition of SBM molecules is governed by the intermolecular charge transfer mechanism, different from the common steric hindrance effect. This study emphasizes the importance of intermolecular charge transfer interactions, offering valuable insights into the chiral recognition of a simple bimolecular system. These findings hold significance for the future advancement in chirality-based electronic sensors and pharmaceuticals, where the chirality of molecules can impact their properties.

Quantum spin liquid signatures in monolayer 1T-NbSe2.

Quantum spin liquids (QSLs) are in a quantum disordered state that is highly entangled and has fractional excitations. As a highly sought-after state of matter, QSLs were predicted to host spinon excitations and to arise in frustrated spin systems with large quantum fluctuations. Here we report on the experimental observation and theoretical modeling of QSL signatures in monolayer 1T-NbSe2, which is a newly emerging two-dimensional material that exhibits both charge-density-wave (CDW) and correlated insulating behaviors. By using scanning tunneling microscopy and spectroscopy (STM/STS), we confirm the presence of spin fluctuations in monolayer 1T-NbSe2 by observing the Kondo resonance as monolayer 1T-NbSe2 interacts with metallic monolayer 1H-NbSe2. Subsequent STM/STS imaging of monolayer 1T-NbSe2 at the Hubbard band energy further reveals a long-wavelength charge modulation, in agreement with the spinon modulation expected for QSLs. By depositing manganese-phthalocyanine (MnPc) molecules with spin S = 3/2 onto monolayer 1T-NbSe2, new STS resonance peaks emerge at the Hubbard band edges of monolayer 1T-NbSe2. This observation is consistent with the spinon Kondo effect induced by a S = 3/2 magnetic impurity embedded in a QSL. Taken together, these experimental observations indicate that monolayer 1T-NbSe2 is a new promising QSL material.

Effects of whole-soil warming on CH4 and N2 O fluxes in an alpine grassland.

Global climate warming could affect the methane (CH4 ) and nitrous oxide (N2 O) fluxes between soils and the atmosphere, but how CH4 and N2 O fluxes respond to whole-soil warming is unclear. Here, we for the first time investigated the effects of whole-soil warming on CH4 and N2 O fluxes in an alpine grassland ecosystem on the Tibetan Plateau, and also studied the effects of experimental warming on CH4 and N2 O fluxes across terrestrial ecosystems through a global-scale meta-analysis. The whole-soil warming (0-100 cm, +4°C) significantly elevated soil N2 O emission by 101%, but had a minor effect on soil CH4 uptake. However, the meta-analysis revealed that experimental warming did not significantly alter CH4 and N2 O fluxes, and it may be that most field warming experiments could only heat the surface soils. Moreover, the warming-induced higher plant litter and available N in soils may be the main reason for the higher N2 O emission under whole-soil warming in the alpine grassland. We need to pay more attention to the long-term response of greenhouse gases (including CH4 and N2 O fluxes) from different soil depths to whole-soil warming over year-round, which could help us more accurately assess and predict the ecosystem-climate feedback under realistic warming scenarios in the future.

Synthesis of α-Diimine Complex Enabling Rapidly Covalent Attachment to Silica Supports and Application of Homo-/Heterogeneous Catalysts in Ethylene Polymerization.

For covalent attachment-supported α-diimine catalysts, on the basis of ensuring the thermal stability and activity of the catalysts, the important problem is that the active group on the catalyst can quickly react with the support, anchoring it firmly on the support, shortening the loading time, reducing the negative impact of the support on the active centers, and further improving the polymer morphology, which makes them suitable for use in industrial polymerization temperatures. Herein, we synthesized a α-diimine nickel(II) catalyst bearing four hydroxyl substituents. The hydroxyl substituents enable the catalyst to be immobilized firmly on silica support by covalent linkage in 5-10 min. Compared with the toluene solvent system, the homogeneous catalysts show high activity and thermal stability in hexane solvent at the same conditions. Compared with homogeneous catalysts, heterogeneous catalysis leads to improvements in catalyst lifetime, polymer morphology control, catalytic activity, and the molecular weight of polyethylene (up to 679 kg/mol). The silica-supported catalysts resulted in higher melting temperatures as well as lower branching densities in polyethylenes. Even at 70 °C, the polyethylene prepared by S-CatA-2 still exhibits dispersed particle morphology, and there is no phenomenon of reactor fouling, which is suitable for industrial polymerization processes.

Plant diversity increases above- and below-ground biomass by regulating multidimensional functional trait characteristics.

BACKGROUND AND AIMS: Nitrogen enrichment affects biodiversity, plant functional traits and ecosystem functions. However, the direct and indirect effects of nitrogen addition and biodiversity on the links between plant traits and ecosystem functions have been largely overlooked, even though multidimensional characteristics of plant functional traits are probably critical predictors of ecosystem functions. METHODS: To investigate the mechanism underlying the links between plant trait identity, diversity, network topology and above- and below-ground biomass along a plant species richness gradient under different nitrogen addition levels, a common garden experiment was conducted in which those driving factors were manipulated. KEY RESULTS: The study found that nitrogen addition increased above-ground biomass but not below-ground biomass, while species richness was positively associated with above- and below-ground biomass. Nitrogen addition had minor effects on plant trait identity and diversity, and on the connectivity and complexity of the trait networks. However, species richness increased above-ground biomass mainly by increasing leaf trait diversity and network modularity, and enhanced below-ground biomass through an increase in root nitrogen concentration and network modularity. CONCLUSIONS: The results demonstrate the mechanistic links between community biomass and plant trait identity, diversity and network topology, and show that the trait network architecture could be an indicator of the effects of global changes on ecosystem functions as importantly as trait identity and diversity.

Ullmann-Like Covalent Bond Coupling without Participation of Metal Atoms.

Ullmann-like on-surface synthesis is one of the most appropriate approaches for the bottom-up fabrication of covalent organic nanostructures and many successes have been achieved. The Ullmann reaction requires the oxidative addition of a catalyst (a metal atom in most cases): the metal atom will insert into a carbon-halogen bond, forming organometallic intermediates, which are then reductively eliminated and form C-C covalent bonds. As a result, traditional Ullmann coupling involves reactions of multiple steps, making it difficult to control the final product. Moreover, forming the organometallic intermediates will potentially poison the metal surface catalytic reactivity. In the study, we used the 2D hBN, an atomically thin sp2-hybridized sheet with a large band gap, to protect the Rh(111) metal surface. It is an ideal 2D platform to decouple the molecular precursor from the Rh(111) surface while maintaining the reactivity of Rh(111). We realize an Ullmann-like coupling of a planar biphenylene-based molecule, i.e., 1,8-dibromobiphenylene (BPBr2), on an hBN/Rh(111) surface with an ultrahigh selectivity of the biphenylene dimer product, containing 4-, 6-, and 8-membered rings. The reaction mechanism, including electron wave penetration and the template effect of the hBN, is elucidated by combining low-temperature scanning tunneling microscopy and density functional theory calculations. Our findings are expected to play an essential role regarding the high-yield fabrication of functional nanostructures for future information devices.

Elaborating the crystal transformation referenced microhydrodynamic model and fracture mechanism combined molecular modelling of irbesartan nanosuspensions formation in wet media milling.

In recent years, polymorphic transformation involved in media milling has become a key factor in inducing the instability of nanosuspensions (NSs). The variation trend of microhydrodynamic parameters, including milling intensity factor (F), can be observed under different milling conditions. Therefore, this study first referenced the microhydrodynamic model to explore how formulations and process parameters affect Irbesartan (IRB) form A crystallinity during wet media milling. As a result, the crystallinity of form A was affected by the intermolecular interactions between drug particles and stabilizers. The crystallinity of form A decreased with decreasing drug loading, increasing stirrer speed and bead loading, which depended on the role of F. Milling could promote the transformation from a 1H to 2H tetrazole ring with stabilizers containing -OH, and form B was changed to form A and finally to an amorphous state. Molecular modelling shows that forms A and B are ductile and fragile materials, respectively, and both present anisotropy. When milling beads hit both polymorphs paralleling to the (010) surface, the bead-bead collisions are more helpful in fracturing IRB particles. The results of this study may provide a foundation for controlling crystal transformation and obtaining ideal crystal forms.

Whole-soil warming shifts species composition without affecting diversity, biomass and productivity of the plant community in an alpine meadow.

The structure and function of plant communities in alpine meadow ecosystems are potentially susceptible to climate warming. Here, we utilized a unique field manipulation experiment in an alpine meadow on the Qinghai-Tibetan Plateau and investigated the responses of plant species diversity, composition, biomass, and net primary productivity (NPP) at both community and functional group levels to whole-soil-profile warming (3-4 °C across 0-100 cm) during 2018-2021. Plant species diversity, biomass and NPP (both above- and belowground) at the community level showed remarkable resistance to warming. However, plant community composition gradually shifted over time. Over the whole experimental warming period, aboveground biomass of legumes significantly decreased by 45%. Conversely, warming significantly stimulated aboveground biomass of forbs by 84%, likely because of better growth and competitive advantages from the warming-induced stimulation of soil water and other variables. However, warming showed minor effects on aboveground biomass of grasses and sedges. Overall, we emphasize that experimental warming may significantly affect plant community composition in a short term by triggering adjustments in plant interspecific competition or survival strategies, which may cause potential changes in plant productivity over a more extended period and lead to changes in carbon source-sink dynamics in the alpine meadow ecosystem.

Slurry Homopolymerization of Ethylene Using Thermostable α-Diimine Nickel Catalysts Covalently Linked to Silica Supports via Substituents on Acenaphthequinone-Backbone.

Four supported α-diimine nickel(II) catalysts covalently linked to silica via hydroxyl functionality on α-diimine acenaphthequinone-backbone were prepared and used in slurry polymerizations of ethylene to produce branched polyethylenes. The catalytic activities of these still reached 106 g/molNi·h at 70 °C. The life of the supported catalyst is prolonged, as can be seen from the kinetic profile. The molecular weight of the polyethylene obtained by the 955 silica gel supported catalyst was higher than that obtained by the 2408D silica gel supported catalyst. The melting points of polyethylene obtained by the supported catalysts S-C1-a/b are all above 110 °C. Compared with the homogeneous catalyst, the branching numbers of the polyethylenes obtained by the supported catalysts S-C1-a/b is significantly lower. The polyethylenes obtained by supported catalyst S-C1-a/b at 30-50 °C are free-flowing particles, which is obviously better than the rubber-like cluster polymer obtained from homogeneous catalyst.

The impacts of agroforestry on soil multi-functionality depending on practices and duration.

Agroforestry systems provide a wide range of soil multiple functions (that is, soil multi-functionality) to human society, including the regulation of nutrients and water in soils and the sequestration of atmospheric carbon dioxide, whereas how these effects varied with agroforestry practices and environmental conditions remain unclear. Here, by comparing the soil multi-functionality in agroforestry systems to forests through the field experiment and global scale meta-analysis, we tested, 1) how agroforestry affected soil multi-functionality in a single field study and at the global scale, 2) whether the effects of agroforestry on soil multi-functionality changed in different agroforestry practices, 3) whether the effects of agroforestry on soil multi-functionality varied with environmental conditions. Our study showed that most of the soil functions in agroforestry systems is higher than in forests at the global scale, but show no significant differences between agroforestry and planted forests in our field study. We also found that the effects of agroforestry on soil multi-functionality were varied with agroforestry practices, showing a greater positive in forest-herbage systems than in other practices. In addition, the positive effects of agroforestry on soil organic carbon and total phosphorus declined with the extension of experimental duration. Furthermore, our analysis found that climate conditions had a minor effect on the effects of agroforestry on soil functions. Our analysis revealing that the effects of agroforestry on soil functions depend on agroforestry practices, highlighting that the effects of agroforestry may be diminished with age, and suggesting that the evaluation of ecological impacts of agroforestry should be based on long-term experiments across multiple practices.

Atomic-scale visualization of chiral charge density wave superlattices and their reversible switching.

Chirality is essential for various phenomena in life and matter. However, chirality and its switching in electronic superlattices, such as charge density wave (CDW) superlattices, remain elusive. In this study, we characterize the chirality switching with atom-resolution imaging in a single-layer NbSe2 CDW superlattice by the technique of scanning tunneling microscopy. The atomic arrangement of the CDW superlattice is found continuous and intact although its chirality is switched. Several intermediate states are tracked by time-resolved imaging, revealing the fast and dynamic chirality transition. Importantly, the switching is reversibly realized with an external electric field. Our findings unveil the delicate switching process of chiral CDW superlattice in a two-dimensional (2D) crystal down to the atomic scale.

Spirocyclic side chain of a non-fullerene acceptor enables efficient organic solar cells with reduced recombination loss and energetic disorder.

Suppressing intramolecular vibration of non-fullerene acceptors (NFAs) by molecular rigidification has been proven to be an effective way to reduce the non-radiative recombination loss and energetic disorder of organic solar cells (OSCs). Thus far, extensive attention has been drawn on rigidifying the fused-ring backbones of NFAs, whereas the highly flexible alkyl side chains are barely concerned. Herein, an effective strategy of side chain rigidification by introducing a spiro-ring is developed for the first time and applied to construct the NFA of Spiro-F. Compared to its counterpart F-2F, the rigid spirocyclic side chain can constrain the vibrational-rotational motion and control the orientation of two highly flexible n-octyl chains effectively. As a result, an optimal molecular packing with enhanced intermolecular actions and lower energetic disorder is achieved by Spiro-F, endowing the OSC based on the as cast blend of PM6:Spiro-F with a significantly improved PCE of 13.56% and much reduced recombination loss compared to that of PM6:F-2F. This work provides a feasible strategy to achieve efficient OSCs through the rigidification of the side chain and could boost the PCEs further if applied to some other efficient systems with smaller bandgaps.

Nanoscale Control of One-Dimensional Confined States in Strongly Correlated Homojunctions.

Construction of lateral junctions is essential to generate one-dimensional (1D) confined potentials that can effectively trap quasiparticles. A series of remarkable electronic phases in one dimension, such as Wigner crystallization, are expected to be realized in such junctions. Here, we demonstrate that we can precisely tune the 1D-confined potential with an in situ manipulation technique, thus providing a dynamic way to modify the correlated electronic states at the junctions. We confirm the existence of 1D-confined potential at the homojunction of two single-layer 1T-NbSe2 islands. Such potential is structurally sensitive and shows a nonmonotonic function of their interspacing. Moreover, there is a change of electronic properties from the correlated insulator to the generalized 1D Wigner crystallization while the confinement becomes strong. Our findings not only establish the capability to fabricate structures with dynamically tunable properties, but also pave the way toward more exotic correlated systems in low dimensions.

The Effect of Money Denomination on Prosocial Behavior: Through the Perspective of Metaphorical Cognitive Theory.

Based on metaphorical cognitive theory, this research did four experiments to examine whether and how one important feature of money, denomination, could influence prosocial behavior. Study 1 was an experiment with a sample size of 209 undergraduates (Mage = 18.97) showed that a larger denomination enhanced the probability of participants engaging in prosocial behavior rather than with a smaller denomination. Study 2 collecting data from 269 undergraduates (Mage = 18.50) further showed that larger denominations condition inspired more prosocial behavior than the control condition; and the small denominations condition produced similar levels of prosocial behavior to the control condition. Study 3 used single factor design with a sample size of 192 undergraduates (Mage = 20.49) repeated the results of Study 2. Furthermore, Study 3 excluded an important alternative explanation that the value rather than the denomination influenced prosocial behavior. Last, Study 4 applied a factorial design experiment with a sample size of 132 undergraduates (Mage = 20.92) which demonstrated that generosity mediated the effect of denomination on prosocial behavior; the effect of denomination on prosocial behavior did not depend on money priming methods. Finally, theoretical and practical implications were discussed.

Warming has a minor effect on surface soil organic carbon in alpine meadow ecosystems on the Qinghai-Tibetan Plateau.

The alpine meadow ecosystem on the Qinghai-Tibetan Plateau (QTP) is very sensitive to warming and plays a key role in regulating global carbon (C) cycling. However, how warming affects the soil organic carbon (SOC) pool and related C inputs and outputs in alpine meadow ecosystems on the QTP remains unclear. Here, we combined two field experiments and a meta-analysis on field experiments to synthesize the responses of the SOC pool and related C cycling processes to warming in alpine meadow ecosystems on the QTP. We found that the SOC content of surface soil (0-10 cm) showed a minor response to warming, but plant respiration was accelerated by warming. In addition, the warming effect on SOC was not correlated with experimental and environmental variables, such as the method, magnitude and duration of warming, initial SOC content, mean annual temperature, and mean annual precipitation. We conclude that the surface SOC content is resistant to climate warming in alpine meadow ecosystems on the QTP.

Visualizing Spatial Evolution of Electron-Correlated Interface in Two-Dimensional Heterostructures.

Microscopically visualizing the evolution of electronic structures at the interface between two electron-correlated domains shows fundamental importance in both material science and physics. Here, we report scanning tunneling microscopy and spectroscopy studies of the interfacial electronic structures evolution in a phase-engineered monolayer NbSe2 heterostructure. The H-NbSe2 metallic state penetrates the Mott insulating T-NbSe2 at the H/T phase interface, with a prominent 2D charge density wave (CDW) proximity effect. Moreover, an insulating Mott gap collapse with the disappearance of the upper Hubbard band is detected at the electronic phase transition region. Theoretical calculations reveal that such insulating Mott gap collapse can be attributed to the electron doping effect induced by the interface. Our findings promote a microscopical understanding of the interactions between different electron-correlated systems and provide an effective method for controlling the Mott insulating states with phase engineering.

Exploring space-energy matching via quantum-molecular mechanics modeling and breakage dynamics-energy dissipation via microhydrodynamic modeling to improve the screening efficiency of nanosuspension prepared by wet media milling.

Introduction: The preparation of nanosuspensions by wet media milling is a promising technique that increases the bioavailability of insoluble drugs. The nanosuspension is thermodynamically unstable, where its stability might be influenced by the interaction energy between the stabilizers and the drugs after milling at a specific collision energy. However, it is difficult to screen the stabilizers and the parameters of milling accurately and quickly by using traditional analysis methods. Quantum-molecular mechanics and microhydrodynamic modeling can be applied to improve screening efficiency.Areas covered: Quantum-molecular mechanics model, which includes molecular docking, molecular dynamics simulations, and data on binding energy, provides insights into screening stabilizers based on their molecular behavior at the atomic level. The microhydrodynamic model explores the mechanical processes and energy dissipation in nanomilling, and even combines information on the mechanical modulus and an energy vector diagram for the milling parameters screening of drug crystals.Expert opinion: These modeling methods improve screening efficiency and support screening theories based on thermodynamics and physical dynamics. However, how to reasonably combine different modeling methods with their theoretical characteristics and further multidimensional and cross-scale simulations of nanosuspension formation remain challenges.

Experimental Evidence of Chiral Symmetry Breaking in Kekulé-Ordered Graphene.

The low-energy excitations of graphene are relativistic massless Dirac fermions with opposite chiralities at valleys K and K^{'}. Breaking the chiral symmetry could lead to gap opening in analogy to dynamical mass generation in particle physics. Here we report direct experimental evidences of chiral symmetry breaking (CSB) from both microscopic and spectroscopic measurements in a Li-intercalated graphene. The CSB is evidenced by gap opening at the Dirac point, Kekulé-O type modulation, and chirality mixing near the gap edge. Our work opens up opportunities for investigating CSB related physics in a Kekulé-ordered graphene.