Obtaining giant Rashba-Dresselhaus spin splitting in two-dimensional chiral metal-organic frameworks.

Two-dimensional (2D) nonmagnetic semiconductors with large Rashba-Dresselhaus (R-D) spin splitting at valence or conduction bands are attractive for magnetic-field-free spintronic applications. However, so far, the number of 2D R-D inorganic semiconductors has been quite limited, and the factors that determine R-D spin splitting as well as rational design of giant spin splitting, remain unclear. For this purpose, by exploiting 2D chiral metal-organic frameworks (CMOFs) as a platform, we theoretically develop a three-step screening method to obtain a series of candidate 2D R-D semiconductors with valence band spin splitting up to 97.2 meV and corresponding R-D coupling constants up to 1.37 eV Å. Interestingly, the valence band spin texture is reversible by flipping the chirality of CMOFs. Furthermore, five keys for obtaining giant R-D spin splitting in 2D CMOFs are successfully identified: (i) chirality, (ii) large spin-orbit coupling, (iii) narrow band gap, (iv) valence and conduction bands having the same symmetry at the Γ point, and (v) strong ligand field.

High-Throughput Computational Screening of Novel Two-Dimensional Covalent Organic Frameworks for Efficient Photocatalytic Overall Water Splitting.

The pursuit of efficient photocatalysts toward photocatalytic water splitting has attracted wide attention. However, the low efficiency of photocatalytic reactions due to the rapid electron-hole recombination and the time-consuming searching process hinder the development of high-performance photocatalysts. Here, we proposed a data-driven screening procedure for covalent organic frameworks (COFs) as overall solar water-splitting photocatalysts. Based on a COF database through assembling different Cores and Linkers, three COFs are predicted to be efficient photocatalysts for overall solar water splitting after high-throughput computational screening. We found that the photogenerated electrons and holes are well separated on single COF photocatalysts without material engineering, and both hydrogen and oxygen evolution reactions can occur spontaneously on the three screened COFs under visible light radiation. This kind of novel COF screened by a data-driven screening procedure offers new perspectives for advancing efficient photocatalysts.

Phase Evolution of Multi-Metal Dichalcogenides With Conversion-Alloying Hybrid Mechanism for Superior Lithium Storage.

Traditional lithium-ion battery (LIB) anodes, whether intercalation-type like graphite or alloying-type like silicon, employing a single lithium storage mechanism, are often limited by modest capacity or substantial volume changes. Here, the kesterite multi-metal dichalcogenide (CZTSSe) is introduced as an anode material that harnesses a conversion-alloying hybrid lithium storage mechanism. Results unveil that during the charge-discharge processes, the CZTSSe undergoes a comprehensive phase evolution, transitioning from kesterite structure to multiple dominant phases of sulfides, selenides, metals, and alloys. The involvement of multi-components facilitates electron transport and mitigates swelling stress; meanwhile, it results in formation of abundant defects and heterojunctions, allowing for increased lithium storage active sites and reduced lithium diffusion barrier. The CZTSSe delivers a high specific capacity of up to 2266 mA h g-1 at 0.1 A g-1; while, maintaining a stable output of 116 mA h g-1 after 10 000 cycles at 20 A g-1. It also demonstrates remarkable low-temperature performance, retaining 987 mA h g-1 even after 600 cycles at -40 °C. When employed in full cells, a high specific energy of 562 Wh kg-1 is achieved, rivalling many state-of-the-art LIBs. This research offers valuable insights into the design of LIB electrodes leveraging multiple lithium storage mechanisms.

To elucidate the bioactive components of Lamiophlomis herba in the treatment of liver fibrosis via plasma pharmacochemistry and network pharmacology.

Lamiophlomis Herba (LH) is a traditional Chinese and Tibetan dual-use herb with hemostatic and analgesic effects, and is widely used in the clinical treatment of traumatic bleeding and pain. In recent years, LH has been proven to treat liver fibrosis (LF), but the chemical components related to the pharmacological properties of LH in the treatment of LF are still unclear. Based on the theory of plasma pharmachemistry, the characteristic components in water extract and drug-containing plasma samples of LH were qualitatively analyzed by UPLC-Q-TOF-MS. The chemical components in plasma were screened and the targets were predicted by network pharmacology. Then, the predicted components and targets were verified in vitro by Elisa and qRT-PCR technology. Finally, the pharmacological effects of LH and its monomeric components were determined by hematoxylin-eosin staining of rat liver. A total of 50 chemical constituents were identified in LH, of which 12 were blood prototypes and 9 were metabolites. In vitro experiments showed that LH and its monomeric components luteolin, shanzhiside methyl ester, loganic acid, loganin, 8-O-acetyl shanzhiside methyl ester could increase the expression of antioxidant genes (NQO-1, HO-1) and decrease the expression of inflammatory genes (IL-6, IL-18), thereby reducing the expression of extracellular matrix-related genes and proteins (COL1A1, COL3A1, LN, α-sma, PC-III, Col-IV). In vivo experiments showed that LH could reduce the area of LF in rats in a dose-dependent manner, and shanzhiside methyl ester and 8-O-acetyl shanzhiside methyl ester may be the main components in pharmacodynamics. These effects may be mediated by LH-mediated Nrf2/NF-κB pathway. This study explored the potential pharmacodynamic components of LH in the treatment of LF, and confirmed that shanzhiside methyl ester and 8-O-acetyl shanzhiside methyl ester play a key role in the treatment of LF with LH.

Quantum-centric high performance computing for quantum chemistry.

High performance computing (HPC) is renowned for its capacity to tackle complex problems. Meanwhile, quantum computing (QC) provides a potential way to accurately and efficiently solve quantum chemistry problems. The emerging field of quantum-centric high performance computing (QCHPC), which merges these two powerful technologies, is anticipated to enhance computational capabilities for solving challenging problems in quantum chemistry. The implementation of QCHPC for quantum chemistry requires interdisciplinary research and collaboration across multiple fields, including quantum chemistry, quantum physics, computer science and so on. This perspective provides an introduction to the quantum algorithms that are suitable for deployment in QCHPC, focusing on conceptual insights rather than technical details. Parallel strategies to implement these algorithms on quantum-centric supercomputers are discussed. We also summarize high performance quantum emulating simulators, which are considered a viable tool to explore QCHPC. We conclude with challenges and outlooks in this field.

Vertical Dipole Dominates Charge Carrier Lifetime in Monolayer Janus MoSSe.

Two-dimensional semiconductor materials with vertical dipoles are promising photocatalysts as vertical dipoles not only promote the electron-hole separation but also enhance the carrier redox ability. However, the influence of vertical dipoles on carrier recombination in such materials, especially the competing relationship between vertical dipoles and band gaps, is not yet clear. Herein, first-principles calculations and nonadiabatic molecular dynamics simulations were combined to clarify the influence of band gap and vertical dipole on the carrier lifetime in Janus MoSSe monolayer. By comparing with the results of MoS2 and MoSe2 as well as exploring the carrier lifetime of MoSSe under strain regulation, it has been demonstrated that the vertical dipole, rather than the band gap, is the dominant factor affecting the carrier lifetime. Strikingly, a linear relationship between the carrier lifetime and vertical dipole is revealed. These findings have important implications for the design of high-performance photocatalysts and optoelectronic devices.

A DNA tetrahedron-based nanosuit for efficient delivery of amifostine and multi-organ radioprotection.

Unnecessary exposure to ionizing radiation (IR) often causes acute and chronic oxidative damages to normal cells and organs, leading to serious physiological and even life-threatening consequences. Amifostine (AMF) is a validated radioprotectant extensively applied in radiation and chemotherapy medicine, but the short half-life limits its bioavailability and clinical applications, remaining as a great challenge to be addressed. DNA-assembled nanostructures especially the tetrahedral framework nucleic acids (tFNAs) are promising nanocarriers with preeminent biosafety, low biotoxicity, and high transport efficiency. The tFNAs also have a relative long-term maintenance for structural stability and excellent endocytosis capacity. We therefore synthesized a tFNA-based delivery system of AMF for multi-organ radioprotection (tFNAs@AMF, also termed nanosuit). By establishing the mice models of accidental total body irradiation (TBI) and radiotherapy model of Lewis lung cancer, we demonstrated that the nanosuit could shield normal cells from IR-induced DNA damage by regulating the molecular biomarkers of anti-apoptosis and anti-oxidative stress. In the accidental total body irradiation (TBI) mice model, the nanosuit pretreated mice exhibited satisfactory alteration of superoxide dismutase (SOD) activities and malondialdehyde (MDA) contents, and functional recovery of hematopoietic system, reducing IR-induced pathological damages of multi-organ and safeguarding mice from lethal radiation. More importantly, the nanosuit showed a selective radioprotection of the normal organs without interferences of tumor control in the radiotherapy model of Lewis lung cancer. Based on a conveniently available DNA tetrahedron-based nanocarrier, this work presents a high-efficiency delivery system of AMF with the prolonged half-life and enhanced radioprotection for multi-organs. Such nanosuit pioneers a promising strategy with great clinical translation potential for radioactivity protection.

Theoretical Insights into Enhancing Catalytic Performance of Al-Cu Alloy for CO2 Electroreduction toward Ethene Production.

The understanding of the reaction mechanism of CO2 electroreduction (CO2RR) is essential for the precise design of catalysts for specific products with high selectivity. In this work, combined with the computational hydrogen electrode model and kinetic energy barrier calculations, CO2RR pathways on Cu(100) and Al1Cu3(100) are intensively investigated. The free energy barrier of the rate-determining step of ethylene formation is reduced from 1.08 eV for *CCOH formation on Cu(100) to 0.51 eV for *CH2OCHOH formation on Al1Cu3(100) and enhances the catalytic activity. The reaction free energy of *CO-*CO coupling is remarkably reduced from 0.86 eV on Cu(100) to -0.43 eV on Al1Cu3(100) and the coupling barrier is reduced from 0.97 to 0.37 eV, suppressing the production of gas phase CO and enhancing the production of C2 products. Furthermore, the selectivity toward C-O breaking of *CH2CHOH on Cu(100) and *CH2CH2OH on Al1Cu3(100) ensures high selectivity toward ethene rather than ethanol.

Chromosome-level Alstonia scholaris genome unveils evolutionary insights into biosynthesis of monoterpenoid indole alkaloids.

Alstonia scholaris of the Apocynaceae family is a medicinal plant with a rich source of bioactive monoterpenoid indole alkaloids (MIAs), which possess anti-cancer activity like vinca alkaloids. To gain genomic insights into MIA biosynthesis, we assembled a high-quality chromosome-level genome for A. scholaris using nanopore and Hi-C data. The 444.95 Mb genome contained 35,488 protein-coding genes. A total of 20 chromosomes were assembled with a scaffold N50 of 21.75 Mb. The genome contained a cluster of strictosidine synthases and tryptophan decarboxylases with synteny to other species and a saccharide-terpene cluster involved in the monoterpenoid biosynthesis pathway of the MIA upstream pathway. The multi-omics data of A. scholaris provide a valuable resource for understanding the evolutionary origins of MIAs and for discovering biosynthetic pathways and synthetic biology efforts for producing pharmaceutically useful alkaloids.

Artificial kagome lattices of Shockley surface states patterned by halogen hydrogen-bonded organic frameworks.

Artificial electronic kagome lattices may emerge from electronic potential landscapes using customized structures with exotic supersymmetries, benefiting from the confinement of Shockley surface-state electrons on coinage metals, which offers a flexible approach to realizing intriguing quantum phases of matter that are highly desired but scarce in available kagome materials. Here, we devise a general strategy to construct varieties of electronic kagome lattices by utilizing the on-surface synthesis of halogen hydrogen-bonded organic frameworks (XHOFs). As a proof of concept, we demonstrate three XHOFs on Ag(111) and Au(111) surfaces, which correspondingly deliver regular, breathing, and chiral breathing diatomic-kagome lattices with patterned potential landscapes, showing evident topological edge states at the interfaces. The combination of scanning tunnelling microscopy and noncontact atomic force microscopy, complemented by density functional theory and tight-binding calculations, directly substantiates our method as a reliable and effective way to achieve electronic kagome lattices for engineering quantum states.

Construction of an Electron Capture and Transfer Center for Highly Efficient and Selective Solar-Light-Driven CO2 Conversion.

Exploring high-efficiency photocatalysts for selective CO2 reduction is still challenging because of the limited charge separation and surface reactions. In this study, a noble-metal-free metallic VSe2 nanosheet was incorporated on g-C3N4 to serve as an electron capture and transfer center, activating surface active sites for highly efficient and selective CO2 photoreduction. Quasi in situ X-ray photoelectron spectroscopy (XPS), soft X-ray absorption spectroscopy (sXAS), and femtosecond transient absorption spectroscopy (fs-TAS) unveiled that VSe2 could capture electrons, which are further transferred to the surface for activating active sites. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations revealed a kinetically feasible process for the formation of a key intermediate and confirmed the favorable production of CO on the VSe2/PCN (protonated C3N4) photocatalyst. As an outcome, the optimized VSe2/PCN composite achieved 97% selectivity for solar-light-driven CO2 conversion to CO with a high rate of 16.3 µmol·g-1·h-1, without any sacrificial reagent or photosensitizer. This work offers new insights into the photocatalyst design toward highly efficient and selective CO2 conversion.

Bacterial c-di-GMP signaling gene affects mussel larval metamorphosis through outer membrane vesicles and lipopolysaccharides.

Biofilms serve as crucial cues for settlement and metamorphosis in marine invertebrates. Within bacterial systems, c-di-GMP functions as a pivotal signaling molecule regulating both biofilm formation and dispersion. However, the molecular mechanism of how c-di-GMP modulates biofilm-induced larval metamorphosis remains elusive. Our study reveals that the deletion of a c-di-GMP related gene in Pseudoalteromonas marina led to an increase in the level of bacterial c-di-GMP by knockout technique, and the mutant strain had an enhanced ability to produce more outer membrane vesicles (OMVs) and lipopolysaccharides (LPS). The mutant biofilms had higher induction activity for larval metamorphosis in mussels Mytilus coruscus, and OMVs play a major role in the induction activity. We further explored the function of LPS in OMVs. Extracted LPS induced high larval metamorphosis rate, and LPS content were subject to c-di-GMP and LPS-biosynthesis gene. Thus, we postulate that the impact of c-di-GMP on biofilm-induced metamorphosis is mediated through OMVs and LPS.

Two-Dimensional Os2Se3 Nanosheet: A Ferroelectric Metal with Room-Temperature Ferromagnetism.

Two-dimensional (2D) ferroelectric metals (FEMs) possess intriguing characteristics, such as unconventional superconductivity and the nonlinear anomalous Hall effect. However, their occurrence is exceedingly rare due to mutual repulsion between ferroelectricity and metallicity. In addition, further incorporating other features like ferromagnetism into FEMs to enhance their functionalities poses a significantly greater challenge. Here, via first-principles calculations, we demonstrate a case of an FEM that features a coexistence of room-temperature ferromagnetism, ferroelectricity, and metallicity in a thermodynamically stable 2D Os2Se3. It presents a vertical electric polarization of 3.00 pC/m that exceeds those of most FEMs and a moderate polarization switching barrier of 0.22 eV per formula unit. Moreover, 2D Os2Se3 exhibits robust ferromagnetism (Curie temperature TC ≈ 527 K) and a sizable magnetic anisotropy energy (-30.87 meV per formula unit). Furthermore, highly magnetization-dependent electrical conductivity is revealed, indicative of strong magnetoelectric coupling. Berry curvature calculation suggests that the FEM might exhibit nontrivial band topology.

Proposed Quantum Twisting Scanning Probe Microscope over Twisted Bilayer Graphene.

Twisted bilayer graphene (TBG) has the natural merits of tunable flat bands and localized states distributed as a triangular lattice. However, the application of this state remains obscure. By density functional theory (DFT) and pz orbital tight-binding model calculations, we investigate the tip-shaped electrostatic potential of top valence electrons of TBG at half filling. Adsorption energy scanning of molecules above the TBG reveals that this tip efficiently attracts molecules selectively to AA-stacked or AB-stacked regions. Tip shapes can be controlled by their underlying electronic structure, with electrons of low bandwidth exhibiting a more localized feature. Our results indicate that TBG tips offer applications in noninvasive and nonpolluting measurements in scanning probe microscopy and theoretical guidance for 2D material-based probes.

First-Principles High-Throughput Inverse Design of Direct Momentum-Matching Band Alignment van der Waals Heterostructures Utilizing Two-Dimensional Indirect Semiconductors.

Two-dimensional (2D) van der Waals (vdW) heterostructures have attracted widespread attention in photocatalysis. Herein, we employ a novel strategy utilizing first-principles high-throughput inverse design of 2D Z-scheme heterojunctions for photocatalysis. This approach is anchored in high-throughput screening conditions, which are fundamentally based on the characteristics of carrier mechanisms influenced significantly by Z-scheme heterojunctions. A pivotal element of our screening process is the integration of the indirect-to-direct bandgap transition with momentum-matching band alignment in k-space, guiding us to combine two 2D indirect bandgap monolayers into direct Z-scheme heterojunctions characterized by pronounced interlayer excitons. Various stacking modes introduce extra and distinct degrees of freedom that can be useful for tuning the properties of heterostructures, encompassing factors such as components, stacking patterns, and sequences. We demonstrate that various stacking modes can facilitate the indirect-to-direct bandgap transition and the emergence of interlayer excitons. These findings provide exciting opportunities for designing Z-scheme heterojunctions in photocatalysis.

Self-Assembly Intermetallic PtCu3 Core with High-Index Faceted Pt Shell for High-Efficiency Oxygen Reduction.

Rational design of well-defined active sites is crucial for promoting sluggish oxygen reduction reactions. Herein, leveraging the surfactant-oriented and solvent-ligand effects, we develop a facile self-assembly strategy to construct a core-shell catalyst comprising a high-index Pt shell encapsulating a PtCu3 intermetallic core with efficient oxygen-reduction performance. Without undergoing a high-temperature route, the ordered PtCu3 is directly fabricated through the accelerated reduction of Cu2+, followed by the deposition of the remaining Pt precursor onto its surface, forming high-index steps oriented by the steric hindrance of surfactant. This approach results in a high half-wave potential of 0.911 V versus reversible hydrogen electrode, with negligible deactivation even after 15000-cycle operation. Operando spectroscopies identify that this core-shell catalyst facilitates the conversion of oxygen-involving intermediates and ensures antidissolution ability. Theoretical investigations rationalize that this improvement is attributed to reinforced electronic interactions around high-index Pt, stabilizing the binding strength of rate-determining OHads species.

Polyelectrolyte Hydrogel-Functionalized Photothermal Sponge Enables Simultaneously Continuous Solar Desalination and Electricity Generation Without Salt Accumulation.

Technologies that can simultaneously generate electricity and desalinate seawater are highly attractive and required to meet the increasing global demand for power and clean water. Here, a bifunctional solar evaporator that features continuous electric generation in seawater without salt accumulation is developed by rational design of polyelectrolyte hydrogel-functionalized photothermal sponge. This evaporator not only exhibits an unprecedentedly high water evaporation rate of 3.53 kg m-2 h-1along with 98.6% solar energy conversion efficiency but can also uninterruptedly deliver a voltage output of 0.972 V and a current density of 172.38 µA cm-2 in high-concentration brine over a prolonged period under one sun irradiation. Many common electronic devices can be driven by simply connecting evaporator units in series or in parallel without any other auxiliaries. Different from the previously proposed power generation mechanism, this study reveals that the water-enabled proton concentration fields in intermediate water region can also induce an additional ion electric field in free water region containing solute, to further enhance electricity output. Given the low-cost materials, simple self-regeneration design, scalable fabrication processes, and stable performance, this work offers a promising strategy for addressing the shortages of clean water and sustainable electricity.

Complex-Valued K-Means Clustering of Interpolative Separable Density Fitting Algorithm for Large-Scale Hybrid Functional Enabled Ab Initio Molecular Dynamics Simulations within Plane Waves.

K-means clustering, as a classic unsupervised machine learning algorithm, is the key step to select the interpolation sampling points in interpolative separable density fitting (ISDF) decomposition for hybrid functional electronic structure calculations. Real-valued K-means clustering for accelerating the ISDF decomposition has been demonstrated for large-scale hybrid functional enabled ab initio molecular dynamics (hybrid AIMD) simulations within plane-wave basis sets where the Kohn-Sham orbitals are real-valued. However, it is unclear whether such K-means clustering works for complex-valued Kohn-Sham orbitals. Here, we propose an improved weight function defined as the sum of the square modulus of complex-valued Kohn-Sham orbitals in K-means clustering for hybrid AIMD simulations. Numerical results demonstrate that the K-means algorithm with a new weight function yields smoother and more delocalized interpolation sampling points, resulting in smoother energy potential, smaller energy drift, and longer time steps for hybrid AIMD simulations compared to the previous weight function used in the real-valued K-means algorithm. In particular, we find that this improved algorithm can obtain more accurate oxygen-oxygen radial distribution functions in liquid water molecules and a more accurate power spectrum in crystal silicon dioxide compared to the previous K-means algorithm. Finally, we describe a massively parallel implementation of this ISDF decomposition to accelerate large-scale complex-valued hybrid AIMD simulations containing thousands of atoms (2,744 atoms), which can scale up to 5,504 CPU cores on modern supercomputers.

Machine Learning K-Means Clustering in Interpolative Separable Density Fitting Algorithm: Advancing Accurate and Efficient Cubic-Scaling Density Functional Perturbation Theory Calculations within Plane Waves.

Density functional perturbation theory (DFPT) is a crucial tool for accurately describing lattice dynamics. The adaptively compressed polarizability (ACP) method reduces the computational complexity of DFPT calculations from O(N4) to O(N3) by combining the interpolative separable density fitting (ISDF) algorithm. However, the conventional QR factorization with column pivoting (QRCP) algorithm, used for selecting the interpolation points in ISDF, not only incurs a high cubic-scaling computational cost, O(N3), but also leads to suboptimal convergence. This convergence issue is particularly pronounced when considering the complex interplay between the external potential and atomic displacement in ACP-based DFPT calculations. Here, we present a machine learning K-means clustering algorithm to select the interpolation points in ISDF, which offers a more efficient quadratic-scaling O(N2) alternative to the computationally intensive cubic-scaling O(N3) QRCP algorithm. We implement this efficient K-means-based ISDF algorithm to accelerate plane-wave DFPT calculations in KSSOLV, which is a MATLAB toolbox for performing Kohn-Sham density functional theory calculations within plane waves. We demonstrate that this K-means algorithm not only offers comparable accuracy to QRCP in ISDF but also achieves better convergence for ACP-based DFPT calculations. In particular, K-means can remarkably reduce the computational cost of selecting the interpolation points by nearly 2 orders of magnitude compared to QRCP in ISDF.

First-Principles Insights into Tungsten Semicarbide-Based Single-Atom Catalysts: Single-Atom Migration and Mechanisms in Oxygen Reduction.

Understanding the structural evolution of single-atom catalysts (SACs) in catalytic reactions is crucial for unraveling their catalytic mechanisms. In this study, we utilize density functional theory calculations to delve into the active phase evolution and the oxygen reduction reaction (ORR) mechanism of tungsten semicarbide-based transition metal SACs (TM1/W2C). The stable crystal phases and optimal surface exposures of W2C are identified by using ab initio atomistic thermodynamics simulations. Focusing on the W-terminated (001) surface, we screen 13 stable TM1/W2C variants, ultimately selecting Pt1/W2C(001) as our primary model. The surface Pourbaix diagram, mapped for this model under ORR conditions, reveals dynamic Pt1 migration on the surface, triggered by surface oxidation. This discovery suggests a novel single-atom evolution pathway. Remarkably, this single-atom migration behavior is also discerned in seven other group VIII SACs, enhancing both their catalytic activity and their stability. Our findings offer insights into the evolution of active phases in SACs, considering substrate structural arrangement, single-atom incorporation, and self-optimization of catalysts under various conditions.