Impact of Nuclear Quantum Effects on the Structural Properties of Protonated Water Clusters.

Nuclear quantum effects (NQEs) play a crucial role in hydrogen-bonded systems due to quantum tunneling and proton fluctuation. Our understanding of how NQEs affect microstructures mainly focuses on bulk phases of liquids and solids but remains deficient for water clusters, including their hydrogen nuclei, hydrogen-bonded configurations, and temperature dependence. Here, we conducted ab initio molecular dynamics (MD) and path integral MD simulations to investigate the influence of NQEs on the structural properties of protonated water clusters H+(H2O)n (n = 3, 6, 9, 12). The results reveal that the NQEs become less evident as the cluster size increases due to the competition between NQEs and electrostatic interactions. Simulations of several H+(H2O)6 isomers at different temperatures indicate that the effect of elevated temperature on proton transfer is related to the initial structure. Interestingly, the process of proton transfer also involves the interconversion between Zundel-type and Eigen-type isomers. These findings significantly deepen our understanding of ion-water and water-water interactions, opening new avenues for the study of hydrated ion clusters and related systems.

Intrinsic Chiroptical Activity and Excitonic Properties of Group II-VI Magic-Size Clusters.

Semiconductor magic-size clusters (MSCs), lying in the local minima of the potential landscape, are important intermediates that emerge during the synthesis of colloidal quantum dots. They have definite geometrical and electronic structures, thus serving as atomically precise building blocks for assembling supramolecular structures and devices with unprecedented functionalities. Here we report the intrinsic chiroptical activity in the magic-size cadmium and zinc chalcogenide clusters with magic numbers of 13, 33, and 34 possessing unique core-shell structures. They are responsive to circularly polarized light from the ultraviolet to visible region, with size-tunable energy gap, absorption wavelength, and excitonic characteristics. The origin of the chiroptical activity and the evolution of excitonic states with magic size are disclosed by time-dependent density functional theory calculations within a correlated electron-hole picture. This molecular-level understanding of the photophysical properties of group II-VI MSCs provides essential guidelines for utilizing them for chiral optoelectronics and photonics.

Doping-mediated excited state dynamics of diphosphine-protected M@Au12 (M = Au, Ir) superatom nanoclusters.

Doping heterometal atoms into ligand-protected gold superatom nanoclusters (Aun NCs) is proposed to further diversify their geometrical and electronic structures and enhance their photoluminescence properties, which is attributed to the mixing and effects between atoms. However, the fundamental principles that govern the optoelectronic properties of the doped Aun NCs remain elusive. Herein, we systematically explored two prototypical 8-electron Aun (n = 11 and 13) NCs with and without Ir dopant atoms using comprehensive ab initio calculations and real-time nonadiabatic molecular dynamics simulations. These doped Aun NCs maintain their parent geometrical structures and 8-electron superatomic configuration (1S21P6). Strong core-shell (Ir-Aun) electronic coupling significantly expands the energy gap, resulting in a weak nonadiabatic coupling matrix element, which in turn increases the carrier lifetime. This increase is mainly governed by the low-frequency vibration mode. We uncovered the relationship between electronic structures, electron-vibration, and carrier dynamics for these doped Aun NCs. These calculated results provide crucial insights for the atomically precise design of metal NCs with superior optoelectronic properties.

Analysis and Modelling of the Predictive Value of PCT, PLR and NLR for Ureteric Sepsis after Ureteral Stone Surgery: A Retrospective Cohort Study.

OBJECTIVE: This study aimed to analyse the value of procalcitonin (PCT), neutrophil-to-lymphocyte ratio (NLR) and platelet-to-lymphocyte ratio (PLR) in predicting postoperative ureteral stone complications of urogenic sepsis. The production of a clinical prediction model could provide additional direction to reduce the likelihood of postoperative urogenital sepsis. METHODS: The clinical data of 520 patients with ureteral stones who underwent surgical treatment from January 2022, to September 2023, in the hospital were retrospectively analysed. The patients were divided into urogenic sepsis group (n = 42) and non-urogenic sepsis group (n = 478) in accordance with the occurrence of urogenic sepsis in the postoperative period. The peripheral blood PCT, PLR and NLR levels were collected within 24 h postoperatively in the two groups. The receiver operating characteristic (ROC) curve was employed to evaluate the predictive value of PCT, PLR and NLR levels for postoperative urogenital sepsis in patients with ureteral stones. RESULTS: Logistic regression analysis showed that PCT (odds ratio (OR) = 4.25, 95% CI: 1.85-9.78), PLR (OR = 4.00, 95% CI: 1.78-9.05) and NLR (OR = 2.29, 95% CI: 1.05-5.01) were risk factors for postoperative complication sepsis in patients with ureteral stones (p < 0.05). The ROC curves showed that the areas under the curve of PCT, PLR and NLR levels alone and in combination for predicting urogenic sepsis complications after emergency ureteral stone surgery were 0.683, 0.692, 0.611 and 0.799, respectively. CONCLUSIONS: Urogenic sepsis leads to increased serum PCT, NLR and PLR levels in patients undergoing surgical treatment for ureteral stones. Physicians should pay close attention to these indices to provide further theoretical support for reducing postoperative urogenic sepsis.

Unraveling the Photocatalytic Mechanism of N2 Fixation on Single Ruthenium Sites.

Photocatalytic N2 fixation offers promise for ammonia synthesis, yet traditional photocatalysts encounter challenges such as low efficiency and short carrier lifetimes. Atomically precise ligand-metal nanoclusters emerge as a solution to address these issues, but the photophysical mechanism remains elusive. Inspired by the synthesis of Au4Ru2 NCs, we investigate the mechanism behind N2 activation on Au4Ru2, focusing on photoactivity and carrier dynamics. Our results reveal that vibration of the Ru-N bond in the low-frequency domain suppresses the deactivation process leading to a long lifetime of the excited N2. By the strategy of isoelectronic substitution, we identify the single Ru sites as the active sites for N2 activation. Furthermore, these ligand-protected M4Ru2 (M = Au, Ag, Cu) NCs show robust thermal stability in explicit solvation and decent photochemical activity for N2 activation and NH3 production. These findings have significant implications for the optimization of catalysts for sustainable ammonia synthesis.

p-block germanenes as a promising electrocatalysts for the oxygen reduction reaction.

The oxygen reduction reaction (ORR), a pivotal process in hydrogen fuel cells crucial for enhancing fuel cell performance through suitable catalysts, remains a challenging aspect of development. This study explores the catalytic potential of germanene on Al (111), taking advantage of the successful preparation of stable reconstructed germanene layers on Al (111) and the excellent catalytic performance exhibited by germanium-based nanomaterials. Through first-principles calculations, we demonstrate that the O2 molecule can be effectively activated on both freestanding and supported germanene nanosheets, featuring kinetic barriers of 0.40 and 0.04 eV, respectively. The presence of the Al substrate not only significantly enhances the stability of the reconstructed germanene but also preserves its exceptional ORR catalytic performance. These theoretical findings offer crucial insights into the substrate-mediated modulation of germanene stability and catalytic efficiency, paving the way for the design of stable and efficient ORR catalysts for future applications.

Luminescence properties of endohedrally doped group-IV clusters.

Endohedrally doped clusters form a large category of cage clusters, with unique structures, diverse elemental compositions, and highly tunable electronic structures and physisochemical properties. They have been widely achieved in laboratory and may serve as functional building blocks for assembling new supermolecular structures and devices. In this paper, for the first time, we disclosed the luminescence properties of endohedrally doped group-IV clusters by time-dependent density functional theory calculations. A total of 64 cage clusters have been explored in terms of stability, emission wavelength, and the energy difference between the first excited singlet and triplet states. The key geometric and electronic factors governing the photophysical properties of these cage clusters were unveiled, to provide crucial insights for crafting atomically precise nanoclusters for optical and optoelectronic applications.

High-dose Vitamin C injection ameliorates against sepsis-induced myocardial injury by anti-apoptosis, anti-inflammatory and pro-autophagy through regulating MAPK, NF-κB and PI3K/AKT/mTOR signaling pathways in rats.

AIMS: This study aimed to evaluate the effects of VC on SIMI in rats. METHODS: In this study, the survival rate of high dose VC for SIMI was evaluated within 7 days. Rats were randomly assigned to three groups: Sham group, CLP group, and high dose VC (500 mg/kg i.v.) group. The animals in each group were treated with drugs for 1 day, 3 days or 5 days, respectively. Echocardiography, myocardial enzymes and HE were used to detect cardiac function. IL-1ß, IL-6, IL-10 and TNF-α) in serum were measured using ELISA kits. Western blot was used to detect proteins related to apoptosis, inflammation, autophagy, MAPK, NF-κB and PI3K/Akt/mTOR signaling pathways. RESULTS: High dose VC improved the survival rate of SIMI within 7 days. Echocardiography, HE staining and myocardial enzymes showed that high-dose VC relieved SIMI in rats in a time-dependent manner. And compared with CLP group, high-dose VC decreased the expressions of pro-apoptotic proteins, while increased the expression of anti-apoptotic protein. And compared with CLP group, high dose VC decreased phosphorylation levels of Erk1/2, P38, JNK, NF-κB and IKK α/ß in SIMI rats. High dose VC increased the expression of the protein Beclin-1 and LC3-II/LC3-I ratio, whereas decreased the expression of P62 in SIMI rats. Finally, high dose VC attenuated phosphorylation of PI3K, AKT and mTOR compared with the CLP group. SIGNIFICANCE: Our results showed that high dose VC has a good protective effect on SIMI after continuous treatment, which may be mediated by inhibiting apoptosis and inflammatory, and promoting autophagy through regulating MAPK, NF-κB and PI3K/AKT/mTOR pathway.

Alloying Driven Antiferromagnetic Skyrmions on NiPS3 Monolayer: A First-Principles Calculation.

Topological magnetic states are promising information carriers for ultrahigh-density and high-efficiency magnetic storage. Recent advances in two-dimensional (2D) magnets provide powerful platforms for stabilizing various nanometer-size topological spin textures within a wide range of magnetic field and temperature. However, non-centrosymmetric 2D magnets with broken inversion symmetry are scarce in nature, making direct observations of the chiral spin structure difficult, especially for antiferromagnetic (AFM) skyrmions. In this work, it is theoretically predicted that intrinsic AFM skyrmions can be easily triggered in XY-type honeycomb magnet NiPS3 monolayer by alloying of Cr atoms, due to the presence of a sizable Dzyaloshinskii-Moriya interaction. More interestingly, the diameter of the AFM skyrmions in Ni3/4Cr1/4PS3 decreases from 12 to 4.4 nm as the external magnetic field increases and the skyrmion phases remain stable up to an external magnetic field of 4 T. These results highlight an effective strategy to generate and modulate the topological spin texture in 2D magnets by alloying with magnetic element.

B63: The Most Stable Bilayer Structure with Dual Aromaticity.

The emergence of a bilayer B48 cluster, which has been both theoretically predicted and experimentally observed, as well as the recent experimental synthesis of bilayer borophene sheets on Ag and Cu surfaces, has generated tremendous curiosity in the bilayer structures of boron clusters. However, the connection between bilayer boron cluster and bilayer borophene remains unknown. By combining a genetic algorithm and density functional theory calculations, a global search for the low-energy structures of the B63 cluster was conducted, revealing that the Cs bilayer structure with three interlayer B-B bonds is the most stable bilayer structure. This structure was further examined in terms of its structural stability, chemical bonding, and aromaticity. Interestingly, the interlayer bonds induce strong electronegativity and robust aromaticity. Furthermore, the dual aromaticity stems from diatropic currents originating from virtual translational transitions for both σ and π electrons. This unprecedent bilayer boron cluster is anticipated to enrich the concept of dual aromaticity and serve as a potential precursor for bilayer borophene.

Tin-oxo nanoclusters for extreme ultraviolet photoresists: Effects of ligands, counterions, and doping.

The extreme ultraviolet (EUV) nanolithography technology is the keystone for developing the next-generation chips. As conventional chemically amplified resists are approaching the resolution limit, metal-containing photoresists, especially tin-oxo clusters, seize the opportunity to embrace this challenge owing to their small sizes, precise atomic structures, and strong EUV absorption. However, atomistic insights into the mechanism for regulating their photolithographic behavior are lacking. Herein, we systematically explored the effects of ligands, counterions, and endohedral doping on the photophysical properties of tin-oxo cage clusters by first-principles calculations combined with molecular dynamics simulations. Photoresists assembled by allyl-protected clusters with small-size OH- or Cl- counterions have a high absorption coefficient at the EUV wavelength of 13.5 nm and a low energy cost for ligand detachment and superior stability to ensure high sensitivity and strong etch resistance, respectively. The photoresist performance can further be improved by endohedral doping of the metal-oxo nanocage with Ag+ and Cd2+ ions, which exhibit superatomic characteristics and are likely to be synthesized in laboratory. These theoretical results provide useful guidance for modification of metal-oxo clusters for high-resolution EUV photolithography.

Efficient Full-Frequency GW Calculations Using a Lanczos Method.

The GW approximation is widely used for reliable and accurate modeling of single-particle excitations. It also serves as a starting point for many theoretical methods, such as its use in the Bethe-Salpeter equation (BSE) and dynamical mean-field theory. However, full-frequency GW calculations for large systems with hundreds of atoms remain computationally challenging, even after years of efforts to reduce the prefactor and improve scaling. We propose a method that reformulates the correlation part of the GW self-energy as a resolvent of a Hermitian matrix, which can be efficiently and accurately computed using the standard Lanczos method. This method enables full-frequency GW calculations of material systems with a few hundred atoms on a single computing workstation. We further demonstrate the efficiency of the method by calculating the defect-state energies of silicon quantum dots with diameters up to 4 nm and nearly 2,000 silicon atoms using only 20 computational nodes.

Identification and validation of biomarkers related to lipid metabolism in osteoarthritis based on machine learning algorithms.

BACKGROUND: Osteoarthritis and lipid metabolism are strongly associated, although the precise targets and regulatory mechanisms are unknown. METHODS: Osteoarthritis gene expression profiles were acquired from the GEO database, while lipid metabolism-related genes (LMRGs) were sourced from the MigSB database. An intersection was conducted between these datasets to extract gene expression for subsequent differential analysis. Following this, functional analyses were performed on the differentially expressed genes (DEGs). Subsequently, machine learning was applied to identify hub genes associated with lipid metabolism in osteoarthritis. Immune-infiltration analysis was performed using CIBERSORT, and external datasets were employed to validate the expression of these hub genes. RESULTS: Nine DEGs associated with lipid metabolism in osteoarthritis were identified. UGCG and ESYT1, which are hub genes involved in lipid metabolism in osteoarthritis, were identified through the utilization of three machine learning algorithms. Analysis of the validation dataset revealed downregulation of UGCG in the experimental group compared to the normal group and upregulation of ESYT1 in the experimental group compared to the normal group. CONCLUSIONS: UGCG and ESYT1 were considered as hub LMRGs in the development of osteoarthritis, which were regarded as candidate diagnostic markers. The effects are worth expected in the early diagnosis and treatment of osteoarthritis.

On the nature of Con±/0 clusters reacting with water and oxygen.

Bulk cobalt does not react with water at room temperature, but cobalt nanometals could yield corrosion at ambient conditions. Insights into the cobalt cluster reactions with water and oxygen enable us to better understand the interface reactivity of such nanometals. Here we report a comprehensive study on the gas-phase reactions of Con±/0 clusters with water and oxygen. All these Con±/0 clusters were found to react with oxygen, but only anionic cobalt clusters give rise to water dissociation whereas the cationic and neutral ones are limited to water adsorption. We elucidate the influences of charge states, bonding modes and dehydrogenation mechanism of water on typical cobalt clusters. It is unveiled that the additional electron of anionic Con- clusters is not beneficial to H2O adsorption, but allows for thermodynamics- and kinetics-favourable H atom transfer and dehydrogenation reactions. Apart from the charge effect, size effect and spin effect play a subtle role in the reaction process. The synergy of multiple metal sites in Con- clusters reduces the energy barrier of the rate-limiting step enabling hydrogen release. This finding of water dissociation on cobalt clusters put forward new connotations on the activity series of metals, providing new insights into the corrosion mechanism of cobalt nanometals.

Optical Activity and Excitonic Characteristics of Chiral CdSe Quantum Dots.

Introduction of chirality to colloidal semiconductor quantum dots (QDs) triggers a chiroptical effect. However, there remains a knowledge gap in the mechanism of chirality transfer and amplification from molecules to QDs. By time-dependent density functional theory calculations combined with a correlated electron-hole picture, we explored the chiroptical activity of CdSe QDs decorated with different chiral monocarboxylic acids from an excitonic perspective. Our calculations showed strong circular dichroism (CD) signals in the visible region for the chiral CdSe QDs. The excitonic states with large CD originate from QDs, while the chiral molecules break the orthogonality between electric and magnetic transition dipoles, which synergistically facilitates the prominent dissymmetric effect. The considered monocarboxylic acid chiral molecules all favor the bidentate adsorption configuration of the carboxyl group on the CdSe surface, endowing an identical CD signature but distinct excitonic characteristics. These findings are crucial for the regulation of chirality and excitons in semiconductor QDs to develop excitonic devices.

Two-dimensional fullerene-based monolayer materials assembled by C80 and Sc3N@C80.

Construction of two-dimensional (2D) materials using fullerenes as building blocks has attracted particular attention, primarily due to their ability to integrate desired functionalities into devices. However, realization of stable 2D phases of polymerized fullerenes remains a big challenge. Here, we propose two stable 2D monolayer phases with covalently bridged C80 cages, namely α-C80-2D and ß-C80-2D, which are semiconductors with strong absorption in the long wave range and appreciable carrier mobility, respectively. The high stability originates from the bond energy released by the [2+2] cycloaddition polymerization of C80 is greater than the deformation energy of a cage. Starting from α-C80-2D, endohedral incorporation of the Sc3N molecule into each C80 cage leads to 2D semiconductors of α-Sc3N@C80-2D and α'-Sc3N@C80-2D, which possess exceptional stability and diverse physical properties, including unique electronic band structures, strong optical absorption in the visible (VIS) to near-infrared (NIR) regime, and anisotropic optical characteristics. Remarkably, a temperature-induced order-disorder transition in the α-Sc3N@C80-2D phase has been observed at elevated temperatures above 600 K. These findings expand the family of 2D carbon materials and provide useful clue for the potential applications of fullerene-assembled monolayer networks.

Effect of fission defects on tensile strength of U3Si2 Σ5(210) grain boundary from first-principles calculations.

U3Si2 is regarded as a promising accident tolerant fuel (ATF) to replace the commercial fuel UO2; however, grain boundary (GB) embrittlement of U3Si2 caused by irradiation-induced defect segregation remains to be clarified. In this work, the U3Si2 Σ5(210) symmetrically tilted GB is taken as a representative to elucidate the individual effect of xenon (Xe) and vacancy on the tensile strength and failure of GBs using first-principles calculations. Compared with the predicted segregation energies of defects at the most energetically favourable positions of GBs, Si vacancy (VSi) has a much stronger preference to segregate to GBs than that of Xe substitution on the Si sublattice (XeSi). Moreover, the strengthening/embrittlement potency of GBs with single vacancy/Xe is evaluated using the first-principles-based uniaxial tensile test. Although both VSi and XeSi yield a weakening effect on the strength of the U3Si2 Σ5(210) GB, such defective GBs exhibit significantly stronger interface strengths compared to the corresponding defects segregated to the UO2 Σ3(111) GB. The underlying mechanism of strength change of U3Si2 GBs is discussed in terms of charge analysis. Our results can provide a fundamental understanding of the mechanical behavior of irradiated GBs from an atomic perspective.

Assisted Self-Assembly of Nanoporous Ices via Carbon Nanomaterial Templates.

Self-assembly is a widely used synthetic method in nanoscience to assemble well-organized structures. Self-assembly processes usually occur in a water solvent environment. However, the self-assembly of water molecules is rarely studied. Herein, we show a strategy to fabricate porous ice via carbon nanomaterial-assisted self-assembly. Diverse frameworks of nanoporous ice are formed by using orthorhombic and tetragonal arrays of carbon nanotubes or carbon-atom chains as templates. In contrast to many bulk ices discovered in nature, nanoporous ices are shown to be stable only under negative pressure. Hence, nanoporous ices cannot be produced through the direct nucleation of water at negative pressure. The template-assisted self-assembly method is shown to be the most effective method to fabricate nanoporous ice in quantity. Several key factors for the self-assembly of nanoporous ices are identified, including proper gap spacings in the carbon nanomaterial template and suitable interactions between water and the carbon nanomaterials.

Rational Design of Full-Color Fluorescent C3N Quantum Dots.

Carbon-based quantum dots (QDs) exhibit unique photoluminescence due to size-dependent quantum confinement, giving rise to fascinating full-color emission properties. Accurate emission calculations using time-dependent density functional theory are a time-costing and expensive process. Herein, we employed an artificial neural network (ANN) combined with statistical learning to establish the relationship between geometrical/electronic structures of ground states and emission wavelength for C3N QDs. The emission energy of these QDs can be doubly modulated by size and edge effects, which are governed by the number of C4N2 rings and the CH group, respectively. Moreover, these two structural characteristics also determine the phonon vibration mode of C3N QDs to harmonize the emission intensity and lifetime of hot electrons in the electron-hole recombination process, as indicated by nonadiabatic molecular dynamics simulation. These computational results provide a general approach to atomically precise design the full-color fluorescent carbon-based QDs with targeted functions and high performance.

Cyclical palmitoylation regulates TLR9 signalling and systemic autoimmunity in mice.

Toll-like receptor 9 (TLR9) recognizes self-DNA and plays intricate roles in systemic lupus erythematosus (SLE). However, the molecular mechanism regulating the endosomal TLR9 response is incompletely understood. Here, we report that palmitoyl-protein thioesterase 1 (PPT1) regulates systemic autoimmunity by removing S-palmitoylation from TLR9 in lysosomes. PPT1 promotes the secretion of IFNα by plasmacytoid dendritic cells (pDCs) and TNF by macrophages. Genetic deficiency in or chemical inhibition of PPT1 reduces anti-nuclear antibody levels and attenuates nephritis in B6.Sle1yaa mice. In healthy volunteers and patients with SLE, the PPT1 inhibitor, HDSF, reduces IFNα production ex vivo. Mechanistically, biochemical and mass spectrometry analyses demonstrated that TLR9 is S-palmitoylated at C258 and C265. Moreover, the protein acyltransferase, DHHC3, palmitoylates TLR9 in the Golgi, and regulates TLR9 trafficking to endosomes. Subsequent depalmitoylation by PPT1 facilitates the release of TLR9 from UNC93B1. Our results reveal a posttranslational modification cycle that controls TLR9 response and autoimmunity.