This paper discussed the setting up of a comeuter automatic system for testing the dy-namic dissociating tension of cooked cocoon filament by means of microcomputer tech-niques.The dynamic dissociating tension of two ...This paper discussed the setting up of a comeuter automatic system for testing the dy-namic dissociating tension of cooked cocoon filament by means of microcomputer tech-niques.The dynamic dissociating tension of two kinds of row cocoons with differentreelability was tested and analysed under different cocoon cooking conditions.More relia-ble data have been obtained by quantitative tests.The conclusions reached by analysingthese data are of practical significance to perfecting the cocoon cooking theory,assessingcocoon quality,improving the cocoon cooking process,etc.展开更多
We theoretically investigate the production of cold CN molecules by photodissociating ICN precursors in a brute-force field. The energy shifts and adiabatic orientation of the rotational ICN precursors are first inves...We theoretically investigate the production of cold CN molecules by photodissociating ICN precursors in a brute-force field. The energy shifts and adiabatic orientation of the rotational ICN precursors are first investigated as a function of the external field strength. The dynamical photofragmentation of ICN precursors is numerically simulated for cases with and without orienting field. The CN products are compared in terms of their velocity distributions. A small portion of the CN fragments are recoiled to near zero speed in the lab frame by appropriately selecting the photo energy for dissociation. With a precursor ICN molecular beam of - 1.5 K in rotational temperature, the production of low speed CN fragments can be improved by more than 5 times when an orienting electrical field of 100 k V/cm is present. The corresponding production rate for decelerated fragments with speeds ≤ 50 m/s is simulated to be about ～2.1×10^-4 and CN number densities of 10^8 –10^10 cm^-3 can be reached with precursor ICN densities of ～10^12 –10^14 cm^-3 from supersonic expansion.展开更多
Composite solid electrolytes(CSEs)are considered among the most promising candidates for solid-state batteries.However,their practical application is hindered by low ionic conductivity and a limited lithium-ion transf...Composite solid electrolytes(CSEs)are considered among the most promising candidates for solid-state batteries.However,their practical application is hindered by low ionic conductivity and a limited lithium-ion transference number,primarily owing to the insufficient mobility of Li+.In this work,we design a heterojunc-tion nanoparticle composed of bimetallic zeolitic imidazolate frameworks(ZIFs)coupled with amorphous tita-nium oxide(TiO_(2)@Zn/Co–ZIF)as a filler to fabricate a composite solid-state electrolyte(PVZT).The amor-phous TiO_(2) coating facilitates salt dissociation through Lewis acid–base interactions with the anions of the lithium salt.Meanwhile,the Zn/Co–ZIF framework not only provides additional selective pathways for Li+transport but also effectively restricts anion migration through its confined pore size.The synergistic effect results in a high room-temperature ionic conductivity(8.8×10^(-4) S·cm^(-1))and a lithium-ion transference number of 0.47 for PVZT.A symmetrical cell using PVZT demonstrates stable Li+deposition/stripping for over 1100 h at a current density of 0.1 mA·cm^(-2).Additionally,a LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/Li full cell using PVZT retains 75.0%of its capacity after 1200 cycles at a 2 C rate.This work offers valuable insights into the design of func-tional fillers for CSEs with highly efficient ion transport.展开更多
For a simple graph G,let A(G)and D(G)be the adjacency matrix and the diagonal degree matrix of G,respectively.[Appl.Anal.Discrete Math.,2017,11(1):81-107]defined the matrix A_(α)(G)of G as A_(α)(G)=αD(G)(1-α)A(G)...For a simple graph G,let A(G)and D(G)be the adjacency matrix and the diagonal degree matrix of G,respectively.[Appl.Anal.Discrete Math.,2017,11(1):81-107]defined the matrix A_(α)(G)of G as A_(α)(G)=αD(G)(1-α)A(G),α∈[0,1].The Aa-spectral radius is the largest eigenvalue of A_(α)(G).Let G_(n,β) be the set graphs with order n and dissociation numberβ.In this paper,we identify the b with maximal A_(α)-spectral radius among all graphs in G_(n,β).展开更多
As antibiotic pollutants cannot be incompletely removed by conventional wastewater treatment plants,ultraviolet(UV)based advanced oxidation processes(AOPs)such as UV/persulfate(UV/PS)and UV/chlorine are increasingly c...As antibiotic pollutants cannot be incompletely removed by conventional wastewater treatment plants,ultraviolet(UV)based advanced oxidation processes(AOPs)such as UV/persulfate(UV/PS)and UV/chlorine are increasingly concerned for the effective removal of antibiotics from wastewaters.However,the specific mechanisms involving degradation kinetics and transformation mechanisms are not well elucidated.Here we report a detailed examination of SO_(4)•−/Cl•-mediated degradation kinetics,products,and toxicities of sulfathiazole(ST),sarafloxacin(SAR),and lomefloxacin(LOM)in the two processes.Both SO_(4)•−/Cl•-mediated transformation kinetics were found to be dependent on pH(P<0.05),which was attributed to the disparate reactivities of their individual dissociated forms.Based on competition kinetic experiments and matrix calculations,the cationic forms(H_(2)ST^(+),H_(2)SAR^(+),and H_(2)LOM^(+))were more highly reactive towards SO_(4)•−in most cases,while the neutral forms(e.g.,HSAR^(0)and HLOM^(0))reacted the fastest with Cl•for the most of the antibiotics tested.Based on the identification of 31 key intermediates using tandem mass spectrometry,these reactions generated different products,of which the majority still retained the core chemical structure of the parent compounds.The corresponding diverse transformation pathways were proposed,involving S−N breaking,hydroxylation,defluorination,and chlorination reactions.Furthermore,the toxicity changes of their reaction solutions as well as the toxicity of each intermediate were evaluated by the vibrio fischeri and ECOSAR model,respectively.Many primary by-products were proven to be more toxic than the parent chemicals,raising the wider issue of extended potency for these compounds with regards to their ecotoxicity.These results have implications for assessing the degradative fate and risk of these chemicals during the AOPs.展开更多
BACKGROUND Left colon cancer surgery relies on laparoscopic hemicolectomy,with digestive tract reconstruction critical.End-to-side anastomosis(ESA)and side-to-side anastomosis(SSA)anastomoses are common,but their comp...BACKGROUND Left colon cancer surgery relies on laparoscopic hemicolectomy,with digestive tract reconstruction critical.End-to-side anastomosis(ESA)and side-to-side anastomosis(SSA)anastomoses are common,but their comparative outcomes,especially in splenic flexure handling and efficacy,need clarification.This study compares ESA and SSA to guide surgical practice.AIM To compare the clinical outcomes of laparoscopically assisted left hemicolectomy with ESA and SSA.METHODS A total of 334 patients were included,with 105 patients from the First Affiliated Hospital of Xiamen University and 229 patients from the First Affiliated Hospital of Fujian Medical University,between January 1,2012,and May 31,2020.The patients were divided into two groups:146 cases in the ESA group and 188 cases in the SSA group.Clinical data from both groups were compared,and the survival prognosis was followed up.RESULTS The operation time for the ESA group was significantly shorter than that of the SSA group(197.1±57.7 minutes vs 218.6±67.5 minutes,χ2=4.298,P=0.039).There were no significant differences between the two groups in intraoperative blood loss,postoperative pain score at 48 hours,time to first bowel movement,number of lymph nodes dissected,or postoperative complications such as anastomotic leakage,bleeding,stenosis.and adhesive intestinal obstruction at 6 months,12 months,and 24 months(P>0.05).Specifically,the incidence of complications like anastomotic leakage was 2.1%in the ESA group vs 4.3%in the SSA group(P=0.264).The 5-year disease-free survival(DFS)rate was 66.4%for the ESA group and 63.9%for the SSA group(P=0.693).There were no significant differences in the overall survival rate between the two groups.The incidence of splenic laceration was significantly higher in the SSA group(3.7%vs 0.7%,P=0.018).Overall,the 5-year DFS was 66.4%for ESA and 63.9%for SSA,with no significant difference in survival between the groups(P=0.693).CONCLUSION Both laparoscopically assisted left hemicolectomy with ESA and SSA are feasible and offer comparable long-term outcomes.ESA may reduce the need for splenic flexure dissociation,particularly when the tumor is located at the descending colon or its junction with the sigmoid colon,and especially in obese patients,elderly individuals with multiple complications,or those with severe adhesions in the splenic flexure of the surgical field.展开更多
Even if dissociation has various facets,it is clear that knowledge of dissociative psychosis and a dissociative schizophrenia-based viewpoint may provide new perspectives on mental disorders.Many researchers screening...Even if dissociation has various facets,it is clear that knowledge of dissociative psychosis and a dissociative schizophrenia-based viewpoint may provide new perspectives on mental disorders.Many researchers screening for comorbid symptoms of“childhood traumatic experiences”and“dissociation”,where specific characteristics are significant to the presence of psychosis and schizophrenia,may lead to an acceptable definition.In recent years,researchers have also reported crucial advances in the understanding of dissociative psychosis and dissociative schizophrenia.Although clinical studies in this area have been ongoing for a long time,research has not demonstrated that a clear and valid relationship exists between dissociation,childhood traumatic experiences,and schizophrenia or psychotic spectrum disorders.However,some results of statistical comparisons have supported the existence of the clinical manifestation known as dissociative psychosis and dissociative schizophrenia.Dissociation,childhood traumatic experiences,and positive psychotic symptoms may be a prominent part of dissociative psychosis and schizophrenia.The intense presence of negative symptoms may indicate classical schizophrenia.In research and clinical practice,researchers and clinicians may use psychometric tests to detect symptoms of dissociative psychosis.Psychotic persons with traumatic experiences likely benefit from treatment focused on trauma symptomatolgy.展开更多
Electrochemical reduction of nitrate(NO_(3^(-)))serves as an eco-friendly friendly alternative to the conventional Haber-Bosch ammonia(NH_(3))synthesis process.The Cu electrocatalyst is widely recognized for its stron...Electrochemical reduction of nitrate(NO_(3^(-)))serves as an eco-friendly friendly alternative to the conventional Haber-Bosch ammonia(NH_(3))synthesis process.The Cu electrocatalyst is widely recognized for its strong adsorption capacity towards nitrate,but its limited H adsorption and slow hydrogenation of oxynitride intermediates hinder the efficiency of converting NO_(3^(-))into NH_(3).Herein,a series of nanocomposite catalysts composed of CuO nanostructure with low NiO content that grow in-situ on carbon paper(Cu O/Ni O_(x)-CP)were synthesized via hydrothermal method and calcination for enhanced nitrate electroreduction utilizing the strong nitrate adsorption capacity of copper and excellent water dissociation ability of NiO to supply hydrogen free radicals(·H).In-situ Raman spectroscopy reveals dynamic reconstruction of Cu/NiO_(x)during the electrochemical nitrate reduction process from Cu O/NiO_(x).Due to the synergistic effect of Cu and NiO,a high Faradaic efficiency(FE,~97.9%)and yield rate(YR,391.5μmol h^(-1)cm^(-2))of ammonia are achieved on CuO/NiO_(2.3%)-CP.Electron paramagnetic resonance(EPR)proves that the presence of Ni O enhances the generation of·H,which can be rapidly consumed during nitrate reduction process.Density functional theory(DFT)calculations indicate that the activation energy of Ni O(0.57 eV)is much lower than Cu(0.84 e V)for water splitting to generate·H,thus facilitating*NO hydrogenations.This drives us to create more effective catalysts for nitrate reduction under neutral conditions by promoting H2O dissociation.展开更多
As a highly reactive reaction intermediate,surface gallium hydride(Ga–H)has garnered significant attention due to its critical role in various catalytic reactions.However,the detailed experimental characterization of...As a highly reactive reaction intermediate,surface gallium hydride(Ga–H)has garnered significant attention due to its critical role in various catalytic reactions.However,the detailed experimental characterization of this unique species remains challenging.Recently,we have demonstrated that solid-state NMR can be an effective tool for studying surface Ga–H.In this work,we report a comparative solid-state NMR study on H_(2) activation over different Ga_(2)O_(3) polymorphs,specificallyα-,β-andγ-Ga_(2)O_(3).^(1)H solid-state NMR enabled the identification of Ga–H species formed on all the three samples following high-temperature H_(2) treatment.The characteristic ^(1)H NMR signals of Ga–H species are resolved using J-coupling-based double-resonance NMR methods,revealing highly similar lineshapes of Ga–H for all the Ga_(2)O_(3) samples.This suggests potentially similar surface Ga–H configurations among different Ga_(2)O_(3) polymorphs.In addition,the local hydrogen environments on the oxide surfaces are further explored using two-dimensional(2D)^(1)H–^(1)H homonuclear correlation spectra,revealing multiple spatially proximate Ga–H and Ga–H/–OH pairs on different Ga_(2)O_(3) polymorphs.These findings provide insights into the potential mechanism of H_(2) dissociation.Overall,this work offers new perspectives on the local structure of surface Ga–H on Ga_(2)O_(3),and the analytical approach presented here can be further extended to the study of other Ga-based catalysts and other metal hydride species.展开更多
Extracting lithium from coal measures can alleviate the shortage of strategic metal resources.However,the lattice substitution characteristics of lithium in carrier minerals and its extremely fine intercalation and en...Extracting lithium from coal measures can alleviate the shortage of strategic metal resources.However,the lattice substitution characteristics of lithium in carrier minerals and its extremely fine intercalation and entrainment behavior are the challenges that constrain the extraction efficiency of lithium from coal series.This study focuses on improving the separation efficiency between lithium-contain-ing minerals and other minerals and the release behavior of lithium in the liquid phase.First,the feasibility of extracting lithium from car-rier minerals is confirmed based on the occurrence state and the process mineralogy characterized by Bgrimm process mineralogy analyz-ing system(BPMA)and time of flight secondary ion mass spectrometry(TOF-SIMS).The optimal selective grinding behavior is achieved within 15 min,allowing Li carrier minerals,including chlorite,kaolinite,and halloysite,to deliver the best dispersion effect with other minerals.Thus,the enriched lithium carrier minerals have been preenriched through screening.The leaching efficiency of Li has reached 97.43%under 1 mol/L hydrochloric acid,15 g/L pulp density,70℃,and 20 min.Leaching kinetics studies indicate that the de-crease in apparent energy validates the impact of grinding on metal leaching,aligning with the rate-controlling step of a chemical reaction.The process proposed in this study achieves the coordinated control of size and components in coal gangue and actualizes the effective se-lective enrichment of lithium through its low energy consumption and environmentally friendly nature.展开更多
Shear strength of hydrate-bearing sediment is an essential parameter for assessing landslide potential ofhydrate reservoirs under exploration conditions. However, the characteristics and simulation of thisshear streng...Shear strength of hydrate-bearing sediment is an essential parameter for assessing landslide potential ofhydrate reservoirs under exploration conditions. However, the characteristics and simulation of thisshear strength under varying dissociation conditions have not been thoroughly investigated. To this end,a series of triaxial compression tests were first carried out on sediments with varying initial hydratesaturations along dissociation pathways. Combining measured data with microscale analysis, the underlyingmechanism for the evolution of shear strength in hydrate-bearing sediment was studied undervarying partial dissociation pathways. Moreover, a shear strength model for hydrate-bearing sedimentwas proposed, taking into account the hydrate saturation and the unhydrated water content. Apart fromthe parameters derived from the hydrate characteristic curve, only one additional model parameter isrequired. The proposed model was validated using measured data on hydrate sediments. The resultsindicate that the proposed model can effectively capture the shear strength behavior of hydrate-bearingsediment under varying dissociation paths. Finally, a sensitivity analysis of the model parameters wasconducted to characterize the proposed model.展开更多
Deuterium(D),a stable and non-radioactive isotope of hydro-gen,is naturally present in the environment and is distinguishedfrom hydrogen by its greater mass.This mass difference resultsin a reduced stretching frequenc...Deuterium(D),a stable and non-radioactive isotope of hydro-gen,is naturally present in the environment and is distinguishedfrom hydrogen by its greater mass.This mass difference resultsin a reduced stretching frequency of the carbon-deuterium(C-D)bond,leading to lower ground state energy and higher bond dis-sociation energy compared to the carbon-hydrogen(C–H)bond.展开更多
Background:Rho GDP dissociation inhibitor 2(ARHGDIB),a key regulator of Rho GTPase,plays a significant role in the onset and progression of cancer by participating in various biological processes.However,the diverse b...Background:Rho GDP dissociation inhibitor 2(ARHGDIB),a key regulator of Rho GTPase,plays a significant role in the onset and progression of cancer by participating in various biological processes.However,the diverse biological roles of ARHGDIB across pan-cancer remain systematically and comprehensively unexplored.We aimed to elucidate the diagnostic and prognostic roles of ARHGDIB and its potential tumor-related mechanisms in human cancers,using bioinformatics approaches.Methods:Data on 33 tumor types were downloaded from The Cancer Genome Atlas,and R software was used to statistically analyze ARHGDIB expression levels and prognostic significance across pan-cancer.Western blot was used to verify the protein expression of ARHGDIB in breast cancer and liver cancer cell lines.Additionally,various databases,including UALCAN,GEPIA,cBioPortal,TIMER,CancerSEA,GSCALite,and GSEA,were used to examine ARHGDIB protein expression across pan-cancer,its correlation with tumor pathological staging,ARHGDIB mutation types and frequencies,and immune cell infiltration.Furthermore,functional analyses at the single-cell level,drug sensitivity assessments,and explorations of related signaling pathways were performed.Results:ARHGDIB exhibits abnormal expression at mRNA and protein levels across various cancers.Western blot results show that ARHGDIB is highly expressed in breast cancer and liver cancer cells.ARHGDIB influences the prognosis of lower-grade glioma,bladder cancer,sarcoma,and skin cutaneous melanoma.It exhibits the highest frequency of gene alterations in uterine carcinosarcoma,primarily characterized by gene amplification.Additionally,ARHGDIB is strongly associated with immune-infiltrating cells and immune checkpoints in the tumor microenvironment.It potentially influences cancer progression through multiple signaling pathways.Conclusions:ARHGDIB is a potential prognostic marker in various cancers and a crucial regulator of the tumor microenvironment.It represents a promising therapeutic target by modulating cancer progression through multiple biological behaviors and signaling pathways.展开更多
The adsorption/desorption of OH*on electrode surfaces is pivotal in numerous electrocatalytic reactions.To understand the effect of electrolyte pH on that process,in this work,an advanced approach combining ab initio ...The adsorption/desorption of OH*on electrode surfaces is pivotal in numerous electrocatalytic reactions.To understand the effect of electrolyte pH on that process,in this work,an advanced approach combining ab initio molecular dynamics(AIMD)with free energy perturbation is employed to calculate the dehydrogenation free energy of water chemisorbed at differently electrified Pt(111)/electrolyte interfaces.Our findings reveal that the onset potential for OH*formation shifts negatively as the pH increases at low pH condition(pH<4.3),aligning with the cyclic voltammetry curves observed in experimental studies.It indicates the dissociation of chemisorbed water is the primary route for OH*adsorption at low pH condition.Furthermore,it is also found that the variation in dehydrogenation energy across different pH is primarily due to the local hydrogen bonding network surrounding the chemisorbed water.In addition,it is proposed that at high pH conditions OH-oxidation emerges as the primary route for OH*adsorption on Pt(111)constrained by the water chemisorption process.This work provides crucial insights into the pH-dependent adsorption behavior of OH*on the Pt(111)surface and aims to guide the optimization of electrolytes to boost the efficiency of related reactions.展开更多
In the context of future electron-ion collision experiments,particularly the Electron-Ion Collider(EIC)and the Electron-Ion Collider in China(EicC),investigating exclusive photoproduction processes is of paramount imp...In the context of future electron-ion collision experiments,particularly the Electron-Ion Collider(EIC)and the Electron-Ion Collider in China(EicC),investigating exclusive photoproduction processes is of paramount importance.These processes offer a distinctive opportunity to probe the gluon structure of nuclei across a broad range of Bjorken x,thereby enabling measurements of nuclear shadowing and facilitating the search for gluon saturation and color glass condensates.This study explores the potential of utilizing neutron tagging via the Coulomb excitation of nuclei to precisely determine the impact parameter for exclusive photoproduction in electron-ion collisions.By developing the equivalent photon approximation for fast electrons,this study incorporates a coordinate-space-dependent photon flux distribution to elucidate the relationship between the photon transverse momentum distribution and the collision impact parameter.Furthermore,the differential cross section for Coulomb excitation of nuclei is derived by leveraging the spatial information from the photon flux.Our calculations demonstrate that neutron tagging can significantly alter the impact parameter distributions,thereby providing a robust method for impact parameter manipulation in electron-ion collisions.This study provides valuable insights and strategies for exploring the impact parameter dependence of exclusive photoproduction,offering novel insights for experimental design and data analysis.Ultimately,it enhances our understanding of the gluon distribution within the nucleus.展开更多
Nucleotide binding domain,leucine-rich repeat,and pyrin domain-containing 3(NLRP3)is an NLR-protein family member that can be activated by diverse exogenous and endogenous stimuli but without direct binding of any of ...Nucleotide binding domain,leucine-rich repeat,and pyrin domain-containing 3(NLRP3)is an NLR-protein family member that can be activated by diverse exogenous and endogenous stimuli but without direct binding of any of these pathogen ligands.Biological studies show that inactive NLRP3 is usually in an as-sembly state and its activation requires a kinase protein,NEK7.However,our re-cent computational studies as well as other biological investigations have demonstrated that NEK7 does not play a significant role in the activation of NLRP3 assembly and activation.In-stead,biological studies suggest that NEK7 is essential in the dissociation of inactive NLRP3 assemblies.Despite extensive research,the dissociation mechanism of the inactive NLRP3 as-sembly remains largely elusive.In this work,an improved MM-PBSA method is applied to the protein-protein binding free energies in the inactive NLRP3 decamer.Combined with the po-tential mean force(PMF)computation for the 0°→5°conformational change,the standard free-energy change,ΔG^(0)is calculated for NEK7-driven association of the inactive NLRP3 de-camer.Our calculations show that in the absence of NEK7,the dissociation of the inactive NLRP3 decamer is an energetically unfavorable process(ΔG^(0)=99.69 kcal/mol),whereas upon NEK7 binding,the overall standard free energy differenceΔG^(0)=-24.21 kcal/mol is obtained for the inactive NLRP3 decamer dissociation.The free-energy difference calcula-tions in this work also disclose an energetically optimized dissociation pathway,along which the inactive NLRP3 decamer is disunited by a one-by-one dissociation mechanism.展开更多
Biology is governed by macromolecular interactions,perturbation of which often lies at the heart of disease.Most therapeutic drugs,whether they are small molecules or biologics,exert their effects through impeding suc...Biology is governed by macromolecular interactions,perturbation of which often lies at the heart of disease.Most therapeutic drugs,whether they are small molecules or biologics,exert their effects through impeding such interactions,whether they are of an enzyme with its substrate or a ligand with its receptor.Conversely,a handful of approved drugs and a larger number of candidates in development have the opposite effect:They either activate or inhibit a biological output by stabilizing a preexisting complex through reducing the rate at which its components dissociate(koff).展开更多
In this study,six-dimensional(6D)time-dependent wave packet calcula-tions were employed to investigate the dissociation of HCl molecules on two bimetallic surfaces,Cu/Ag(111)and Cu/Au(111).These calculations were base...In this study,six-dimensional(6D)time-dependent wave packet calcula-tions were employed to investigate the dissociation of HCl molecules on two bimetallic surfaces,Cu/Ag(111)and Cu/Au(111).These calculations were based on two accurate potential energy surfaces(PESs)constructed using neu-ral network methodology.Density functional theory(DFT)calculations revealed that the static barrier heights for HCl on Cu/Ag(111)and Cu/Au(111)were 0.32 eV and 0.28 eV,respectively.These values are significantly lower than the barrier height on pure Cu(111)(0.52 eV),primarily due to surface strain effects.However,it was found that the 6D dissociation probability of HCl in(v=0,1,j=0)states on Cu/Au(111)was considerably lower,despite its barrier height being 0.04 eV lower than that for Cu/Ag(111).The underlying mechanism for this observation was attributed to the non-monotonic dependence of the minimum energy path(MEP)on the molecular orientation,which was induced by charge transfer effect for HCl+Cu/Au(111).In contrast,HCl+Cu/Ag(111)exhibited a monotonic dependence.These contrasting behaviors led to dis-tinct differences in rotational alignment and excitation effects for the two reactions.展开更多
Density functional theory(DFT)was performed to systematically study the adsorption and dissociation of N_(2)on Ir(100)and Ir(110)surfaces.By analyzing the properties,including adsorption energies,reaction barriers,and...Density functional theory(DFT)was performed to systematically study the adsorption and dissociation of N_(2)on Ir(100)and Ir(110)surfaces.By analyzing the properties,including adsorption energies,reaction barriers,and optimal adsorption sites,the hollow(H)sites were finally identified as favorable dissociation sites for N_(2).The dissociation barriers of N_(2)are 0.87eV on Ir(100)and 1.12eV on Ir(110),which can be overcome at around 348 and 448 K,respectively.Therefore,Ir(100)is screened as a promising catalyst for N_(2)dissociation compared to Ir(110).This can be attributed to the significantly higher adsorption energy of N_(2)on the H site of Ir(100)(−0.48 eV)compared to that on Ir(110)(−0.22 eV),leading to different dissociation mechanisms on Ir(100)and Ir(110).Ir(100)can dissociate N_(2)directly on H site and Ir(110)should firstly capture N_(2)via bridge site and further transfer the adsorbed N_(2)to the H site,which will dramatically deteriorate the reactivity of N_(2)dissociation.In addition,the following protonation processes of dissociated∗N atoms are all exothermal at 348 K on Ir(100),indicating that the ammonia synthesis can occur spontaneously as the temperature higher than 348 K.These results have provided a reasonable materials design scheme for subsequent ammonia synthesis.展开更多
Synergistic interplays involving multiple active centers originating from TiO2 nanotube layers(TNT)and ruthenium(Ru)species comprising of both single atoms(SAs)and nanoparticles(NPs)augment the alkaline hydrogen evolu...Synergistic interplays involving multiple active centers originating from TiO2 nanotube layers(TNT)and ruthenium(Ru)species comprising of both single atoms(SAs)and nanoparticles(NPs)augment the alkaline hydrogen evolution reaction(HER)by enhancing Volmer kinetics from rapid water dissociation and improving Tafel kinetics from efficient H*desorption.Atomic layer deposition of Ru with 50 process cycles results in a mixture of Ru SAs and 2.8-0.4 nm NPs present on TNT layers,and it emerges with the highest HER activity among all the electrodes synthesized.A detailed study of the Ti and Ru species using different high-resolution techniques confirmed the presence of Ti^(3+)states and the coexistence of Ru SAs and NPs.With insights from literature,the role of Ti^(3+),appropriate work functions of TNT layers and Ru,and the synergistic effect of Ru SAs and Ru NPs in improving the performance of alkaline HER were elaborated and justified.The aforementioned characteristics led to a remarkable performance by having 9mV onset potentials and 33 mV dec^(-1) of Tafel slopes and a higher turnover frequency of 1.72 H2 s^(-1) at 30 mV.Besides,a notable stability from 28 h staircase chronopotentiometric measurements for TNT@Ru surpasses TNT@Pt in comparison.展开更多
文摘This paper discussed the setting up of a comeuter automatic system for testing the dy-namic dissociating tension of cooked cocoon filament by means of microcomputer tech-niques.The dynamic dissociating tension of two kinds of row cocoons with differentreelability was tested and analysed under different cocoon cooking conditions.More relia-ble data have been obtained by quantitative tests.The conclusions reached by analysingthese data are of practical significance to perfecting the cocoon cooking theory,assessingcocoon quality,improving the cocoon cooking process,etc.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11504112,91536218,and 11604100)
文摘We theoretically investigate the production of cold CN molecules by photodissociating ICN precursors in a brute-force field. The energy shifts and adiabatic orientation of the rotational ICN precursors are first investigated as a function of the external field strength. The dynamical photofragmentation of ICN precursors is numerically simulated for cases with and without orienting field. The CN products are compared in terms of their velocity distributions. A small portion of the CN fragments are recoiled to near zero speed in the lab frame by appropriately selecting the photo energy for dissociation. With a precursor ICN molecular beam of - 1.5 K in rotational temperature, the production of low speed CN fragments can be improved by more than 5 times when an orienting electrical field of 100 k V/cm is present. The corresponding production rate for decelerated fragments with speeds ≤ 50 m/s is simulated to be about ～2.1×10^-4 and CN number densities of 10^8 –10^10 cm^-3 can be reached with precursor ICN densities of ～10^12 –10^14 cm^-3 from supersonic expansion.
基金supported by National Science Fund for Distinguished Young Scholars(Grant No.52325206)National Key Research and Development Program of China(Grant No.2021YFF0500600)+3 种基金National Natural Science Foundation of China(Grant Nos.U2001220 and 52203298)Shenzhen Technical Plan Project(Grant Nos.RCJC20200714114436091,JCYJ20220530143012027,JCYJ20220818101003008,and JCYJ20220818101003007)Tsinghua Shenzhen International Graduate School-Shenzhen Pengrui Young Faculty Program of Shenzhen Pengrui Foundation(Grant No.SZPR2023006)Shenzhen Science and Technology Program(Grant No.WDZC20231126160733001).
文摘Composite solid electrolytes(CSEs)are considered among the most promising candidates for solid-state batteries.However,their practical application is hindered by low ionic conductivity and a limited lithium-ion transference number,primarily owing to the insufficient mobility of Li+.In this work,we design a heterojunc-tion nanoparticle composed of bimetallic zeolitic imidazolate frameworks(ZIFs)coupled with amorphous tita-nium oxide(TiO_(2)@Zn/Co–ZIF)as a filler to fabricate a composite solid-state electrolyte(PVZT).The amor-phous TiO_(2) coating facilitates salt dissociation through Lewis acid–base interactions with the anions of the lithium salt.Meanwhile,the Zn/Co–ZIF framework not only provides additional selective pathways for Li+transport but also effectively restricts anion migration through its confined pore size.The synergistic effect results in a high room-temperature ionic conductivity(8.8×10^(-4) S·cm^(-1))and a lithium-ion transference number of 0.47 for PVZT.A symmetrical cell using PVZT demonstrates stable Li+deposition/stripping for over 1100 h at a current density of 0.1 mA·cm^(-2).Additionally,a LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/Li full cell using PVZT retains 75.0%of its capacity after 1200 cycles at a 2 C rate.This work offers valuable insights into the design of func-tional fillers for CSEs with highly efficient ion transport.
基金Supported by NSFC (Nos.12171089,12271235)NSF of Jiangsu (No.BK20190919)NSF of Fujian (No.2021J02048)。
文摘For a simple graph G,let A(G)and D(G)be the adjacency matrix and the diagonal degree matrix of G,respectively.[Appl.Anal.Discrete Math.,2017,11(1):81-107]defined the matrix A_(α)(G)of G as A_(α)(G)=αD(G)(1-α)A(G),α∈[0,1].The Aa-spectral radius is the largest eigenvalue of A_(α)(G).Let G_(n,β) be the set graphs with order n and dissociation numberβ.In this paper,we identify the b with maximal A_(α)-spectral radius among all graphs in G_(n,β).
基金supported by the Key Research and Development Program of Shaanxi Province(No.2024SF-YBXM-567)the National Natural Science Foundation of China(Nos.21976045,22076112)the China Scholarship Council(CSC)Scholarship(No.202308610123).
文摘As antibiotic pollutants cannot be incompletely removed by conventional wastewater treatment plants,ultraviolet(UV)based advanced oxidation processes(AOPs)such as UV/persulfate(UV/PS)and UV/chlorine are increasingly concerned for the effective removal of antibiotics from wastewaters.However,the specific mechanisms involving degradation kinetics and transformation mechanisms are not well elucidated.Here we report a detailed examination of SO_(4)•−/Cl•-mediated degradation kinetics,products,and toxicities of sulfathiazole(ST),sarafloxacin(SAR),and lomefloxacin(LOM)in the two processes.Both SO_(4)•−/Cl•-mediated transformation kinetics were found to be dependent on pH(P<0.05),which was attributed to the disparate reactivities of their individual dissociated forms.Based on competition kinetic experiments and matrix calculations,the cationic forms(H_(2)ST^(+),H_(2)SAR^(+),and H_(2)LOM^(+))were more highly reactive towards SO_(4)•−in most cases,while the neutral forms(e.g.,HSAR^(0)and HLOM^(0))reacted the fastest with Cl•for the most of the antibiotics tested.Based on the identification of 31 key intermediates using tandem mass spectrometry,these reactions generated different products,of which the majority still retained the core chemical structure of the parent compounds.The corresponding diverse transformation pathways were proposed,involving S−N breaking,hydroxylation,defluorination,and chlorination reactions.Furthermore,the toxicity changes of their reaction solutions as well as the toxicity of each intermediate were evaluated by the vibrio fischeri and ECOSAR model,respectively.Many primary by-products were proven to be more toxic than the parent chemicals,raising the wider issue of extended potency for these compounds with regards to their ecotoxicity.These results have implications for assessing the degradative fate and risk of these chemicals during the AOPs.
文摘BACKGROUND Left colon cancer surgery relies on laparoscopic hemicolectomy,with digestive tract reconstruction critical.End-to-side anastomosis(ESA)and side-to-side anastomosis(SSA)anastomoses are common,but their comparative outcomes,especially in splenic flexure handling and efficacy,need clarification.This study compares ESA and SSA to guide surgical practice.AIM To compare the clinical outcomes of laparoscopically assisted left hemicolectomy with ESA and SSA.METHODS A total of 334 patients were included,with 105 patients from the First Affiliated Hospital of Xiamen University and 229 patients from the First Affiliated Hospital of Fujian Medical University,between January 1,2012,and May 31,2020.The patients were divided into two groups:146 cases in the ESA group and 188 cases in the SSA group.Clinical data from both groups were compared,and the survival prognosis was followed up.RESULTS The operation time for the ESA group was significantly shorter than that of the SSA group(197.1±57.7 minutes vs 218.6±67.5 minutes,χ2=4.298,P=0.039).There were no significant differences between the two groups in intraoperative blood loss,postoperative pain score at 48 hours,time to first bowel movement,number of lymph nodes dissected,or postoperative complications such as anastomotic leakage,bleeding,stenosis.and adhesive intestinal obstruction at 6 months,12 months,and 24 months(P>0.05).Specifically,the incidence of complications like anastomotic leakage was 2.1%in the ESA group vs 4.3%in the SSA group(P=0.264).The 5-year disease-free survival(DFS)rate was 66.4%for the ESA group and 63.9%for the SSA group(P=0.693).There were no significant differences in the overall survival rate between the two groups.The incidence of splenic laceration was significantly higher in the SSA group(3.7%vs 0.7%,P=0.018).Overall,the 5-year DFS was 66.4%for ESA and 63.9%for SSA,with no significant difference in survival between the groups(P=0.693).CONCLUSION Both laparoscopically assisted left hemicolectomy with ESA and SSA are feasible and offer comparable long-term outcomes.ESA may reduce the need for splenic flexure dissociation,particularly when the tumor is located at the descending colon or its junction with the sigmoid colon,and especially in obese patients,elderly individuals with multiple complications,or those with severe adhesions in the splenic flexure of the surgical field.
文摘Even if dissociation has various facets,it is clear that knowledge of dissociative psychosis and a dissociative schizophrenia-based viewpoint may provide new perspectives on mental disorders.Many researchers screening for comorbid symptoms of“childhood traumatic experiences”and“dissociation”,where specific characteristics are significant to the presence of psychosis and schizophrenia,may lead to an acceptable definition.In recent years,researchers have also reported crucial advances in the understanding of dissociative psychosis and dissociative schizophrenia.Although clinical studies in this area have been ongoing for a long time,research has not demonstrated that a clear and valid relationship exists between dissociation,childhood traumatic experiences,and schizophrenia or psychotic spectrum disorders.However,some results of statistical comparisons have supported the existence of the clinical manifestation known as dissociative psychosis and dissociative schizophrenia.Dissociation,childhood traumatic experiences,and positive psychotic symptoms may be a prominent part of dissociative psychosis and schizophrenia.The intense presence of negative symptoms may indicate classical schizophrenia.In research and clinical practice,researchers and clinicians may use psychometric tests to detect symptoms of dissociative psychosis.Psychotic persons with traumatic experiences likely benefit from treatment focused on trauma symptomatolgy.
基金supported by the National Natural Science Foundation of China(No.U22A20253)。
文摘Electrochemical reduction of nitrate(NO_(3^(-)))serves as an eco-friendly friendly alternative to the conventional Haber-Bosch ammonia(NH_(3))synthesis process.The Cu electrocatalyst is widely recognized for its strong adsorption capacity towards nitrate,but its limited H adsorption and slow hydrogenation of oxynitride intermediates hinder the efficiency of converting NO_(3^(-))into NH_(3).Herein,a series of nanocomposite catalysts composed of CuO nanostructure with low NiO content that grow in-situ on carbon paper(Cu O/Ni O_(x)-CP)were synthesized via hydrothermal method and calcination for enhanced nitrate electroreduction utilizing the strong nitrate adsorption capacity of copper and excellent water dissociation ability of NiO to supply hydrogen free radicals(·H).In-situ Raman spectroscopy reveals dynamic reconstruction of Cu/NiO_(x)during the electrochemical nitrate reduction process from Cu O/NiO_(x).Due to the synergistic effect of Cu and NiO,a high Faradaic efficiency(FE,~97.9%)and yield rate(YR,391.5μmol h^(-1)cm^(-2))of ammonia are achieved on CuO/NiO_(2.3%)-CP.Electron paramagnetic resonance(EPR)proves that the presence of Ni O enhances the generation of·H,which can be rapidly consumed during nitrate reduction process.Density functional theory(DFT)calculations indicate that the activation energy of Ni O(0.57 eV)is much lower than Cu(0.84 e V)for water splitting to generate·H,thus facilitating*NO hydrogenations.This drives us to create more effective catalysts for nitrate reduction under neutral conditions by promoting H2O dissociation.
基金financially supported by the National Key R&D Program of China(No.2021YFA1502803)the National Natural Science Foundation of China(Nos.22325405,22372160,22432005 and 22321002)Dalian Science and Technology Talent Innovation Program(No.2024RG009).
文摘As a highly reactive reaction intermediate,surface gallium hydride(Ga–H)has garnered significant attention due to its critical role in various catalytic reactions.However,the detailed experimental characterization of this unique species remains challenging.Recently,we have demonstrated that solid-state NMR can be an effective tool for studying surface Ga–H.In this work,we report a comparative solid-state NMR study on H_(2) activation over different Ga_(2)O_(3) polymorphs,specificallyα-,β-andγ-Ga_(2)O_(3).^(1)H solid-state NMR enabled the identification of Ga–H species formed on all the three samples following high-temperature H_(2) treatment.The characteristic ^(1)H NMR signals of Ga–H species are resolved using J-coupling-based double-resonance NMR methods,revealing highly similar lineshapes of Ga–H for all the Ga_(2)O_(3) samples.This suggests potentially similar surface Ga–H configurations among different Ga_(2)O_(3) polymorphs.In addition,the local hydrogen environments on the oxide surfaces are further explored using two-dimensional(2D)^(1)H–^(1)H homonuclear correlation spectra,revealing multiple spatially proximate Ga–H and Ga–H/–OH pairs on different Ga_(2)O_(3) polymorphs.These findings provide insights into the potential mechanism of H_(2) dissociation.Overall,this work offers new perspectives on the local structure of surface Ga–H on Ga_(2)O_(3),and the analytical approach presented here can be further extended to the study of other Ga-based catalysts and other metal hydride species.
基金supported by the National Key R&D Program of China(No.2023YFC2907701)This work was also supported by the Fundamental Research Program of Shanxi Province,China(No.202103021223045)+4 种基金the Shanxi Scholarship Council of China(No.2022-062)the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi,China(No.2021L064)This study was also funded by Open Foundation of State Key Laboratory of Mineral Processing(No.BGRIMM-KJSKL-2025-26)This work was supported by the National Natural Science Foundation of China(No.52104260)This work was supported by Young Elite Scientists Sponsorship Program by CAST(No.2022QNRC001).
文摘Extracting lithium from coal measures can alleviate the shortage of strategic metal resources.However,the lattice substitution characteristics of lithium in carrier minerals and its extremely fine intercalation and entrainment behavior are the challenges that constrain the extraction efficiency of lithium from coal series.This study focuses on improving the separation efficiency between lithium-contain-ing minerals and other minerals and the release behavior of lithium in the liquid phase.First,the feasibility of extracting lithium from car-rier minerals is confirmed based on the occurrence state and the process mineralogy characterized by Bgrimm process mineralogy analyz-ing system(BPMA)and time of flight secondary ion mass spectrometry(TOF-SIMS).The optimal selective grinding behavior is achieved within 15 min,allowing Li carrier minerals,including chlorite,kaolinite,and halloysite,to deliver the best dispersion effect with other minerals.Thus,the enriched lithium carrier minerals have been preenriched through screening.The leaching efficiency of Li has reached 97.43%under 1 mol/L hydrochloric acid,15 g/L pulp density,70℃,and 20 min.Leaching kinetics studies indicate that the de-crease in apparent energy validates the impact of grinding on metal leaching,aligning with the rate-controlling step of a chemical reaction.The process proposed in this study achieves the coordinated control of size and components in coal gangue and actualizes the effective se-lective enrichment of lithium through its low energy consumption and environmentally friendly nature.
基金supported by the National Natural Science Foundation of China(Grant No.51939011)the Science and Technology Program of CNOOC Research Institute(Grant No.2023OTKK03)supported by the program of the Youth Innovation Promotion Association,Chinese Academy of Sciences(Grant No.2020326).
文摘Shear strength of hydrate-bearing sediment is an essential parameter for assessing landslide potential ofhydrate reservoirs under exploration conditions. However, the characteristics and simulation of thisshear strength under varying dissociation conditions have not been thoroughly investigated. To this end,a series of triaxial compression tests were first carried out on sediments with varying initial hydratesaturations along dissociation pathways. Combining measured data with microscale analysis, the underlyingmechanism for the evolution of shear strength in hydrate-bearing sediment was studied undervarying partial dissociation pathways. Moreover, a shear strength model for hydrate-bearing sedimentwas proposed, taking into account the hydrate saturation and the unhydrated water content. Apart fromthe parameters derived from the hydrate characteristic curve, only one additional model parameter isrequired. The proposed model was validated using measured data on hydrate sediments. The resultsindicate that the proposed model can effectively capture the shear strength behavior of hydrate-bearingsediment under varying dissociation paths. Finally, a sensitivity analysis of the model parameters wasconducted to characterize the proposed model.
基金Financial support from Science and Technology Innovation Program of Hunan Province(No.2022RC4044)。
文摘Deuterium(D),a stable and non-radioactive isotope of hydro-gen,is naturally present in the environment and is distinguishedfrom hydrogen by its greater mass.This mass difference resultsin a reduced stretching frequency of the carbon-deuterium(C-D)bond,leading to lower ground state energy and higher bond dis-sociation energy compared to the carbon-hydrogen(C–H)bond.
基金supported by a grant from the Hefei Municipal Health Commission Applied Medical Research Project(No.Hwk2023zd007)。
文摘Background:Rho GDP dissociation inhibitor 2(ARHGDIB),a key regulator of Rho GTPase,plays a significant role in the onset and progression of cancer by participating in various biological processes.However,the diverse biological roles of ARHGDIB across pan-cancer remain systematically and comprehensively unexplored.We aimed to elucidate the diagnostic and prognostic roles of ARHGDIB and its potential tumor-related mechanisms in human cancers,using bioinformatics approaches.Methods:Data on 33 tumor types were downloaded from The Cancer Genome Atlas,and R software was used to statistically analyze ARHGDIB expression levels and prognostic significance across pan-cancer.Western blot was used to verify the protein expression of ARHGDIB in breast cancer and liver cancer cell lines.Additionally,various databases,including UALCAN,GEPIA,cBioPortal,TIMER,CancerSEA,GSCALite,and GSEA,were used to examine ARHGDIB protein expression across pan-cancer,its correlation with tumor pathological staging,ARHGDIB mutation types and frequencies,and immune cell infiltration.Furthermore,functional analyses at the single-cell level,drug sensitivity assessments,and explorations of related signaling pathways were performed.Results:ARHGDIB exhibits abnormal expression at mRNA and protein levels across various cancers.Western blot results show that ARHGDIB is highly expressed in breast cancer and liver cancer cells.ARHGDIB influences the prognosis of lower-grade glioma,bladder cancer,sarcoma,and skin cutaneous melanoma.It exhibits the highest frequency of gene alterations in uterine carcinosarcoma,primarily characterized by gene amplification.Additionally,ARHGDIB is strongly associated with immune-infiltrating cells and immune checkpoints in the tumor microenvironment.It potentially influences cancer progression through multiple signaling pathways.Conclusions:ARHGDIB is a potential prognostic marker in various cancers and a crucial regulator of the tumor microenvironment.It represents a promising therapeutic target by modulating cancer progression through multiple biological behaviors and signaling pathways.
基金support from the National Natural Science Foundation of China(Nos.22272193,22225302,21991151,and 21991150)the Ningbo Natural Science Foundation(No.2022J294)+1 种基金the Yongjiang Talent Introduction Program(No.2021A-115-G)Key Laboratory of Advanced Marine Materials,Ningbo Institute of Materials Technology and Engineering,Chinese Academy of Sciences,Ningbo.(No.2021A-115-G).
文摘The adsorption/desorption of OH*on electrode surfaces is pivotal in numerous electrocatalytic reactions.To understand the effect of electrolyte pH on that process,in this work,an advanced approach combining ab initio molecular dynamics(AIMD)with free energy perturbation is employed to calculate the dehydrogenation free energy of water chemisorbed at differently electrified Pt(111)/electrolyte interfaces.Our findings reveal that the onset potential for OH*formation shifts negatively as the pH increases at low pH condition(pH<4.3),aligning with the cyclic voltammetry curves observed in experimental studies.It indicates the dissociation of chemisorbed water is the primary route for OH*adsorption at low pH condition.Furthermore,it is also found that the variation in dehydrogenation energy across different pH is primarily due to the local hydrogen bonding network surrounding the chemisorbed water.In addition,it is proposed that at high pH conditions OH-oxidation emerges as the primary route for OH*adsorption on Pt(111)constrained by the water chemisorption process.This work provides crucial insights into the pH-dependent adsorption behavior of OH*on the Pt(111)surface and aims to guide the optimization of electrolytes to boost the efficiency of related reactions.
基金supported in part by the National Key Research and Development Program of China under Contract No.2022YFA1604900the National Natural Science Foundation of China(NSFC)under Contract No.12175223 and 12005220+1 种基金W.Zha is supported by Anhui Provincial Natural Science Foundation No.2208085J23Youth Innovation Promotion Association of Chinese Academy of Science.
文摘In the context of future electron-ion collision experiments,particularly the Electron-Ion Collider(EIC)and the Electron-Ion Collider in China(EicC),investigating exclusive photoproduction processes is of paramount importance.These processes offer a distinctive opportunity to probe the gluon structure of nuclei across a broad range of Bjorken x,thereby enabling measurements of nuclear shadowing and facilitating the search for gluon saturation and color glass condensates.This study explores the potential of utilizing neutron tagging via the Coulomb excitation of nuclei to precisely determine the impact parameter for exclusive photoproduction in electron-ion collisions.By developing the equivalent photon approximation for fast electrons,this study incorporates a coordinate-space-dependent photon flux distribution to elucidate the relationship between the photon transverse momentum distribution and the collision impact parameter.Furthermore,the differential cross section for Coulomb excitation of nuclei is derived by leveraging the spatial information from the photon flux.Our calculations demonstrate that neutron tagging can significantly alter the impact parameter distributions,thereby providing a robust method for impact parameter manipulation in electron-ion collisions.This study provides valuable insights and strategies for exploring the impact parameter dependence of exclusive photoproduction,offering novel insights for experimental design and data analysis.Ultimately,it enhances our understanding of the gluon distribution within the nucleus.
基金supported by Ministry of Science and Technology of China(2022YFA1303100)the National Natural Science Foundation of China(No.32090040)。
文摘Nucleotide binding domain,leucine-rich repeat,and pyrin domain-containing 3(NLRP3)is an NLR-protein family member that can be activated by diverse exogenous and endogenous stimuli but without direct binding of any of these pathogen ligands.Biological studies show that inactive NLRP3 is usually in an as-sembly state and its activation requires a kinase protein,NEK7.However,our re-cent computational studies as well as other biological investigations have demonstrated that NEK7 does not play a significant role in the activation of NLRP3 assembly and activation.In-stead,biological studies suggest that NEK7 is essential in the dissociation of inactive NLRP3 assemblies.Despite extensive research,the dissociation mechanism of the inactive NLRP3 as-sembly remains largely elusive.In this work,an improved MM-PBSA method is applied to the protein-protein binding free energies in the inactive NLRP3 decamer.Combined with the po-tential mean force(PMF)computation for the 0°→5°conformational change,the standard free-energy change,ΔG^(0)is calculated for NEK7-driven association of the inactive NLRP3 de-camer.Our calculations show that in the absence of NEK7,the dissociation of the inactive NLRP3 decamer is an energetically unfavorable process(ΔG^(0)=99.69 kcal/mol),whereas upon NEK7 binding,the overall standard free energy differenceΔG^(0)=-24.21 kcal/mol is obtained for the inactive NLRP3 decamer dissociation.The free-energy difference calcula-tions in this work also disclose an energetically optimized dissociation pathway,along which the inactive NLRP3 decamer is disunited by a one-by-one dissociation mechanism.
文摘Biology is governed by macromolecular interactions,perturbation of which often lies at the heart of disease.Most therapeutic drugs,whether they are small molecules or biologics,exert their effects through impeding such interactions,whether they are of an enzyme with its substrate or a ligand with its receptor.Conversely,a handful of approved drugs and a larger number of candidates in development have the opposite effect:They either activate or inhibit a biological output by stabilizing a preexisting complex through reducing the rate at which its components dissociate(koff).
基金supported by the National Key R&D Program of China(No.2018YFE0203003)the National Natural Science Foundation of China(Nos.22173101,22173099,22288201,21703242)+3 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0970203)the Innovation Program for Quantum Science and Technology(No.2021ZD0303305)Dalian Talents Innovation Support Program(No.2021RD05)the Open Fund(SKLMRD-K202508)of the State Key Laboratory of Molecular Reaction Dynamics in Dalian Institute of Chemical Physics,Chinese Academy of Sciences.The computational resources are supported by SongShan Lake HPC Center(SSL-HPC)in Great Bay University.
文摘In this study,six-dimensional(6D)time-dependent wave packet calcula-tions were employed to investigate the dissociation of HCl molecules on two bimetallic surfaces,Cu/Ag(111)and Cu/Au(111).These calculations were based on two accurate potential energy surfaces(PESs)constructed using neu-ral network methodology.Density functional theory(DFT)calculations revealed that the static barrier heights for HCl on Cu/Ag(111)and Cu/Au(111)were 0.32 eV and 0.28 eV,respectively.These values are significantly lower than the barrier height on pure Cu(111)(0.52 eV),primarily due to surface strain effects.However,it was found that the 6D dissociation probability of HCl in(v=0,1,j=0)states on Cu/Au(111)was considerably lower,despite its barrier height being 0.04 eV lower than that for Cu/Ag(111).The underlying mechanism for this observation was attributed to the non-monotonic dependence of the minimum energy path(MEP)on the molecular orientation,which was induced by charge transfer effect for HCl+Cu/Au(111).In contrast,HCl+Cu/Ag(111)exhibited a monotonic dependence.These contrasting behaviors led to dis-tinct differences in rotational alignment and excitation effects for the two reactions.
基金funded by the Natural Science Foundation of China(No.21603109)the Henan Joint Fund of the National Natural Science Foundation of China(No.U1404216)+1 种基金the Scientific Research Program Funded by Shaanxi Provincial Education Department(No.20JK0676)supported by Natural Science Basic Research Program of Shanxi(Nos.2022JQ-108,2022JQ096)。
文摘Density functional theory(DFT)was performed to systematically study the adsorption and dissociation of N_(2)on Ir(100)and Ir(110)surfaces.By analyzing the properties,including adsorption energies,reaction barriers,and optimal adsorption sites,the hollow(H)sites were finally identified as favorable dissociation sites for N_(2).The dissociation barriers of N_(2)are 0.87eV on Ir(100)and 1.12eV on Ir(110),which can be overcome at around 348 and 448 K,respectively.Therefore,Ir(100)is screened as a promising catalyst for N_(2)dissociation compared to Ir(110).This can be attributed to the significantly higher adsorption energy of N_(2)on the H site of Ir(100)(−0.48 eV)compared to that on Ir(110)(−0.22 eV),leading to different dissociation mechanisms on Ir(100)and Ir(110).Ir(100)can dissociate N_(2)directly on H site and Ir(110)should firstly capture N_(2)via bridge site and further transfer the adsorbed N_(2)to the H site,which will dramatically deteriorate the reactivity of N_(2)dissociation.In addition,the following protonation processes of dissociated∗N atoms are all exothermal at 348 K on Ir(100),indicating that the ammonia synthesis can occur spontaneously as the temperature higher than 348 K.These results have provided a reasonable materials design scheme for subsequent ammonia synthesis.
基金support from the European Union Horizon 2020 program(project HERMES,nr.952184)the Ministry of Education,Youth and Sports of the Czech Republic for supporting CEMNAT(LM2023037)+1 种基金Czech-NanoLab(LM2023051)infrastructures for providing ALD,SEM,EDX,XPS,TEM,and XRDCzech Science Foundation(project 23-08019X,EXPRO).
文摘Synergistic interplays involving multiple active centers originating from TiO2 nanotube layers(TNT)and ruthenium(Ru)species comprising of both single atoms(SAs)and nanoparticles(NPs)augment the alkaline hydrogen evolution reaction(HER)by enhancing Volmer kinetics from rapid water dissociation and improving Tafel kinetics from efficient H*desorption.Atomic layer deposition of Ru with 50 process cycles results in a mixture of Ru SAs and 2.8-0.4 nm NPs present on TNT layers,and it emerges with the highest HER activity among all the electrodes synthesized.A detailed study of the Ti and Ru species using different high-resolution techniques confirmed the presence of Ti^(3+)states and the coexistence of Ru SAs and NPs.With insights from literature,the role of Ti^(3+),appropriate work functions of TNT layers and Ru,and the synergistic effect of Ru SAs and Ru NPs in improving the performance of alkaline HER were elaborated and justified.The aforementioned characteristics led to a remarkable performance by having 9mV onset potentials and 33 mV dec^(-1) of Tafel slopes and a higher turnover frequency of 1.72 H2 s^(-1) at 30 mV.Besides,a notable stability from 28 h staircase chronopotentiometric measurements for TNT@Ru surpasses TNT@Pt in comparison.
