Millions of men each year are faced with a clinical suspicion of prostate cancer （PCa） but the prostate biopsy fails to detect the disease. For the urologists, how to select the appropriate candidate for repeat biop...Millions of men each year are faced with a clinical suspicion of prostate cancer （PCa） but the prostate biopsy fails to detect the disease. For the urologists, how to select the appropriate candidate for repeat biopsy is a significant clinical dilemma. Traditional risk-stratification tools in this setting such as prostate-specific antigen （PSA） related markers and histopathology findings have met with limited correlation with cancer diagnosis or with significant disease. Thus, an individualized approach using predictive models such as an online risk calculator （RC） or updated biomarkers is more suitable in counseling men about their risk of harboring clinically significant prostate cancer, This review will focus on the available risk-stratification tools in the population of men with prior negative biopsies and persistent suspicion of PCa. The underlying methodology and platforms of the available tools are reviewed to better understand the development and validation of these models. The index patient is then assessed with different RCs to determine the range of heterogeneity among various RCs. This should allow the urologists to better incorporate these various risk-stratification tools into their clinical practice and improve patient counseling.展开更多
Risk calculators have offered a viable tool for clinicians to stratify patients at risk of prostate cancer(PCa)and to mitigate the low sensitivity and specificity of screening prostate specific antigen(PSA).While init...Risk calculators have offered a viable tool for clinicians to stratify patients at risk of prostate cancer(PCa)and to mitigate the low sensitivity and specificity of screening prostate specific antigen(PSA).While initially based on clinical and demographic data,incorporation of multiparametric magnetic resonance imaging(MRI)and the validated prostate imaging reporting and data system suspicion scoring system has standardized and improved risk stratification beyond the use of PSA and patient parameters alone.Biopsy-naïve patients with lower risk profiles for harboring clinically significant PCa are often subjected to uncomfortable,invasive,and potentially unnecessary prostate biopsy procedures.Incorporating risk calculator data into prostate MRI reports can broaden the role of radiologists,improve communication with clinicians primarily managing these patients,and help guide clinical care in directing the screening,detection,and risk stratification of PCa.展开更多
Risk prediction models including the Prostate Health Index(phi)for prostate cancer have been well established and evaluated in the Western population.The aim of this study is to build phi-based risk calculators in a p...Risk prediction models including the Prostate Health Index(phi)for prostate cancer have been well established and evaluated in the Western population.The aim of this study is to build phi-based risk calculators in a prostate biopsy population and evaluate their performanee in predicting prostate cancer(PCa)and high-grade PCa(Gleason score 27)in the Chinese population.We developed risk calculators based on 635 men who underwent initial prostate biopsy.Then,we validated the performance of prostate-specific antigen(PSA),phi,and the risk calculators in an additional observational cohort of 1045 men.We observed that the phi-based risk calculators(risk calculators 2 and 4)outperformed the PSA-based risk calculator for predicting PCa and high-grade PCa in the training cohort.In the validation study,the area under the receiver operating characteristic curve(AUC)for risk calculators 2 and 4 reached 0.91 and 0.92,respectively,for predicting PCa and high-grade PCa,respectively;the AUC values were better than those for risk calculator 1(PSA-based model with an AUC of 0.81 and 0.82,respectively)(all P<0.001).Such superiority was also observed in the stratified population with PSA ranging from 2.0 ng ml^-1 to 10.0 ng ml^-1.Decision curves confirmed that a considerable proportion of unnecessary biopsies could be avoided while applying phi-based risk calculators.In this study,we showed that,compared to risk calculators without phi,phi-based risk calculators exhibited superior discrimination and calibration for PCa in the Chinese biopsy population.Applying these risk calculators also considerably reduced the number of unnecessary biopsies for PCa.展开更多
The performances of the Prostate Cancer Prevention Trial （PCPT） risk calculator and other risk calculators for prostate cancer （PCa） prediction in Chinese populations were poorly understood. We performed this stud...The performances of the Prostate Cancer Prevention Trial （PCPT） risk calculator and other risk calculators for prostate cancer （PCa） prediction in Chinese populations were poorly understood. We performed this study to build risk calculators （Huashan risk calculators） based on Chinese population and validated the performance of prostate-specific antigen （PSA）, PCPT risk calculator, and Huashan risk calculators in a validation cohort. We built Huashan risk calculators based on data from 1059 men who underwent initial prostate biopsy from January 2006 to December 2010 in a training cohort. Then, we validated the performance of PSA, PCPT risk calculator, and Huashan risk calculators in an observational validation study from January 2011 to December 2014. All necessary clinical information were collected before the biopsy. The results showed that Huashan risk calculators 1 and 2 outperformed the PCPT risk calculator for predicting PCa in both entire training cohort and stratified population （with PSA from 2.0 ng ml^-1 to 20.0 ng ml^-1）. In the validation study, Huashan risk calculator 1 still outperformed the PCPT risk calculator in the entire validation cohort （0.849 vs 0.779 in area under the receiver operating characteristic curve [AUC]） and stratified population. A considerable reduction of unnecessary biopsies （approximately 30%） was also observed when the Huashan risk calculators were used. Thus, we believe that the Huashan risk calculators （especially Huashan risk calculator 1） may have added value for predicting PCa in Chinese population. However, these results still needed further evaluation in larger populations.展开更多
Risk calculators are widely used in many clinical fields, and integrate several important risk factors through the conversion of a risk function into a single measure of risk. Several studies have been carried out to ...Risk calculators are widely used in many clinical fields, and integrate several important risk factors through the conversion of a risk function into a single measure of risk. Several studies have been carried out to create risk calculators for the prediction of hepatocellular carcinoma (HCC) in patients with chronic hepatitis B (CHB). Most of them were hospital-based, with limited sample sizes and insufficient external validation. These study groups collaborated to establish the REACH-B risk score, which incorporated five clinical variables to predict HCC risk. This risk score was then validated in international clinical cohorts. Evidence suggests that quantitative serum HBsAg level provides additional predictability of HCC, especially in patients with low levels of hepatitis B virus DNA. This novel marker was incorporated into a risk calculator and was internally validated. This tool will hopefully be externally validated in the near future. Risk calculators can be used to support clinical practice, and to establish preventive measures; several “off-label” extension usages have also been implemented. Albeit beneficial, several precautions and discussions should be noted in using the risk calculators. The future development of risk calculators for CHB patients can be extended by applying them to additional CHB-related outcomes, and by incorporating emerging risk parameters.展开更多
Over the last few decades,the evolution of liver resection has progressed through numerous milestones in peri-operative management,operative techniques and novel technologies that have dramatically improved patient sa...Over the last few decades,the evolution of liver resection has progressed through numerous milestones in peri-operative management,operative techniques and novel technologies that have dramatically improved patient safety and outcomes(1).Consequently,such developments have enabled surgeons to embark on liver resections of lesions in technically challenging locations,whereby extended resection or bilovascular reconstruction may be required to ensure oncologic clearance.In the context of extended resections or resection of lesions from heavily diseased livers,concerns remain regarding the adequacy of the remnant future liver remnant(FLR)and liver function,placing patients at risk of the clinical phenomenon known as post-hepatectomy liver failure(PHLF).Although relatively uncommon,PHLF has a reported incidence of up to 32%in the literature and remains an important cause of post-hepatectomy morbidity and mortality(2).Presently,several definitions have been proposed to describe PHLF,the most recent of which was proposed by the International Study Group of Liver Surgery(ISGLS).In this definition,PHLF was defined as an increased international normalized ratio(INR)or hyperbilirubinemia on or after post-operative day 5,with further stratification of severity grades(A,B or C)based on the extent of clinical management(3).While definitions in PHLF assist in providing a common diagnostic framework among physicians,establishing predictors in PHLF is conceivably more helpful as it allows surgeons to have important decision-making details prior to planned liver resection.展开更多
The defect regulation and p-n heterojunction of composites have gained significant attention due to their potential applications.Nitrogen(N)as doping heteroatoms and perylene-3,4,9,10-tetracarboximide(PDINH)as an appr...The defect regulation and p-n heterojunction of composites have gained significant attention due to their potential applications.Nitrogen(N)as doping heteroatoms and perylene-3,4,9,10-tetracarboximide(PDINH)as an appropriate n-type semiconductor were innovatively and reasonably selected to enhance the photocatalytic performance of pristine p-type cuprous oxide(Cu_(2)O).In this study,the defect regula-tion of N doping(1)achieved the small-size effect of Cu_(2)O,(2)optimized the electron features,and(3)improved the kinetics of reactive oxygen species.The p-n heterojunction with PDINH was developed to sharply improve the light utilization of Cu_(2)O,from the UV region to the near-infrared region.As expected,the optimized Cu_(2)N_(x)O_(1–x)/PDINH(x=0.02)exhibited excellent long-term photocatalytic antibacterial ac-tivities,with antibacterial rates exceeding 91%against Staphylococcus aureus and Pseudomonas aeruginosa.Defect regulation and p-n heterojunction of Cu_(2)O-based composites thus provide a great deal of potential for future advancements in photocatalysis.展开更多
Up-and-coming high-temperature materials,refractory high entropy alloys,are suffering from lower oxidation resistance,restricting their applications in the aerospace field.In this study,two novel treatments of Al-depo...Up-and-coming high-temperature materials,refractory high entropy alloys,are suffering from lower oxidation resistance,restricting their applications in the aerospace field.In this study,two novel treatments of Al-deposited and remelted were developed to refine the microstructure and enhance the oxidation resistance of refractory high entropy alloy using electron beam freeform fabrication(EBF3).Finer and short-range ordering structures were observed in the remelted sample,whereas the Al-deposited sample showcased the formation of silicide and intermetallic phases.High-temperature cyclic and isothermal oxidation tests at 1000℃ were carried out.The total weight gain after 60 h of cyclic oxidation decreased by 17.49%and 30.46%for the remelted and deposited samples,respectively,compared to the as-cast state.Oxidation kinetics reveal an evident lower mass gain and oxidation rate in the treated samples.A multilayer oxide consisting of TiO_(2)+Al_(2)O_(3)+SiO_(2)+AlNbO_(4) was studied for its excellent oxidation resistance.The oxidation behavior of rutile,corundum and other oxides was analyzed using first principles calculations and chemical defect analysis.Overall,this research,which introduces novel treatments,offers promising insights for enhancing the inherent oxidation resistance of refractory high entropy alloys.展开更多
Nitrogen-doping of carbon support(N-C)for platinum(Pt)nanoparticles to form Pt/N-C catalyst represents an effective strategy to promote the electrocatalysis of cathodic oxygen reduction reaction(ORR)in proton exchange...Nitrogen-doping of carbon support(N-C)for platinum(Pt)nanoparticles to form Pt/N-C catalyst represents an effective strategy to promote the electrocatalysis of cathodic oxygen reduction reaction(ORR)in proton exchange membrane fuel cells.For fundamental understanding,clearly identifying the metalsupport effect on enhancement mechanisms of ORR electrocatalysis is definitely needed.In this work,the impact of Pt-support interaction via interfacial Pt-N coordination on electrocatalytic ORR activity and stability in Pt/N-C catalyst is deeply studied through structural/compositional characterizations,electrochemical measurements and theoretical DFT-calculations/AIMD-simulations.The resulting Pt/N-C catalyst exhibits a superior electrocatalytic performance compared to the commercial Pt/C catalyst in both half-cell and H_(2)-O_(2)fuel cell.Experimental and theoretical results reveal that the interfacial Pt-N coordination enables electron transfer from N-C support to Pt nanoparticles,which can weaken the adsorption strength of oxygen intermediates on Pt surface to improve ORR activity and induce the strong Pt-support interaction to enhance electrochemical stability.展开更多
The quest for high-energy-density magnesium-air batteries is hindered by the efficiency-voltage trade-off,ultimately leading to an unsatisfactory energy density.Here,we effectively mitigate the inherent efficiency-vol...The quest for high-energy-density magnesium-air batteries is hindered by the efficiency-voltage trade-off,ultimately leading to an unsatisfactory energy density.Here,we effectively mitigate the inherent efficiency-voltage trade-off by introducing a novel anode material,specifically,Mg-0.5Sn-0.5In-0.5Ga.This anode demonstrates exceptional anodic efficiency,achieving 60.5±2.5%at 1 mA cm^(-2),65.3±2.7%at 10 mA cm^(-2),and 71.4±1.2%at 20 mA cm^(-2).Furthermore,the discharge voltage is significantly enhanced,reaching 1.76±0.01 V at 1 mA cm^(-2),1.44±0.02 V at 10 mA cm^(-2),and 1.21±0.08 V at 20 mA cm^(-2).Consequently,our newly developed anode exhibits a remarkable energy density of 2312±98 W h kg^(-1),placing it among the top-performing magnesium anodes documented in the literature.Density functional theory calculations and experimental investigations have unveiled that the exceptional performance can be attributed to the inhibition of water reduction,facilitated by the hybridization between solute atoms and neighboring Mg atoms.Furthermore,the activation of the second phase,introducing additional galvanic couples,significantly contributes to this performance.This study presents valuable insights that can guide the design of novel anodes,contributing to the advancement of high-performance magnesium-air batteries.展开更多
As a means of quantitative interpretation,forward calculations of the global lithospheric magnetic field in the Spherical Harmonic(SH)domain have been widely used to reveal geophysical,lithological,and geothermal vari...As a means of quantitative interpretation,forward calculations of the global lithospheric magnetic field in the Spherical Harmonic(SH)domain have been widely used to reveal geophysical,lithological,and geothermal variations in the lithosphere.Traditional approaches either do not consider the non-axial dipolar terms of the inducing field and its radial variation or do so by means of complicated formulae.Moreover,existing methods treat the magnetic lithosphere either as an infinitesimally thin layer or as a radially uniform spherical shell of constant thickness.Here,we present alternative forward formulae that account for an arbitrarily high maximum degree of the inducing field and for a magnetic lithosphere of variable thickness.Our simulations based on these formulae suggest that the satellite magnetic anomaly field is sensitive to the non-axial dipolar terms of the inducing field but not to its radial variation.Therefore,in forward and inverse calculations of satellite magnetic anomaly data,the non-axial dipolar terms of the inducing field should not be ignored.Furthermore,our results show that the satellite magnetic anomaly field is sensitive to variability in the lateral thickness of the magnetized shell.In particular,we show that for a given vertically integrated susceptibility distribution,underestimating the thickness of the magnetic layer overestimates the induced magnetic field.This discovery bridges the greatest part of the alleged gap between the susceptibility values measured from rock samples and the susceptibility values required to match the observed magnetic field signal.We expect the formulae and conclusions of this study to be a valuable tool for the quantitative interpretation of the Earth's global lithospheric magnetic field,through an inverse or forward modelling approach.展开更多
Establishing an energy-saving and affordable hydrogen production route from infinite seawater presents a promising strategy for achieving carbon neutrality and low-carbon development.Compared with the kinetically slug...Establishing an energy-saving and affordable hydrogen production route from infinite seawater presents a promising strategy for achieving carbon neutrality and low-carbon development.Compared with the kinetically sluggish oxygen evolution reaction(OER),the thermodynamically advantageous sulfion oxidation reaction(SOR)enables the S^(2-)pollutants recovery while reducing the energy input of water electrolysis.Here,a nanoporous NiMo alloy ligament(np-NiMo)with AlNi_(3)/Al_(5)Mo heterostructure was prepared for hydrogen evolution reaction(HER,-0.134V versus reversible hydrogen electrode(vs.RHE)at 50mA/cm^(2)),which needs an Al_(89)Ni_(10)Mo_(1)as a precursor and dealloying operation.Further,the np-NiMo alloy was thermal-treated with S powder to generate Mo-doped NiS_(2)(np-NiMo-S)for OER(1.544V vs.RHE at 50mA/cm^(2))and SOR(0.364 V vs.RHE at 50mA/cm^(2)),while still maintaining the nanostructuring advantages.Moreover,for a two-electrode electrolyzer system with np-NiMo cathode(1M KOH+seawater)coupling np-NiMo-S anode(1mol/L KOH+seawater+1 mol/L Na_(2)S),a remarkably ultra-low cell potential of 0.532 V is acquired at 50mA/cm^(2),which is about 1.015 V below that of normal alkaline seawater splitting.The theory calculations confirmed that the AlNi_(3)/Al_(5)Mo heterostructure within np-NiMo promotes H_(2)O dissociation for excellent HER,while the Mo-dopant of np-NiMo-S lowers energy barriers for the rate-determining step from^(*)S_(4)to^(*)S_(8).This work develops two kinds of NiMo alloy with tremendous prominence for achieving energy-efficient hydrogen production from alkaline seawater and sulfur recycling from sulfion-rich sewage.展开更多
The stability and electrocatalytic efficiency of transition metal oxides for water splitting is determined by geometric and electronic structure,especially under high current densities.Herein,a newly designed lamella-...The stability and electrocatalytic efficiency of transition metal oxides for water splitting is determined by geometric and electronic structure,especially under high current densities.Herein,a newly designed lamella-heterostructured nanoporous CoFe/CoFe_(2)O_(4) and CeO_(2−x),in situ grown on nickel foam(NF),holds great promise as a high-efficient bifunctional electrocatalyst(named R-CoFe/Ce/NF)for water splitting.Experimental characterization verifies surface reconstruction from CoFe alloy/oxide to highly active CoFeOOH during in situ electrochemical polarization.By virtues of three-dimensional nanoporous architecture and abundant electroactive CoFeOOH/CeO_(2−x) heterostructure interfaces,the R-CoFe/Ce/NF electrode achieves low overpotentials for oxygen evolution(η_(10)=227 mV;η_(500)=450 mV)and hydrogen evolution(η_(10)=35 mV;η_(408)=560 mV)reactions with high normalized electrochemical active surface areas,respectively.Additionally,the alkaline full water splitting electrolyzer of R-CoFe/Ce/NF||R-CoFe/Ce/NF achieves a current density of 50 mA·cm^(−2) only at 1.75 V;the decline of activity is satisfactory after 100-h durability test at 300 mA·cm^(−2).Density functional theory also demonstrates that the electron can transfer from CeO_(2−x) by virtue of O atom to CoFeOOH at CoFeOOH/CeO_(2−x) heterointerfaces and enhancing the adsorption of reactant,thus optimizing electronic structure and Gibbs free energies for the improvement of the activity for water splitting.展开更多
INTERNAL DOSE RESEARCH PAPERS INTDOSKIT:An R-Code for Calculation of Dose Coefficients and Studying Their Uncertainties Bastian Breustedt 1,Niranjan Chavan 2,Thomas Makumbi 2(1.Karlsruhe Institute of Technology,Instit...INTERNAL DOSE RESEARCH PAPERS INTDOSKIT:An R-Code for Calculation of Dose Coefficients and Studying Their Uncertainties Bastian Breustedt 1,Niranjan Chavan 2,Thomas Makumbi 2(1.Karlsruhe Institute of Technology,Institute of Biomedical Engineering(IBT),Fritz-Haber-Weg 1,D-76131 Karlsruhe,Germany;2.Karlsruhe Institute of Technology,Institute for Thermal Energy Technology and Safety(ITES),Hermann-von-Helmholtz-Platz 1,76344 EggensteinLeopoldshafen,Germany)Abstract:An R-code,which allows the calculation of the time dependent activity distribution based on ICRP reference models,the number of decays in a commitment period,and the dose coefficients for tissues and organs of the human body,has been developed.R Language was chosen due to its powerful mathematical and statistical modeling features,as well as its graphical capabilities.展开更多
Al-Cu-Mg-Ag alloys have become a research hotspot because of its good heat resistance.Its excellent mechanical properties are inseparable from the regulation of the structure by researchers.The method of material stru...Al-Cu-Mg-Ag alloys have become a research hotspot because of its good heat resistance.Its excellent mechanical properties are inseparable from the regulation of the structure by researchers.The method of material structure simulation has become more and more perfect.This study employs numerical simulation to investigate the microstructure evolution of Al-Cu-Mg-Ag alloys during solidification with the aim of controlling its structure.The size distribution of Ti-containing particles in an Al-Ti-B master alloy was characterized via microstructure observation,serving as a basis for optimizing the nucleation density parameters for particles of varying radii in the phase field model.The addition of refiner inhibited the growth of dendrites and no longer produced coarse dendrites.With the increase of refiner,the grains gradually tended to form cellular morphology.The refined grains were about 100μm in size.Experimental validation of the simulated as-cast grain morphology was conducted.The samples were observed by metallographic microscope and scanning electron microscope.The addition of refiner had a significant effect on the refinement of the alloy,and the average grain size after refinement was also about 100μm.At the same time,the XRD phase identification of the alloy was carried out.The observation of the microstructure morphology under the scanning electron microscope showed that the precipitated phase was mainly concentrated on the grain boundary.The Al_(2)Cu accounted for about 5%,and the matrix phase FCC accounted for about 95%,which also corresponded well with the simulation results.展开更多
Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atm...Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atmospheric pollutant NO but also produces valuable ammonia(NH_(3)).Hence,through the synthesis and modification of Fe_(3)C nanocrystal cata-lysts,the as-obtained optimal sample of Fe_(3)C/C-900 was adopted as the NORR catalyst at ambient conditions.As a result,the Fe_(3)C/C-900 catalyst showed an NH_(3)Faraday efficiency of 76.5%and an NH_(3)yield rate of 177.5μmol·h^(-1)·cm^(-2)at the working potentials of-0.8 and-1.2 V versus reversible hydrogen electrode(vs.RHE),respectively.And it delivered a stable NORR activity during the electrolysis.Moreover,we attribute the high NORR properties of Fe_(3)C/C-900 to two aspects:one is the enhanced intrinsic activity of Fe_(3)C nanocrystals,including the lowering of the energy barrier of rate-limiting step(*NOH→*N)and the inhibition of hydrogen evolution;on the other hand,the favorable dispersion of active components,the effective adsorption of gaseous NO,and the release of liquid NH_(3)products facilitated by the porous carbon substrate.展开更多
This study aims to enhance the photocatalytic performance of 2D/2D heterojunctions for NO removal from marine vessel effluents.SnS_(2)/g-C_(3)N_(4) composites were successfully constructed via a facile solvothermal me...This study aims to enhance the photocatalytic performance of 2D/2D heterojunctions for NO removal from marine vessel effluents.SnS_(2)/g-C_(3)N_(4) composites were successfully constructed via a facile solvothermal method,demonstrating a significant improvement in photocatalytic NO removal under visible light irradiation.For high-flux simulated flue gas,the composite with 10%SnS_(2)(denoted as SNCN-10)showed exceptional NO removal efficiency,reaching up to 66.8%,along with excellent reusability over five consecutive cycles.Detailed band structure and density of states(DOS)calculations confirmed the formation of a characteristic heterojunction.Spin-trapping ESR spectroscopy identified·O_(2)^(-)−as the key reactive species driving NO oxidation.Additionally,in situ DRIFT spectroscopy revealed that SNCN-10 facilitated the conversion of NO to nitrate through intermediate species,including bridging nitrite and cis-nitrite(N_(2)O_(2)^(2-)).Kinetic studies further indicated that NO oxidation followed the Langmuir-Hinshelwood(L-H)mechanism.Based on density functional theory(DFT)calculations of free energy changes,a comprehensive reaction pathway for NO oxidation was proposed.These findings provide valuable insights for the development of efficient photocatalytic strategies for NO removal.展开更多
Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfull...Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy,elemental analyses,single-crystal X-ray diffraction,powder X-ray diffraction,and thermogravimetric analysis.The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.Meanwhile,complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.In addition,both 1and 2 exhibited luminescent properties in the solid state.Furthermore,quantum chemical calculations were carried out on the"molecular fragments"extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian 16 program.The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ)ions.CCDC:2332173,1;2332176,2.展开更多
In the past decade,people have conducted extensive research on the synthesis and application properties of various functionalized pillararenes.Pillararenes show good application prospects in the field of sensors due t...In the past decade,people have conducted extensive research on the synthesis and application properties of various functionalized pillararenes.Pillararenes show good application prospects in the field of sensors due to the rich host-vip recognition in their rigid electron-rich cavities.However,most reported pillararenes are functionalized by alkoxy modification,which results in poor charge transfer nature and weak fluorescence response.A π-conjugated charge-transfer system P5BN was obtained by introducing electron-donating triarylamine(Ar_(3)N)and electron-deficient triarylborane(Ar_(3)B)into pillar[5]arene skeleton,which significantly improved its luminescence behavior and was further used for fluorescence detection applications.The molecular structure showed that P5BN provided a good macrocyclic cavity to encapsulate amino acids molecules of suitable size.It was found that P5BN,as a fluorescent sensor,showed a highly sensitive and selective response to L-arginine(L-Arg),resulting in a significant enhancement of the fluorescence at 408 nm of P5BN with the lowest detection concentration being 2.21×10^(-8) mol/L.The recognition mechanism was demonstrated through experiments and DFT theoretical calculations.展开更多
文摘Millions of men each year are faced with a clinical suspicion of prostate cancer （PCa） but the prostate biopsy fails to detect the disease. For the urologists, how to select the appropriate candidate for repeat biopsy is a significant clinical dilemma. Traditional risk-stratification tools in this setting such as prostate-specific antigen （PSA） related markers and histopathology findings have met with limited correlation with cancer diagnosis or with significant disease. Thus, an individualized approach using predictive models such as an online risk calculator （RC） or updated biomarkers is more suitable in counseling men about their risk of harboring clinically significant prostate cancer, This review will focus on the available risk-stratification tools in the population of men with prior negative biopsies and persistent suspicion of PCa. The underlying methodology and platforms of the available tools are reviewed to better understand the development and validation of these models. The index patient is then assessed with different RCs to determine the range of heterogeneity among various RCs. This should allow the urologists to better incorporate these various risk-stratification tools into their clinical practice and improve patient counseling.
文摘Risk calculators have offered a viable tool for clinicians to stratify patients at risk of prostate cancer(PCa)and to mitigate the low sensitivity and specificity of screening prostate specific antigen(PSA).While initially based on clinical and demographic data,incorporation of multiparametric magnetic resonance imaging(MRI)and the validated prostate imaging reporting and data system suspicion scoring system has standardized and improved risk stratification beyond the use of PSA and patient parameters alone.Biopsy-naïve patients with lower risk profiles for harboring clinically significant PCa are often subjected to uncomfortable,invasive,and potentially unnecessary prostate biopsy procedures.Incorporating risk calculator data into prostate MRI reports can broaden the role of radiologists,improve communication with clinicians primarily managing these patients,and help guide clinical care in directing the screening,detection,and risk stratification of PCa.
文摘Risk prediction models including the Prostate Health Index(phi)for prostate cancer have been well established and evaluated in the Western population.The aim of this study is to build phi-based risk calculators in a prostate biopsy population and evaluate their performanee in predicting prostate cancer(PCa)and high-grade PCa(Gleason score 27)in the Chinese population.We developed risk calculators based on 635 men who underwent initial prostate biopsy.Then,we validated the performance of prostate-specific antigen(PSA),phi,and the risk calculators in an additional observational cohort of 1045 men.We observed that the phi-based risk calculators(risk calculators 2 and 4)outperformed the PSA-based risk calculator for predicting PCa and high-grade PCa in the training cohort.In the validation study,the area under the receiver operating characteristic curve(AUC)for risk calculators 2 and 4 reached 0.91 and 0.92,respectively,for predicting PCa and high-grade PCa,respectively;the AUC values were better than those for risk calculator 1(PSA-based model with an AUC of 0.81 and 0.82,respectively)(all P<0.001).Such superiority was also observed in the stratified population with PSA ranging from 2.0 ng ml^-1 to 10.0 ng ml^-1.Decision curves confirmed that a considerable proportion of unnecessary biopsies could be avoided while applying phi-based risk calculators.In this study,we showed that,compared to risk calculators without phi,phi-based risk calculators exhibited superior discrimination and calibration for PCa in the Chinese biopsy population.Applying these risk calculators also considerably reduced the number of unnecessary biopsies for PCa.
文摘The performances of the Prostate Cancer Prevention Trial （PCPT） risk calculator and other risk calculators for prostate cancer （PCa） prediction in Chinese populations were poorly understood. We performed this study to build risk calculators （Huashan risk calculators） based on Chinese population and validated the performance of prostate-specific antigen （PSA）, PCPT risk calculator, and Huashan risk calculators in a validation cohort. We built Huashan risk calculators based on data from 1059 men who underwent initial prostate biopsy from January 2006 to December 2010 in a training cohort. Then, we validated the performance of PSA, PCPT risk calculator, and Huashan risk calculators in an observational validation study from January 2011 to December 2014. All necessary clinical information were collected before the biopsy. The results showed that Huashan risk calculators 1 and 2 outperformed the PCPT risk calculator for predicting PCa in both entire training cohort and stratified population （with PSA from 2.0 ng ml^-1 to 20.0 ng ml^-1）. In the validation study, Huashan risk calculator 1 still outperformed the PCPT risk calculator in the entire validation cohort （0.849 vs 0.779 in area under the receiver operating characteristic curve [AUC]） and stratified population. A considerable reduction of unnecessary biopsies （approximately 30%） was also observed when the Huashan risk calculators were used. Thus, we believe that the Huashan risk calculators （especially Huashan risk calculator 1） may have added value for predicting PCa in Chinese population. However, these results still needed further evaluation in larger populations.
基金Supported by The Department of Health,Executive Yuan,Taipei,Taiwan,Bristol-Myers Squibb Co.,United StatesAcademia Sinica,Taipei,Taiwan+1 种基金the National Science Council No.NSC101-2314-B-039-029-MY3,Taipei,Taiwanthe National Health Research Institutes(NHRI-EX98-9806PI),Chunan,Taiwan
文摘Risk calculators are widely used in many clinical fields, and integrate several important risk factors through the conversion of a risk function into a single measure of risk. Several studies have been carried out to create risk calculators for the prediction of hepatocellular carcinoma (HCC) in patients with chronic hepatitis B (CHB). Most of them were hospital-based, with limited sample sizes and insufficient external validation. These study groups collaborated to establish the REACH-B risk score, which incorporated five clinical variables to predict HCC risk. This risk score was then validated in international clinical cohorts. Evidence suggests that quantitative serum HBsAg level provides additional predictability of HCC, especially in patients with low levels of hepatitis B virus DNA. This novel marker was incorporated into a risk calculator and was internally validated. This tool will hopefully be externally validated in the near future. Risk calculators can be used to support clinical practice, and to establish preventive measures; several “off-label” extension usages have also been implemented. Albeit beneficial, several precautions and discussions should be noted in using the risk calculators. The future development of risk calculators for CHB patients can be extended by applying them to additional CHB-related outcomes, and by incorporating emerging risk parameters.
文摘Over the last few decades,the evolution of liver resection has progressed through numerous milestones in peri-operative management,operative techniques and novel technologies that have dramatically improved patient safety and outcomes(1).Consequently,such developments have enabled surgeons to embark on liver resections of lesions in technically challenging locations,whereby extended resection or bilovascular reconstruction may be required to ensure oncologic clearance.In the context of extended resections or resection of lesions from heavily diseased livers,concerns remain regarding the adequacy of the remnant future liver remnant(FLR)and liver function,placing patients at risk of the clinical phenomenon known as post-hepatectomy liver failure(PHLF).Although relatively uncommon,PHLF has a reported incidence of up to 32%in the literature and remains an important cause of post-hepatectomy morbidity and mortality(2).Presently,several definitions have been proposed to describe PHLF,the most recent of which was proposed by the International Study Group of Liver Surgery(ISGLS).In this definition,PHLF was defined as an increased international normalized ratio(INR)or hyperbilirubinemia on or after post-operative day 5,with further stratification of severity grades(A,B or C)based on the extent of clinical management(3).While definitions in PHLF assist in providing a common diagnostic framework among physicians,establishing predictors in PHLF is conceivably more helpful as it allows surgeons to have important decision-making details prior to planned liver resection.
基金supported by the National Natural Science Foundation Joint Fund(Nos.U1806223 and U2106226)the National Natural Science Foundation of China(No.52371081)the Key Technology Research and Development Program of Shandong Province(No.2020CXGC010703).
文摘The defect regulation and p-n heterojunction of composites have gained significant attention due to their potential applications.Nitrogen(N)as doping heteroatoms and perylene-3,4,9,10-tetracarboximide(PDINH)as an appropriate n-type semiconductor were innovatively and reasonably selected to enhance the photocatalytic performance of pristine p-type cuprous oxide(Cu_(2)O).In this study,the defect regula-tion of N doping(1)achieved the small-size effect of Cu_(2)O,(2)optimized the electron features,and(3)improved the kinetics of reactive oxygen species.The p-n heterojunction with PDINH was developed to sharply improve the light utilization of Cu_(2)O,from the UV region to the near-infrared region.As expected,the optimized Cu_(2)N_(x)O_(1–x)/PDINH(x=0.02)exhibited excellent long-term photocatalytic antibacterial ac-tivities,with antibacterial rates exceeding 91%against Staphylococcus aureus and Pseudomonas aeruginosa.Defect regulation and p-n heterojunction of Cu_(2)O-based composites thus provide a great deal of potential for future advancements in photocatalysis.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFF0609000)National Natural Science Foundation of China(Grant Nos.52171034 and 52101037)Postdoctoral Fellowship Program of CPSFara(No.GZB20230944).
文摘Up-and-coming high-temperature materials,refractory high entropy alloys,are suffering from lower oxidation resistance,restricting their applications in the aerospace field.In this study,two novel treatments of Al-deposited and remelted were developed to refine the microstructure and enhance the oxidation resistance of refractory high entropy alloy using electron beam freeform fabrication(EBF3).Finer and short-range ordering structures were observed in the remelted sample,whereas the Al-deposited sample showcased the formation of silicide and intermetallic phases.High-temperature cyclic and isothermal oxidation tests at 1000℃ were carried out.The total weight gain after 60 h of cyclic oxidation decreased by 17.49%and 30.46%for the remelted and deposited samples,respectively,compared to the as-cast state.Oxidation kinetics reveal an evident lower mass gain and oxidation rate in the treated samples.A multilayer oxide consisting of TiO_(2)+Al_(2)O_(3)+SiO_(2)+AlNbO_(4) was studied for its excellent oxidation resistance.The oxidation behavior of rutile,corundum and other oxides was analyzed using first principles calculations and chemical defect analysis.Overall,this research,which introduces novel treatments,offers promising insights for enhancing the inherent oxidation resistance of refractory high entropy alloys.
基金supported by the National Natural Science Foundation of China(Nos.22272105 and 22002110)Natural Science Foundation of Shanghai(No.23ZR1423900)。
文摘Nitrogen-doping of carbon support(N-C)for platinum(Pt)nanoparticles to form Pt/N-C catalyst represents an effective strategy to promote the electrocatalysis of cathodic oxygen reduction reaction(ORR)in proton exchange membrane fuel cells.For fundamental understanding,clearly identifying the metalsupport effect on enhancement mechanisms of ORR electrocatalysis is definitely needed.In this work,the impact of Pt-support interaction via interfacial Pt-N coordination on electrocatalytic ORR activity and stability in Pt/N-C catalyst is deeply studied through structural/compositional characterizations,electrochemical measurements and theoretical DFT-calculations/AIMD-simulations.The resulting Pt/N-C catalyst exhibits a superior electrocatalytic performance compared to the commercial Pt/C catalyst in both half-cell and H_(2)-O_(2)fuel cell.Experimental and theoretical results reveal that the interfacial Pt-N coordination enables electron transfer from N-C support to Pt nanoparticles,which can weaken the adsorption strength of oxygen intermediates on Pt surface to improve ORR activity and induce the strong Pt-support interaction to enhance electrochemical stability.
基金the R&D Program of Beijing Municipal Education Commission(No.KM202310005010)the National Natural Science Foundation of China(No.52001015)for their financial support.
文摘The quest for high-energy-density magnesium-air batteries is hindered by the efficiency-voltage trade-off,ultimately leading to an unsatisfactory energy density.Here,we effectively mitigate the inherent efficiency-voltage trade-off by introducing a novel anode material,specifically,Mg-0.5Sn-0.5In-0.5Ga.This anode demonstrates exceptional anodic efficiency,achieving 60.5±2.5%at 1 mA cm^(-2),65.3±2.7%at 10 mA cm^(-2),and 71.4±1.2%at 20 mA cm^(-2).Furthermore,the discharge voltage is significantly enhanced,reaching 1.76±0.01 V at 1 mA cm^(-2),1.44±0.02 V at 10 mA cm^(-2),and 1.21±0.08 V at 20 mA cm^(-2).Consequently,our newly developed anode exhibits a remarkable energy density of 2312±98 W h kg^(-1),placing it among the top-performing magnesium anodes documented in the literature.Density functional theory calculations and experimental investigations have unveiled that the exceptional performance can be attributed to the inhibition of water reduction,facilitated by the hybridization between solute atoms and neighboring Mg atoms.Furthermore,the activation of the second phase,introducing additional galvanic couples,significantly contributes to this performance.This study presents valuable insights that can guide the design of novel anodes,contributing to the advancement of high-performance magnesium-air batteries.
基金supported by the National Natural Science Foundation of China(Grant Nos.42250103 and 42174090)the Opening Fund of Key Laboratory of Geological Survey and Evaluation of Ministry of Education(Grant No.GLAB2023ZR02)the Ministry of Science and Technology(MOST)Special Fund from the State Key Laboratory of Geological Processes and Mineral Resources(Grant No.MSFGPMR2022-4)。
文摘As a means of quantitative interpretation,forward calculations of the global lithospheric magnetic field in the Spherical Harmonic(SH)domain have been widely used to reveal geophysical,lithological,and geothermal variations in the lithosphere.Traditional approaches either do not consider the non-axial dipolar terms of the inducing field and its radial variation or do so by means of complicated formulae.Moreover,existing methods treat the magnetic lithosphere either as an infinitesimally thin layer or as a radially uniform spherical shell of constant thickness.Here,we present alternative forward formulae that account for an arbitrarily high maximum degree of the inducing field and for a magnetic lithosphere of variable thickness.Our simulations based on these formulae suggest that the satellite magnetic anomaly field is sensitive to the non-axial dipolar terms of the inducing field but not to its radial variation.Therefore,in forward and inverse calculations of satellite magnetic anomaly data,the non-axial dipolar terms of the inducing field should not be ignored.Furthermore,our results show that the satellite magnetic anomaly field is sensitive to variability in the lateral thickness of the magnetized shell.In particular,we show that for a given vertically integrated susceptibility distribution,underestimating the thickness of the magnetic layer overestimates the induced magnetic field.This discovery bridges the greatest part of the alleged gap between the susceptibility values measured from rock samples and the susceptibility values required to match the observed magnetic field signal.We expect the formulae and conclusions of this study to be a valuable tool for the quantitative interpretation of the Earth's global lithospheric magnetic field,through an inverse or forward modelling approach.
基金financially supported by the Guangxi Natural Science Fund for Distinguished Young Scholars(No.2024GXNSFFA010008)the Natural Science Foundation of Jilin Province of China(No.20240101098JC)the National Natural Science Foundation of China(No.22469002)。
文摘Establishing an energy-saving and affordable hydrogen production route from infinite seawater presents a promising strategy for achieving carbon neutrality and low-carbon development.Compared with the kinetically sluggish oxygen evolution reaction(OER),the thermodynamically advantageous sulfion oxidation reaction(SOR)enables the S^(2-)pollutants recovery while reducing the energy input of water electrolysis.Here,a nanoporous NiMo alloy ligament(np-NiMo)with AlNi_(3)/Al_(5)Mo heterostructure was prepared for hydrogen evolution reaction(HER,-0.134V versus reversible hydrogen electrode(vs.RHE)at 50mA/cm^(2)),which needs an Al_(89)Ni_(10)Mo_(1)as a precursor and dealloying operation.Further,the np-NiMo alloy was thermal-treated with S powder to generate Mo-doped NiS_(2)(np-NiMo-S)for OER(1.544V vs.RHE at 50mA/cm^(2))and SOR(0.364 V vs.RHE at 50mA/cm^(2)),while still maintaining the nanostructuring advantages.Moreover,for a two-electrode electrolyzer system with np-NiMo cathode(1M KOH+seawater)coupling np-NiMo-S anode(1mol/L KOH+seawater+1 mol/L Na_(2)S),a remarkably ultra-low cell potential of 0.532 V is acquired at 50mA/cm^(2),which is about 1.015 V below that of normal alkaline seawater splitting.The theory calculations confirmed that the AlNi_(3)/Al_(5)Mo heterostructure within np-NiMo promotes H_(2)O dissociation for excellent HER,while the Mo-dopant of np-NiMo-S lowers energy barriers for the rate-determining step from^(*)S_(4)to^(*)S_(8).This work develops two kinds of NiMo alloy with tremendous prominence for achieving energy-efficient hydrogen production from alkaline seawater and sulfur recycling from sulfion-rich sewage.
基金sponsored by the National Natural Science Foundation of China(Nos.5210125 and 52375422)the Science Research Project of Hebei Education Department(No.BJK2023058)the Natural Science Foundation of Hebei Province(Nos.E2020208069,B2020208083 and E202320801).
文摘The stability and electrocatalytic efficiency of transition metal oxides for water splitting is determined by geometric and electronic structure,especially under high current densities.Herein,a newly designed lamella-heterostructured nanoporous CoFe/CoFe_(2)O_(4) and CeO_(2−x),in situ grown on nickel foam(NF),holds great promise as a high-efficient bifunctional electrocatalyst(named R-CoFe/Ce/NF)for water splitting.Experimental characterization verifies surface reconstruction from CoFe alloy/oxide to highly active CoFeOOH during in situ electrochemical polarization.By virtues of three-dimensional nanoporous architecture and abundant electroactive CoFeOOH/CeO_(2−x) heterostructure interfaces,the R-CoFe/Ce/NF electrode achieves low overpotentials for oxygen evolution(η_(10)=227 mV;η_(500)=450 mV)and hydrogen evolution(η_(10)=35 mV;η_(408)=560 mV)reactions with high normalized electrochemical active surface areas,respectively.Additionally,the alkaline full water splitting electrolyzer of R-CoFe/Ce/NF||R-CoFe/Ce/NF achieves a current density of 50 mA·cm^(−2) only at 1.75 V;the decline of activity is satisfactory after 100-h durability test at 300 mA·cm^(−2).Density functional theory also demonstrates that the electron can transfer from CeO_(2−x) by virtue of O atom to CoFeOOH at CoFeOOH/CeO_(2−x) heterointerfaces and enhancing the adsorption of reactant,thus optimizing electronic structure and Gibbs free energies for the improvement of the activity for water splitting.
文摘INTERNAL DOSE RESEARCH PAPERS INTDOSKIT:An R-Code for Calculation of Dose Coefficients and Studying Their Uncertainties Bastian Breustedt 1,Niranjan Chavan 2,Thomas Makumbi 2(1.Karlsruhe Institute of Technology,Institute of Biomedical Engineering(IBT),Fritz-Haber-Weg 1,D-76131 Karlsruhe,Germany;2.Karlsruhe Institute of Technology,Institute for Thermal Energy Technology and Safety(ITES),Hermann-von-Helmholtz-Platz 1,76344 EggensteinLeopoldshafen,Germany)Abstract:An R-code,which allows the calculation of the time dependent activity distribution based on ICRP reference models,the number of decays in a commitment period,and the dose coefficients for tissues and organs of the human body,has been developed.R Language was chosen due to its powerful mathematical and statistical modeling features,as well as its graphical capabilities.
文摘Al-Cu-Mg-Ag alloys have become a research hotspot because of its good heat resistance.Its excellent mechanical properties are inseparable from the regulation of the structure by researchers.The method of material structure simulation has become more and more perfect.This study employs numerical simulation to investigate the microstructure evolution of Al-Cu-Mg-Ag alloys during solidification with the aim of controlling its structure.The size distribution of Ti-containing particles in an Al-Ti-B master alloy was characterized via microstructure observation,serving as a basis for optimizing the nucleation density parameters for particles of varying radii in the phase field model.The addition of refiner inhibited the growth of dendrites and no longer produced coarse dendrites.With the increase of refiner,the grains gradually tended to form cellular morphology.The refined grains were about 100μm in size.Experimental validation of the simulated as-cast grain morphology was conducted.The samples were observed by metallographic microscope and scanning electron microscope.The addition of refiner had a significant effect on the refinement of the alloy,and the average grain size after refinement was also about 100μm.At the same time,the XRD phase identification of the alloy was carried out.The observation of the microstructure morphology under the scanning electron microscope showed that the precipitated phase was mainly concentrated on the grain boundary.The Al_(2)Cu accounted for about 5%,and the matrix phase FCC accounted for about 95%,which also corresponded well with the simulation results.
基金supported by the Guangxi Natural Science Fund for Distinguished Young Scholars(2024GXNSFFA010008)Shenzhen Science and Technology Program(JCYJ20230807112503008).
文摘Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atmospheric pollutant NO but also produces valuable ammonia(NH_(3)).Hence,through the synthesis and modification of Fe_(3)C nanocrystal cata-lysts,the as-obtained optimal sample of Fe_(3)C/C-900 was adopted as the NORR catalyst at ambient conditions.As a result,the Fe_(3)C/C-900 catalyst showed an NH_(3)Faraday efficiency of 76.5%and an NH_(3)yield rate of 177.5μmol·h^(-1)·cm^(-2)at the working potentials of-0.8 and-1.2 V versus reversible hydrogen electrode(vs.RHE),respectively.And it delivered a stable NORR activity during the electrolysis.Moreover,we attribute the high NORR properties of Fe_(3)C/C-900 to two aspects:one is the enhanced intrinsic activity of Fe_(3)C nanocrystals,including the lowering of the energy barrier of rate-limiting step(*NOH→*N)and the inhibition of hydrogen evolution;on the other hand,the favorable dispersion of active components,the effective adsorption of gaseous NO,and the release of liquid NH_(3)products facilitated by the porous carbon substrate.
基金The project was supported by Natural Science Foundation of Shandong Province(ZR2021MB104)National Natural Science Foundation of China(22078174).
文摘This study aims to enhance the photocatalytic performance of 2D/2D heterojunctions for NO removal from marine vessel effluents.SnS_(2)/g-C_(3)N_(4) composites were successfully constructed via a facile solvothermal method,demonstrating a significant improvement in photocatalytic NO removal under visible light irradiation.For high-flux simulated flue gas,the composite with 10%SnS_(2)(denoted as SNCN-10)showed exceptional NO removal efficiency,reaching up to 66.8%,along with excellent reusability over five consecutive cycles.Detailed band structure and density of states(DOS)calculations confirmed the formation of a characteristic heterojunction.Spin-trapping ESR spectroscopy identified·O_(2)^(-)−as the key reactive species driving NO oxidation.Additionally,in situ DRIFT spectroscopy revealed that SNCN-10 facilitated the conversion of NO to nitrate through intermediate species,including bridging nitrite and cis-nitrite(N_(2)O_(2)^(2-)).Kinetic studies further indicated that NO oxidation followed the Langmuir-Hinshelwood(L-H)mechanism.Based on density functional theory(DFT)calculations of free energy changes,a comprehensive reaction pathway for NO oxidation was proposed.These findings provide valuable insights for the development of efficient photocatalytic strategies for NO removal.
文摘Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy,elemental analyses,single-crystal X-ray diffraction,powder X-ray diffraction,and thermogravimetric analysis.The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.Meanwhile,complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.In addition,both 1and 2 exhibited luminescent properties in the solid state.Furthermore,quantum chemical calculations were carried out on the"molecular fragments"extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian 16 program.The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ)ions.CCDC:2332173,1;2332176,2.
文摘In the past decade,people have conducted extensive research on the synthesis and application properties of various functionalized pillararenes.Pillararenes show good application prospects in the field of sensors due to the rich host-vip recognition in their rigid electron-rich cavities.However,most reported pillararenes are functionalized by alkoxy modification,which results in poor charge transfer nature and weak fluorescence response.A π-conjugated charge-transfer system P5BN was obtained by introducing electron-donating triarylamine(Ar_(3)N)and electron-deficient triarylborane(Ar_(3)B)into pillar[5]arene skeleton,which significantly improved its luminescence behavior and was further used for fluorescence detection applications.The molecular structure showed that P5BN provided a good macrocyclic cavity to encapsulate amino acids molecules of suitable size.It was found that P5BN,as a fluorescent sensor,showed a highly sensitive and selective response to L-arginine(L-Arg),resulting in a significant enhancement of the fluorescence at 408 nm of P5BN with the lowest detection concentration being 2.21×10^(-8) mol/L.The recognition mechanism was demonstrated through experiments and DFT theoretical calculations.
