The intramolecular aromatic-ring stacking interaction of mixed- ligand complex Pd(A)(UTP)^(2-)in the system pd^(2+)-A-UTP^(4-)has been determined by ~1HNMR,where A=1,10-phenanthroline(phen),2,2'-bipyridyl(bpy)and ...The intramolecular aromatic-ring stacking interaction of mixed- ligand complex Pd(A)(UTP)^(2-)in the system pd^(2+)-A-UTP^(4-)has been determined by ~1HNMR,where A=1,10-phenanthroline(phen),2,2'-bipyridyl(bpy)and DL- tryptophan(trp^-);UTP^(4-)=uridine 5-triphosphate.The result indicates that it is the partial stacking between the uracil ring of UTP^(4-)and the heterocyclic ring of A that makes H(5),H(6)and H(1')in the UTP^(4-)shift upfield signifi- cantly.Accordingly,the order of aromatic-ring interaction in the mixed- ligand complex has been obtained as follows:Pd(phen)(UTP)^(2-)(?)Pd(bpy)(UTP)^(2-) Pd(trp)(UTP)^(3-).展开更多
The stability constants of some ternary mixed-ligand complexes, Pt(Phen)(CA)+, where Phen=1,10-phenanthroline and CA- =carboxylate, were determined by means of potentiometric pH titration in aqueous solutions(I=0.1 mo...The stability constants of some ternary mixed-ligand complexes, Pt(Phen)(CA)+, where Phen=1,10-phenanthroline and CA- =carboxylate, were determined by means of potentiometric pH titration in aqueous solutions(I=0.1 mol/L, KNO 3; 25 ℃), and the stability of them was compared with that of the corresponding binary complexes. It was revealed that the ternary complexes containing phenylalkane carboxylates ligands(PCA-) are much more stable than those formed with formate and acetate. The results indicate that there exist the intramolecular aromatic-ring interactions between the phenanthroline ring of Phen and the phenyl moiety of ligand PCA- in the ternary mixed-ligand Pt(Phen)(PCA)- complexes. The extent of the stacking interactions, which depends on the number of methylene groups between the phenyl moieties and the coordinated phenylalkane carboxylate groups, was calculated. The best-fitted stack was obtained for the complexes with 2-phenylacetate and 3-phenylpropionate as the ligands.展开更多
Effects of alloying elements Ni,Co,Mn,Cr,and H on the stacking fault energy(SFE)ofγ-Fe and its microscopic mechanisms were systematically investigated.Generalized SFE calculations show that individual alloying elemen...Effects of alloying elements Ni,Co,Mn,Cr,and H on the stacking fault energy(SFE)ofγ-Fe and its microscopic mechanisms were systematically investigated.Generalized SFE calculations show that individual alloying elements Ni,Co,and H increase SFE ofγ-Fe,whereas Mn and Cr decrease SFE.The influence of alloying elements on SFE exhibits short-range characteristics.The effect of synergistic interaction of alloying elements and H on SFE was further investigated.Results show that the co-alloying of Ni/Co with H exacerbates the effect of H on the increase in SFE.In contrast,the synergistic effect of Mn/Cr with H tends to inhibit H from the increasing SFE.Finally,the electronic structure analysis elucidated the microscopic mechanism of the change in SFE.Alloying elements modulate SFE by changing the interatomic charge density at the stacking fault plane and the density of states of the stacking fault structure at the Fermi level.The present results add to the knowledge of alloying related influence on the mechanical property and hydrogen embrittlement ofγ-Fe.展开更多
In physics,our expectations for system behavior are often guided by intuitive arithmetic.For systems composed of identical units,we anticipate synergy of the contributions from these units,where 1+1=2.Conversely,for s...In physics,our expectations for system behavior are often guided by intuitive arithmetic.For systems composed of identical units,we anticipate synergy of the contributions from these units,where 1+1=2.Conversely,for systems built from opposing units,we expect cancellation of their contributions,where 1-1=0.This intuitive arithmetic has long underpinned our understanding of physical properties of materials,from electronic transport to optical responses.However,scientific breakthroughs often occur when nature reveals ways to circumvent these seemingly fundamental rules,opening new possibilities that challenge our deepest assumptions about material behavior.展开更多
One of the typical phenomena of intramolecular ligand-ligand interaction in complexes is the aromatic-ring stacking which depends on the stacking of those non-coordinating aromatic rings. Since 1974 H. Sigel reported ...One of the typical phenomena of intramolecular ligand-ligand interaction in complexes is the aromatic-ring stacking which depends on the stacking of those non-coordinating aromatic rings. Since 1974 H. Sigel reported that the stacking interaction was observed between pyridine ring of bpy（bpy=2, 2′-bipyridyl） and purine ring of ATP<sup>4-</sup>(ATP<sup>4-</sup>=adenosine 5′-triphosphate) among the mixed-ligand Cu（bpy） （ATP）<sup>2-</sup> complexes. The study on this field has been extended to a large amount of ligands such as nucleotides, xanthosines,展开更多
THE mechanism of the action of the classic platinum antitumor drugs can be interpreted accord-ing to their bidentate, bifunctional interaction with the DNA of the tumor cell, resulting in in-hibition of the DNA replic...THE mechanism of the action of the classic platinum antitumor drugs can be interpreted accord-ing to their bidentate, bifunctional interaction with the DNA of the tumor cell, resulting in in-hibition of the DNA replication. Recently, it was found that a new class of compounds withthe general formula cis-[Pt（NH<sub>3</sub>）<sub>2</sub>（N-het）Cl]Cl（N-het is a heteroaromatic N-base like pyri-dine） show effective antitumor activities. However, two possible mechanisms of action展开更多
文摘The intramolecular aromatic-ring stacking interaction of mixed- ligand complex Pd(A)(UTP)^(2-)in the system pd^(2+)-A-UTP^(4-)has been determined by ~1HNMR,where A=1,10-phenanthroline(phen),2,2'-bipyridyl(bpy)and DL- tryptophan(trp^-);UTP^(4-)=uridine 5-triphosphate.The result indicates that it is the partial stacking between the uracil ring of UTP^(4-)and the heterocyclic ring of A that makes H(5),H(6)and H(1')in the UTP^(4-)shift upfield signifi- cantly.Accordingly,the order of aromatic-ring interaction in the mixed- ligand complex has been obtained as follows:Pd(phen)(UTP)^(2-)(?)Pd(bpy)(UTP)^(2-) Pd(trp)(UTP)^(3-).
基金Supported by the Foundation of Academ y L eader of Zhejiang Gongshang U niversity(No.19972 0 0 2 )
文摘The stability constants of some ternary mixed-ligand complexes, Pt(Phen)(CA)+, where Phen=1,10-phenanthroline and CA- =carboxylate, were determined by means of potentiometric pH titration in aqueous solutions(I=0.1 mol/L, KNO 3; 25 ℃), and the stability of them was compared with that of the corresponding binary complexes. It was revealed that the ternary complexes containing phenylalkane carboxylates ligands(PCA-) are much more stable than those formed with formate and acetate. The results indicate that there exist the intramolecular aromatic-ring interactions between the phenanthroline ring of Phen and the phenyl moiety of ligand PCA- in the ternary mixed-ligand Pt(Phen)(PCA)- complexes. The extent of the stacking interactions, which depends on the number of methylene groups between the phenyl moieties and the coordinated phenylalkane carboxylate groups, was calculated. The best-fitted stack was obtained for the complexes with 2-phenylacetate and 3-phenylpropionate as the ligands.
文摘董志塬地区位于黄土高原中心地带,滑坡灾害频发,亟需明确滑坡易发性分区,以支持该区域滑坡隐患的科学防控。因此,本文以董志塬为研究区,选取高程、坡向和NDVI等12个影响因素作为评价因子,基于频率比(frequency ratio,FR)模型,结合随机森林(random forest,RF)与人工神经网络(artificial neural network,ANN)模型开展滑坡静态易发性评价,并分析各因子对评价精度的贡献。结果表明,FRRF和FR-ANN模型的曲线下面积(area under the curve,AUC)值分别为0.922和0.918,表明FR-RF模型在董志塬滑坡易发性评价中的精度更高。坡度、坡向和道路密度对滑坡易发性的贡献率分别为16.7%、15.3%和1.4%。为克服地形复杂和数据更新滞后的问题,本文将FR-RF模型的易发性结果与InSAR Stacking结果相结合,将静态滑坡易发性评价精度由6.9%提升到8.1%。动态易发性结果表明,董志塬滑坡高易发区主要分布于河流沿岸,占总面积的6.5%,该区域的滑坡数量占总滑坡数的23.6%,滑坡密度15.7个/km^(2)。低易发区主要位于远离河流的中部区域,占总面积的81.7%,滑坡数量占总滑坡数的57.8%,滑坡密度4.7个/km^(2)。本研究通过融合InSAR Stacking方法,解决了静态滑坡易发性评价数据更新滞后问题,减少了假阴性错误,为传统滑坡易发性评价赋予了时效性,可以实现董志塬滑坡易发性动态评价,为灾害防治提供了重要数据支持。
基金supported by National Science and Technology Major Project(2025ZD0618901)National Natural Science Foundation of China(U2241245 and 52321001)+2 种基金Aeronautical Science Foundation of China(2022Z053092001)Natural Science Foundation of Shenyang(23-503-6-05)Science and Technology Major Project of Liaoning Province(2024JH1/11700028).
文摘Effects of alloying elements Ni,Co,Mn,Cr,and H on the stacking fault energy(SFE)ofγ-Fe and its microscopic mechanisms were systematically investigated.Generalized SFE calculations show that individual alloying elements Ni,Co,and H increase SFE ofγ-Fe,whereas Mn and Cr decrease SFE.The influence of alloying elements on SFE exhibits short-range characteristics.The effect of synergistic interaction of alloying elements and H on SFE was further investigated.Results show that the co-alloying of Ni/Co with H exacerbates the effect of H on the increase in SFE.In contrast,the synergistic effect of Mn/Cr with H tends to inhibit H from the increasing SFE.Finally,the electronic structure analysis elucidated the microscopic mechanism of the change in SFE.Alloying elements modulate SFE by changing the interatomic charge density at the stacking fault plane and the density of states of the stacking fault structure at the Fermi level.The present results add to the knowledge of alloying related influence on the mechanical property and hydrogen embrittlement ofγ-Fe.
基金supported by the National Natural Science Foundation of China (Grant No.12374109)the National Key Research and Development Program of China (Grant No.2023YFA1406600)。
文摘In physics,our expectations for system behavior are often guided by intuitive arithmetic.For systems composed of identical units,we anticipate synergy of the contributions from these units,where 1+1=2.Conversely,for systems built from opposing units,we expect cancellation of their contributions,where 1-1=0.This intuitive arithmetic has long underpinned our understanding of physical properties of materials,from electronic transport to optical responses.However,scientific breakthroughs often occur when nature reveals ways to circumvent these seemingly fundamental rules,opening new possibilities that challenge our deepest assumptions about material behavior.
基金Project supported by the National Natural Science Foundation of China
文摘One of the typical phenomena of intramolecular ligand-ligand interaction in complexes is the aromatic-ring stacking which depends on the stacking of those non-coordinating aromatic rings. Since 1974 H. Sigel reported that the stacking interaction was observed between pyridine ring of bpy（bpy=2, 2′-bipyridyl） and purine ring of ATP<sup>4-</sup>(ATP<sup>4-</sup>=adenosine 5′-triphosphate) among the mixed-ligand Cu（bpy） （ATP）<sup>2-</sup> complexes. The study on this field has been extended to a large amount of ligands such as nucleotides, xanthosines,
文摘THE mechanism of the action of the classic platinum antitumor drugs can be interpreted accord-ing to their bidentate, bifunctional interaction with the DNA of the tumor cell, resulting in in-hibition of the DNA replication. Recently, it was found that a new class of compounds withthe general formula cis-[Pt（NH<sub>3</sub>）<sub>2</sub>（N-het）Cl]Cl（N-het is a heteroaromatic N-base like pyri-dine） show effective antitumor activities. However, two possible mechanisms of action
