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
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
So far, more attention was paid to the fact that the kind, position and properties of the substituted radicals of coordinating or non-coordinating groups in the complexes exert an important influence on the stability ...So far, more attention was paid to the fact that the kind, position and properties of the substituted radicals of coordinating or non-coordinating groups in the complexes exert an important influence on the stability of the complexes, but less to the interaction between those non-coordinating groups. Although the existence of hydrogen bonds between ligands and the formation of covalent and ionic bonds have been reported, it is only about ten展开更多
The complex [Cu(phen)2(POAc)3]ClO·4H2O has been synthesized and investigated by elemental analysis, IR spec-troscopy and X-ray diffraction methods, where phen = 1,10-phenanthroline, POAc = phenylacetate group). T...The complex [Cu(phen)2(POAc)3]ClO·4H2O has been synthesized and investigated by elemental analysis, IR spec-troscopy and X-ray diffraction methods, where phen = 1,10-phenanthroline, POAc = phenylacetate group). The complex crystallizes in the triclinic space group PI with two molecules in a unit cell of dimensions a = 1.0579(2) nm, b = 1.2423(3) nm, c = 1.9190(4) nm, α = 71.84(1)°, β = 80.50(2)°, γ = 88.60(1)°, V = 2.3625(9) nm3, R = 0.0407 and Rw = 0.0656. The complex results from bridging of two Cu(phen)2+ units by three carboxylate groups, and each Cu2+ ion is in a distorted square pyramidal geometry with two nitrogen atoms of phen and three carboxylate oxygen atoms of POAc. It has been showed that intramolecular stacking interactions occur between the phenyl moieties of POAc and aromatic rings of phen, leading to a novel molecule structure with two coordinating modes of carboxylate ligands, of which two phenylacetates are μ2-carboxylate-O-bridging ligands, and the other is a μ2-carboxylate-O, O'-bridging ligand.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.
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
基金Project supported by the National Natural Science Foundation of China.
文摘So far, more attention was paid to the fact that the kind, position and properties of the substituted radicals of coordinating or non-coordinating groups in the complexes exert an important influence on the stability of the complexes, but less to the interaction between those non-coordinating groups. Although the existence of hydrogen bonds between ligands and the formation of covalent and ionic bonds have been reported, it is only about ten
基金Project supported by the National Natural Science Foundation of China (No. 29571033) and the Natural Science Foundation of Guangdong Province (No.974207).
文摘The complex [Cu(phen)2(POAc)3]ClO·4H2O has been synthesized and investigated by elemental analysis, IR spec-troscopy and X-ray diffraction methods, where phen = 1,10-phenanthroline, POAc = phenylacetate group). The complex crystallizes in the triclinic space group PI with two molecules in a unit cell of dimensions a = 1.0579(2) nm, b = 1.2423(3) nm, c = 1.9190(4) nm, α = 71.84(1)°, β = 80.50(2)°, γ = 88.60(1)°, V = 2.3625(9) nm3, R = 0.0407 and Rw = 0.0656. The complex results from bridging of two Cu(phen)2+ units by three carboxylate groups, and each Cu2+ ion is in a distorted square pyramidal geometry with two nitrogen atoms of phen and three carboxylate oxygen atoms of POAc. It has been showed that intramolecular stacking interactions occur between the phenyl moieties of POAc and aromatic rings of phen, leading to a novel molecule structure with two coordinating modes of carboxylate ligands, of which two phenylacetates are μ2-carboxylate-O-bridging ligands, and the other is a μ2-carboxylate-O, O'-bridging ligand.
文摘为了解决单个神经网络预测的局限性和时间序列的波动性,提出了一种奇异谱分析(singular spectrum analysis,SSA)和Stacking框架相结合的短期负荷预测方法。利用随机森林筛选出与历史负荷相关性强烈的特征因素,采用SSA为负荷数据降噪,简化模型计算过程;基于Stacking框架,结合长短期记忆(long and short-term memory,LSTM)-自注意力机制(self-attention mechanism,SA)、径向基(radial base functions,RBF)神经网络和线性回归方法集成新的组合模型,同时利用交叉验证方法避免模型过拟合;选取PJM和澳大利亚电力负荷数据集进行验证。仿真结果表明,与其他模型比较,所提模型预测精度高。
