铜与缓冲剂Bicine及芳香氮碱三元混配配合物的稳定性研究

用pH电位滴定法测定了HL的酸常数（L＝苯并咪唑，吡啶，3，4－二甲基吡啶，异喹啉）以及二元配合物CuL2＋和三元混配配合物Cu（Bic）L＋（Bic-＝Bicine的单电荷阴离子）的稳定常数．三元混配配合物相对于二元配合物的稳定性用△lgKCu＝lgKCu(Bic)Cu(Bic)L-lgKCuCuL来表示．结果表明由于δ-π协同效应和疏水作用，三元混配配合物有较强的稳定性     

Intramolecular stacking interaction in mixed-ligand complexes containing ATP4- and aromatic N-heterocyclic ligands

The stability constants of the binary ML2+ and ternary M(ATP)L2- complexes,where L=Iq (isoquinoline) or BIm (benzimidazole) and M=Zn2+ or Cd2+,have been determined by poten-tiometric pH titration in aqueous solution at I=0.1 mol/L (NaClO4),T=25℃.The stability of the ternary complexes characterized by corresponding to the equilibrium M(ATP)2-+ML2+=M(ATP)L2-+M2+ is higher than what would be expected on statistical grounds.The increase may be related to the stacking interaction between the aromatic ring of the ligands L and the purine moiety of ATP4- 1H NMR studies of Zn2+/ATP4-/L confirm the presence of stacking in the ternary complexes.It is concluded that the strength of the intramolecular stacking interaction is dependent on the structure of the aromatic ring of the ligand L and the formation of a metal ion bridge.Possible implications are discussed briefly.     

Bicine单电荷阴离子与芳香氮碱形成的三元金属离子混配配合物的稳定性研究

用pH电位滴定法首次研究了水溶液中三元混配配合物M(Bic)L+(M2+=Ni2+或Zn2+,L=苯并咪唑、吡啶、3,4-二甲基吡啶、异喹啉,Bic- = N,N-双(羟乙基)甘氨酸的单电荷阴离子)的稳定性.三元混配配合物相对于二元配合物的稳定性差值用ΔlgKM =lgKM(Bic)M(Bic)L-lgKMML来表示.结果表明这些三元混配配合物比统计规律所估计的要稳定得多,且ΔlgKZn 大于ΔlgKNi.三元混配配合物稳定性增大可归因于πA-πB协同作用和Zn2+配位构型的转变.     

干涉法测量光学材料非线性折射率的方法研究

提出了一种基于楔形平板等厚干涉原理测量光学玻璃非线性折射率变化的方法。在理论分析的基础上,建立了变形的等厚干涉条纹变化△e／e与待测玻璃平片（K9玻璃）折射率变化量△nb之间的数学模型;在选取一定的实验条件下,获得等厚干涉实验测量干涉图样,并利用MATLAB对实验所得的干涉图进行图像数据处理分析计算,恢复出非线性变化光学玻璃材料的折射率变化量△nb该方法的测量精度可达10^-6。     

The ternary metal mixed ligand complexes formed by benzimidazole and N, N-bis(2-hydroxyethyl) glycine

The stability constants of the ternary M(Bic)(Bzim)~ complexes, where M~(2 )=Cu~(2 ), Ni~(2 ) or Zn~(2 ), Bic~-=the anion of N, N-bis(2-hydroxyethyl) glycine and Bzim = benzimidazole, were determined by potentiometric pH titration in aqueous solution. One of them (M~(2 ) = Cu~(2 )) was also separately determined by spectrophotometry. The results show that these ternary complexes are stabler than expected on statistical grounds. The enhanced stability of the ternary M(Bic) (Bzim)~ complexes is attributed to the π_A-π_B cooperative effect between Bic~- and benzimidazole. Besides, compared with Cu(Bic) (Bzim)~ and Ni(Bic) (Bzim)~ , the ternary Zn(Bic)(Bzim)~ complex has relatively high stability. The crystal structure of [Cu(Bic)(Bzim)]ClO_4 was determined by single crystal X-ray diffraction techniques. The copper atom has a trigonal-bipyramidal geometry, the basal plane is formed by an oxygen atom of the carboxylato group and two hydroxyl oxygen atoms, the apical position is occupied by a nitrogen a     

新型钌(Ⅱ)多吡啶配合物与DNA作用的黏度法研究

用黏度法系统地研究了新型钌(Ⅱ)多吡啶配合物与DNA的相互作用.结果显示:在一定程度上增大配体的刚性平面,将增大钌(Ⅱ)多吡啶配合物插入DNA碱基对的能力,但当配体的刚性平面太大时,却又由于位阻作用而阻碍了配体对DNA的插入;能够使配体平面性增强的分子内氢键的形成,有利于配合物对DNA的插入作用;配体中引入较大体积的取代基而引起的配体芳环间的扭转,将导致钌(Ⅱ)多吡啶配合物只能“部分地”或“非经典地”插入DNA.     

苯并咪唑和N,N-双(羟乙基)甘氨酸三元金属混配配合物的研究

M(Bic) (Bzim) (M2 =Cu2 ,Ni2 和Zn2 ,Bic-=N ,N 双 (羟乙基 )甘氨酸的单电荷阴离子 ,Bzim =苯并咪唑 )在水溶液中的稳定常数用pH电位滴定法进行了测定 ,同时Cu(Bic) (Bzim) 的稳定常数还用分光光度法进行对比 .结果表明 ,Bic-和苯并咪唑的πA πB 协同作用使得三元金属混配配合物具有较强的稳定性 ,其中Zn(Bic) (Bzim) 比其他 2个金属配合物具有相对较高的稳定性 .[Cu(Bic) (Bzim) ]·ClO4的单晶X衍射分析表明 ,铜原子位于三角双锥的中心 ,三角平面由 1个羧基氧原子和 2个羟基氧原子组成 ,轴向位置由Bic-的氮原子和苯并咪唑的氮原子占据 .在水溶液中Cu(Bic) (Bzim) 的结构与其晶体结构有所不同 ,ESR和电子吸收光谱结果指出 ,此配合物在水溶液中是八面体构型 .     

Bicine单电荷阴离子与芳香氮碱形式的三元金属离子混配配合物的 …

用ＰＨ电位滴定法首次研究了水溶液中三元混配配合物Ｍ（Ｂｉｃ）Ｌ＾＋（Ｍ＾２＋＝Ｎｉ＾２＋或Ｚｎ＾２＋,Ｌ＝苯并咪唑、啶、３,４－二甲基吡啶、异喹啉、Ｂｉｃ＾－＝Ｎ,Ｎ－双（羟乙基）甘氨酸的单电荷阴离子）的稳定性。三元混配配合物相对于二元配合物的稳定性差值用△ｌｇＫＭ＝ｌｇＫ＾Ｍ（Ｂｉｃ）Ｍ（Ｂｉｃ）Ｌ－ｌｇＫ＾Ｍ ＭＬ来表示。结果表明这些三元混配配合物比统计规律所估计的要稳定得多,且△ｌｇＫＮｉ。