氧钒配合物[VO(o-Van-Asn)(Phen)]·1.5CH_3OH的合成、晶体结构及与DNA和BSA的相互作用  

Synthesis, Crystal Structure and Interactions with DNA and BSA of a Oxovanadium(IV) Complex [VO(o-Van-Asn)(Phen)]·1.5CH_3OH

作　　者：郭琼[1] 李连之[1] 董建方[1,2] 刘鸿雁[1] 薛泽春[1] 许涛[1] 

机构地区：[1]聊城大学化学化工学院,聊城252059 [2]山东工程技师学院材料科学系,聊城252027

出　　处：《化学学报》2012年第15期1617-1624,共8页Acta Chimica Sinica

基　　金：山东省自然科学基金(No.Y2004B02)资助~~

摘　　要：合成了一种新的L-天冬酰胺邻香草醛席夫碱和1,10-邻菲咯啉的氧钒配合物[VO(o-Van-L-Asn)(Phen)]1.5CH3OH(o-Van-L-Asn=邻香草醛与L-天冬酰胺形成的席夫碱,Phen=1,10-邻菲咯啉).利用红外光谱对其进行了表征,并通过X射线单晶衍射测定了其晶体结构.该晶体属于三斜晶系,P-1空间群,晶胞参数为:a=0.98990(10)nm,b=1.21591(11)nm,c=1.28349(12)nm,α=66.8180(10)°,β=83.816(2)o,γ=66.4150(10)o,V=1.2992(2)nm3,Dc=1.430 g cm-3,Z=1,F(000)=580,R1=0.0626,wR2=0.1631.通过紫外吸收光谱、荧光光谱、圆二色光谱(CD)和粘度测定等方法研究了该配合物与小牛胸腺DNA(CT-DNA)的相互作用.结果表明,配合物以插入方式与CT-DNA结合.光谱法研究该配合物与牛血清白蛋白(BSA)的相互作用表明,它主要以静态猝灭方式使BSA的内源性荧光发生猝灭,可引起蛋白构象的变化.计算得到了其结合常数Kb和结合位点数n.A new oxovanadium（IV） complex,[VO（o-Van-Asn）（Phen）] 1.5CH 3 OH（o-Van-Asn is the Schiff base derived from o-vanillin and L-asparagine,Phen=1,10-phenanthroline） has been synthesized.In the synthetic procedure of title complex,a methanol solution of o-vanillin（0.1522 g,1 mmol） was added to a stirred mixture of L-asparagine（0.1321 g,1.0 mmol） and potassium hydroxide（0.0561 g,1 mmol） in hot methanol.The resultant yellow solution was then stirred at 333 K for 1 h.Subsequently,an aqueous solution（2 mL） of vanadyl sulfate hydrate（0.2540 g,1 mmol） was added dropwise and stirred for 2 h continuously.Finally,a methanol solution（5 mL） of 1,10-phenanthroline（0.1980 g,1 mmol） was then added dropwise,and the mixture was stirred continuously for 3 h.The resultant solution was filtered and kept at room temperature,and reddish brown blocky crystals suitable for X-ray diffraction were obtained after several days.It was characterized by IR and single crystal X-ray diffraction.It crystallized in triclinic crystal system,P-1 space group with the cell parameters： a= 0.98990（10） nm,b=1.21591（11） nm,c=1.28349（12） nm,α=66.8180（10）o,β=83.816（2）o,γ=66.4150（10）o,V=1.2992（2） nm 3,D c =1.430 g cm-3,Z=1,F（000）=580,R 1 =0.0626,wR 2 =0.1631.The interactions of the complex with calf thymus DNA（CT-DNA） and bovine serum albumin（BSA） were carried out in 10 mmol L-1 Tris-HCl/10 mmol L-1 NaCl（pH 7.1） buffer solutions.In the experiment of interactions with CT-DNA,absorption titrations were carried out by using a fixed complex concentration to which increments of DNA stock solutions were added.The complex-DNA solutions were incubated for 2 h before the absorption spectra in the 150～250 nm wavelength range were recorded.For fluorescence experiments,the complex solution was added to the fixed concentration CT-DNA solutions treated with ethidium bromide.The emission spectra was recorded range from 535 to 675 nm at the excitation wavelength of 258 nm.Circular dichr

关 键 词：氧钒配合物 L-天冬酰胺席夫碱 晶体结构 DNA BSA 

分 类 号：O627.53[理学—有机化学]