3-羟基-1-金刚烷甲酸轻稀土配合物的合成、晶体结构及与DNA作用

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以3-羟基-1-金刚烷甲酸(Hhata=C11H16O3),邻菲啰啉(phen)和稀土硝酸盐为原料,合成了7个轻稀土配合物(1)~(7)[RE2(hata)6(phen)2].4H2O(RE=La(1),Ce(2),Pr(3),Nd(4),Sm(5),Eu(6),Gd(7))。其中(1)为单晶样,其余6个样为粉末样;用元素分析、红外光谱、摩尔电导、热重分析等手段表征了配合物;用单晶X射线衍射法测定了(1)的晶体结构,该配合物[La2(hata)6(phen)2].4H2O(C90H114La2N4O22)属于单斜晶系,空间群P2(1)/c,a=1.33979(13)nm,b=2.6395(2)nm,c=1.31321(14)nm,β=112.174(4)°,V=4.3005(7)nm3,Z=2,Mr=1881.67,F(000)=1944.0,Dc=1.453 g.cm-3,μ(Mo Kα)=1.056 mm-1。结果表明:两个镧原子与两个邻菲啰啉中的4个氮原子和6个3-羟基-1-金刚烷甲酸根中的羧基氧原子配位,中心原子的配位数为9。用溴化乙锭荧光探针法测试了7个配合物对EB-DNA复合体系的荧光猝灭效应,实验结果显示配合物均与DNA发生了不同程度的插入作用。 Seven light rare earth complexes (1) ~ (7) [RE2 (hata)) were synthesized from 3-hydroxy-1-adamantanecarboxylic acid (Hhata = C11H16O3), phenanthroline and rare earth nitrate 6 (phen) 2] .4H2O (RE = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7)). Among them, (1) was monocrystalline and the other six samples were powder samples. The complexes were characterized by elemental analysis, infrared spectroscopy, molar conductance and thermogravimetric analysis. The crystallites of (1) were determined by single crystal X-ray diffraction Crystal structure, the complex [La2 (hata) 6 (phen) 2] 4H2O (C90H114La2N4O22) belongs to the monoclinic system with space group P2 (1) /c,a=1.33979 (13) nm and b = 2.6395 ), c = 1.31321 (14) nm, β = 112.174 (4) °, V = 4.3005 (7) nm3, Z = 2, Mr = 1881.67, F (000) = 1944.0, Dc = 1.453 g.cm-3 , μ (Mo Kα) = 1.056 mm-1. The results show that the two lanthanum atoms coordinate with the four nitrogen atoms in two phenanthrolines and the carboxyl oxygen atoms in six 3-hydroxy-1-adamantanecarboxylates, and the coordination number of the central atom is 9. The fluorescence quenching effect of seven complexes on EB-DNA complex system was tested by ethidium bromide fluorescent probe method. The experimental results showed that the complexes were inserted into DNA with different degrees.
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