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1. 内蒙古大学 化学化工学院,内蒙古 呼和浩特,010021
2. 内蒙古化工职业学院,内蒙古 呼和浩特,010011
收稿日期:2013-10-09,
修回日期:2013-12-16,
纸质出版日期:2014-03-03
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魏峰, 李欣, 王爱玲等. 水杨醛甘氨酸席夫碱-含氮杂环稀土配合物的合成及其与DNA作用的光谱研究[J]. 发光学报, 2014,35(3): 366-371
WEI Feng, LI Xin, WANG Ai-ling etc. Synthesis, Spectral Studies on The Interaction of DNA and Rare Earth with Salicylideneglycine Schiff and Nitrogen-heterocyclic Complexes[J]. Chinese Journal of Luminescence, 2014,35(3): 366-371
魏峰, 李欣, 王爱玲等. 水杨醛甘氨酸席夫碱-含氮杂环稀土配合物的合成及其与DNA作用的光谱研究[J]. 发光学报, 2014,35(3): 366-371 DOI: 10.3788/fgxb20143503.0366.
WEI Feng, LI Xin, WANG Ai-ling etc. Synthesis, Spectral Studies on The Interaction of DNA and Rare Earth with Salicylideneglycine Schiff and Nitrogen-heterocyclic Complexes[J]. Chinese Journal of Luminescence, 2014,35(3): 366-371 DOI: 10.3788/fgxb20143503.0366.
合成了以水杨醛甘氨酸席夫碱(Sal-GlyK)、邻菲罗啉(Phen)和2,2-联吡啶(Bipy)为配体、Eu
3+
、La
3+
为中心的配合物。对其进行了元素分析和摩尔电导、红外光谱及紫外吸收光谱测定,推测配合物的组成分别为
RE
(Sal-Gly)(NO
3
)2H
2
O和
RE
(Sal-Gly)(Phen)(NO
3
)H
2
O、
RE
(Sal-Gly)(Bipy)(NO
3
)H
2
O(
RE
3+
=Eu
3+
,La
3+
)。通过紫外吸收光谱及荧光光谱研究了稀土配合物与小牛胸腺DNA的作用方式及其结合常数。结果表明,本文合成的配合物与DNA的结合能力的顺序为
RE
(Sal-Gly)(Phen)(NO
3
)H
2
O
>
RE
(Sal-Gly)(Bipy)(NO
3
)H
2
O
>
RE
(Sal-Gly)(NO
3
)2H
2
O,表明配合物是以插入方式与DNA结合,含有良好平面性和较大表面积配体的配合物可以更好地插入到DNA的碱基对中。
A series of novel rare earth complexes were synthesized with salicylideneglycine schiff base (Sal-GlyK)
l
10-phenanthroline (Phen) and 2
2'-bipyridine (Bipy). The complexes were characterized by elemental analysis
rare earth coordination titration
molar conductivity measurement
IR spectroscopy and UV-Vis absorption spectroscopy. They were confirmed to be
RE
(Sal-Gly)(NO
3
)2H
2
O
RE
(Sal-Gly)(Phen)(NO
3
)H
2
O and
RE
(Sal-Gly)(Bipy)(NO
3
)H
2
O (
RE
3+
=Eu
3+
La
3+
) as the results of those measurement. The interaction between the rare earth complexes and calf thymus DNA (CT-DNA) was investigated by UV-Vis spectrophotometry and fluorescence spectroscopy. Red shift and hypochromicity of the absorption peak from UV spectra of the complexes were founded in the presence of DNA
and fluorescence quench experiment was used to confirm that the complexes can quench the fluorescence of ethidium bromide-DNA (EB-DNA) system. All these results indicate that intercalation model exists between the complexes and DNA
and good planarity and large surface area of the ligand have a positive effect on the intercalative reaction
so the sequence of binding ability of the complexes to DNA is
RE
(Sal-Gly)(Phen)(NO
3
)H
2
O
>
RE
(Sal-Gly)(Bipy)(NO
3
)H
2
O
>
RE
(Sal-Gly)(NO
3
)2H
2
O.
Da Silva C M, Da Silva D L, Modolo L V, et al. A short review of their antimicrobial activities[J]. J. Adv. Res., 2011, 2 (1):1-8. [2] Shahabadi N, Kashanian S, Darabi F. DNA binding and DNA cleavage studies of a water soluble cobalt (Ⅱ) complex containing dinitrogen Schiff base ligand: The effect of metal on the mode of binding[J]. Eur. J. Med. Chem., 2010, 45 (9):4239-4245. [3] Xi X L, Li Z C. Progress in the studies on antibacterial and antitumor acivitles of amino acid Schiff base and its metal complexes[J]. Amino Acids & Biotic Resources(氨基酸和生物资源), 1998, 20(4):40-43 (in Chinese). [4] Huang C H. Rare Earth Coordination Chemistry [M]. Beijing: Science Press, 1997 (in Chinese). [5] Reichmann M E, Rice S A, Thomas C A, et al. A further examination of the molecular weight and size of desoxypentose nucleic acid[J]. J. Am. Chem. Soc., 1954, 76(11):3047-3053. [6] Marmur J, Doty P. Thermal renaturation of deoxyribonucleic acids[J]. J. Mol. Biol., 1961, 3(5):585-594. [7] Wu Z S, Lu Z P, Yan Z H. Synthesis, characterization scavenger effect on O2- of copper(Ⅱ) and zinc(Ⅱ) complexes derived from thiosemi-carbazide[J]. Transit. Metal. Chem., 1993, 18:291-297. [8] Nakamoto K. Infrared Spectra of Inorganic and Coordination Compounds [M]. New York: Wiley, 1970. [9] Wu H X, Xin C Y. Syntheses and photoluminescence properties of Dy3+ acetylacetone-1, 10-phenanthroline ternary complexes doped with rare earth ions[J]. Chin. J. Lumin.(发光学报), 2006, 27(2):270-274 (in Chinese). [10] Barton J K, Danishefsky A, Goldberg J. Tris(phenanthroline)ruthenium(Ⅱ): Stereoselectivity in binding to DNA[J]. J. Am. Chem. Soc., 1984, 106(7):2172-2176. [11] Pyle A M, Rehmann J P, Meshoyrer R, et al. Mixed-ligand complexes of ruthenium(Ⅱ): Factors governing binding to DNA[J]. J. Am. Chem. Soc., 1989, 111(8):3051-3058. [12] Tysoe S A, Morgan R J, Baker A D, et al. Spectroscopic investigation of differential binding modes of delta and lambda-Ru(bpy)2(ppz)+2 with calf thymus DNA[J]. J. Phys. Chem., 1993, 97(8):1707-1711. [13] Wolfe A, Shimer G H, Meehan T. Polycyclic aromatic hydrocarbons physically intercalate into duplex regions of denatured DNA[J]. Biochem., 1987, 26(20):6392-6396. [14] Wang B D, Yang Z Y, Li T R. Synthesis, characterization, and DNA-binding properties of the Ln(Ⅲ) complexes with 6-hydroxy chromone-3-carbaldehyde-(2'-hydroxy) benzoyl hydrazine[J]. Bioorg. Med. Chem., 2006, 14(17):6012-6021. [15] Lakowicz J R, Weber G. Quenching of protein fluorescence by oxygen. Detection of structural fluctuations in proteins on the nanosecond time scale[J]. Biochem., 1973, 12(21):4171-4179.
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