N_3非对称配体、稀土配合物的合成及其在DNA传感器中的应用
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摘要
合成具有三脚架形结构的配体L及其稀土配合物。用元素分析、红外光谱、核磁共振波谱、热分析、紫外吸收光谱、荧光光谱等方法对L及其配合物的结构进行表证,用光谱法和电化学法分析配合物与BSA,DNA之间的相互作用,并考查其作为杂交探针在DNA传感器方面的应用。结果表明,每1个L中C=O,P=O,P-O上O均可与稀土离子Eu~(3+),Y~(3+)配位,L与苦味酸配体以1∶1配位,化学式为RE(pic)_3L·3H_2O (RE=Eu,Y); Eu(Ⅲ)配合物对BSA内源荧光以静态方式淬灭,能量为非辐射转移,两者之间主要存在氢键和范德华力; Eu(Ⅲ)配合物与ct-DNA之间以嵌插作用结合,且在实验范围内有电化学活性; Eu(Ⅲ)配合物可以识别电极上的杂交过程,对互补、非互补、错配序列有较好的选择性。
The article is about the synthesis of Ligand L and its rare earth complex with tripod shaped structure.The structures of L and its coordination compound were characterized according to the methods of elemental analysis,infrared spectroscopy,nuclear magnetic resonance spectrum,thermal analysis,ultraviolet absorption spectrum,and fluorescence spectrum. The interaction between compounds and BSA,DNA with spectroscopy and electrochemical methods,and its application as hybridization probe to DNA sensor were investigated. The result showed that O is coordinated with rare earth ion Eu~(3+),Tb~(3+) of C = O,P = O,P-O in each L,and L is coordinated with picric acid ligand at the rate of 1∶ 1,and the chemical formula RE( pic)_3L·3H_2O( RE = Eu,Y); Eu( Ⅲ) complex quenches BSA intrinsic fluorescence statically,the energy transferred nonradiatively,and hydrogen bond and Van der Waals' forces are the main existence among them. Eu( Ⅲ) complex is interacted with ct-DNA by intercalation,and there is electrochemical activity in the experimental range. Eu( Ⅲ) complex can identify the hybridization process in electrodes which has good selectivity for complementary,non complementary and mismatched sequences.
The article is about the synthesis of Ligand L and its rare earth complex with tripod shaped structure.The structures of L and its coordination compound were characterized according to the methods of elemental analysis,infrared spectroscopy,nuclear magnetic resonance spectrum,thermal analysis,ultraviolet absorption spectrum,and fluorescence spectrum. The interaction between compounds and BSA,DNA with spectroscopy and electrochemical methods,and its application as hybridization probe to DNA sensor were investigated. The result showed that O is coordinated with rare earth ion Eu~(3+),Tb~(3+) of C = O,P = O,P-O in each L,and L is coordinated with picric acid ligand at the rate of 1∶ 1,and the chemical formula RE( pic)_3L·3H_2O( RE = Eu,Y); Eu( Ⅲ) complex quenches BSA intrinsic fluorescence statically,the energy transferred nonradiatively,and hydrogen bond and Van der Waals' forces are the main existence among them. Eu( Ⅲ) complex is interacted with ct-DNA by intercalation,and there is electrochemical activity in the experimental range. Eu( Ⅲ) complex can identify the hybridization process in electrodes which has good selectivity for complementary,non complementary and mismatched sequences.
引文
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[17] Liu W,Li X H,Huo L N,Yang T L. Synthesis,luminescence and DNA-binding properties of Eu(Ⅲ)and Tb(Ⅲ)complexes with amide-based 2, 3-dihydroxynaphthalene derivative[J]. Asian. J. Chem.,2013,25(18):10465.
[18] Ding Y T,Wang Q X,Gao F,Gao F. Highly sensitive and selective DNA biosensor using a dumbbell-shaped bis-groove binder of bi-acetylferrocene ethylenediamine complex as electrochemical indicator[J]. Electrochim.Acta,2013,106:35.
[19] Rajendiran V,Karthik R,Palaniandavar M,StoeckliEvans H,Periasamy V S,Akbarsha M A,Srinag B S,Krishnamurthy H. Mixed-ligand copper(II)-phenolate complexes:Effect of coligand on enhanced DNA and protein binding, DNA cleavage, and anticancer activity[J]. Inorg. Chem.,2007,46(20):8208.
[20] Tarushi A,Karaflou Z,Kljun J,Turel L,Psomas G,Papadopoulos A N,Kessissoglou D P. Antioxidant capacity and DNA-interaction studies of zinc complexes with a non-steroidal anti-inflammatory drug,mefenamic acid[J]. J. Inorg. Biochem.,2013,128:85.
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[22] Hu Y J,Liu Y,Zhang L X. Studies of interaction between colchicine and bovine serum albumin by fluores-cence quenching method[J]. J. Mol. Struct.,2005,750(1/3):174.
[23] Jayabharathi J,Thanikachalam V,Sathishkumar R,Jayamoorthy K. Fluorescence investigation of the interaction of 2-(4-fluorophenyl)-1-phenyl-1H-phenanthro[9,10-d] imidazole with bovine serum albumin[J]. J.Photochem. Photobiol. B,2012,117:222.
[24] Zhang J,Li W X,Ao B Y,Feng S Y,Xin X D. Fluorescence enhancement of europium(III)perchlorate by benzoic acid on bis(benzylsulfinyl)methane complex and its binding characteristics with the bovine serum albumin(BSA)[J]. Spectrochim. Acta A. Mol. Biomol. Spectrosc.,2014,118:972.
[25]杨树平,韩立军,潘燕,王大奇,赵翠,王波.N,N'-双(4-氯苄基)-1,2-丙二胺合铜(Ⅱ)配合物的合成、晶体结构、抑菌活性及与BSA的相互作用[J].高等学校化学学报,2012,33(1):14.Yang S P,Han L J,Pan Y,Wang D Q,Zhao C,Wang B. Synthesis,crystal structure,antibacterial activity and interaction with BSA of copper(II)complex with ligand N,N'-Bis(4-chlorobenzyl)propane-1,2-diamine[J]. Chemical Journal of Chinese Universities,2012,33(1):14.
[26] Tang R R,Tang C H,Tang C Q. Synthesis,luminescence properties of a novel aromatic carboxylic acid(L)and corresponding Eu(III)and Tb(III)compounds as well as the binding characteristics of L with bovine serum albumin(BSA)[J]. J. Organomet. Chem.,2011,696(10):2040.
[27]高继红,杨天林.酰胺型开链冠醚类稀土配合物的合成及其与DNA的作用研究[J].中国稀土学报,2014,32(4):453.Gao J H,Yang T L. Synthesis of amide-type openchain crown ether rare earth complex and its interaction with DNA[J]. Journal of the Chinese Society of Rare Earths,2014,32(4):453.
[28] Guo Q,Li L Z,Dong J F,Liu H Y,Xu T,Li J H.Synthesis,crystal structure and interaction of L-valine schiff base divanadium(V)complex containing a V2O3core with DNA and BSA[J]. Spectrochim. Acta A.Mol. Biomol. Spectrosc.,2013,106:155.
[29] Kamatchi T S,Chitrapriya N,Ahamed J V S,Moon S S,Fronczek F R. Ruthenium(II)complexes of 2,2'-bipyridine-5,5'-dicarboxylic acid:Synthesis,structure,DNA binding,cytotoxicity and antioxidant activity[J].Inorg. Chim. Acta,2013,404:58.
[30] Sampath K,Sathiyaraj S,Raja G,Jayabalakrishna C.Mixed ligand ruthenium(III)complexes of benzaldehyde4-methyl-3-thiosemicarbazones with triphenylphosphine/triphenylarsine co-ligands:Synthesis, DNA binding,DNA cleavage,antioxidative and cytotoxic activity[J].J. Mol. Struct.,2013,1046:82.
[31] Hu H,Chen Y F,Zhou H,Pan Z Q. Synthesis,crystal structure,and DNA cleavage activity of a dinuclear nickel(II)complex with a macrocyclic ligand[J].Trans. Met. Chem.,2011,36(4):395.
[32]丁应涛,王立衡,郑成凤,蒋淑恋,黄立漳,高飞,汪庆祥.一种席夫碱钴(Ⅱ)配合物的合成及其与DNA的相互作用[J].化学试剂,2013,35(4):313.Ding Y T,Wang L H,Zheng C F,Jiang S L,Huang L Z,Gao F,Wang Q X. Synthesis of a schiff base cobalt(Ⅱ)complex and its interaction with DNA[J]. Chemical Reagents,2013,35(4):313.
[33]夏洪齐,顾婷婷.杂交型DNA电化学生物传感器研究进展[J].辽宁科技大学学报,2012,35(1):9.Xia H Q,Gu T T. Development of electrochemical DNA hybridization biosensor[J]. Journal of University of Science and Technology Liaoning,2012,35(1):9.
[34]尹娟. DNA生物传感器的应用及展望[J].科学之友,2012,(4):3.Yin J. Application and prospect of DNA biosensor[J]. Friend of Science Amateurs,2012,(4):3.
[2] Janicki R. Synthesis,crystal structure and spectral properties of diammonium dihydrogen N-(Methylene-2-pyridine)-N,N-di-(Methylenephosphonate)[J]. J.Mol. Struct.,2013,1036:35.
[3] Taddei M,Costantino F,Lenco A,Comotti A,Dau P V,Cohen S M. Synthesis breathing,and gas sorption study of the first isoreticular mixed-linker phosphonate based metal-ogranic frameworks[J]. Chem. Commun.,2013,49(13):1315.
[4] Wu J,Campuzano S,Halford C,Haake D A,Wang J.Ternary surface monolayers for ultrasensitive(zeptomole)amperometric detection of nucleic acid hybridization without signal amplification[J]. Anal. Chem.,2010,82(21):8830.
[5] Wang Q X,Gao F,Gao F,Li S X,Weng W,Liu F Q,Jiao K. A novel hybridization indicator for the lowbackground detection of short DNA fragments based on an electrically neutral cobalt(Ⅱ)complex[J]. Biosens. Bioelectron.,2010,32(1):50.
[6]汪庆祥,袁显龙,焦奎,谢江坤,张波.非标记电化学DNA杂交指示剂[J].化学进展,2007,19(6):1007.Wang Q X,Yuan X L,Jiao K,Xie J K,Zhang B.The nor labeling electrochemical active deoxyribonucleic acid hybridization indicators[J]. Progress in Chemistry,2007,19(6):1007.
[7]杨频,宋宇飞.金属配合物键合DNA的研究进展[J].化学进展,2000,12(1):32.Yang P,Song Y F. Progress of metal-complex binding DNA[J]. Progress in Chemistry,2000,12(1):32.
[8] Chen J Y,Selvin P R. Lifetime-and color-tailored fluorophores in the micro-to millisecond time regime[J].J. Am. Chem. Soc.,2000,122(4):657.
[9]刘伟.几种含磷三足体衍生物稀土配合物的合成及性质研究[D].银川:宁夏大学,2014.Liu W. Synthesis and Properties of Some Tripodal Phosphorus Ligands and Their Function Complexes[D].Yinchuan:Ningxia University,2014.
[10] Moedritzer K,Irani R R. The direct synthesis ofα-aminomethylphosphonic acids. mannich-type reactions with ortho-phosphorous acid[J]. J. Org. Chem.,1996,31(5):1063.
[11]魏峰,李欣,王爱玲,赵艳芳,康洁,岳彬,褚海斌,赵永亮.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.Wei F,Li X,Wang A L,Zhao Y F,Kang J,Yue B,Chu H B,Zhao Y L. 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.
[12] Villemin E,Elias B,Marchand-Brynaert J. Europium(III)coordination complex with a novel phosphonated ligand[J]. J. Mol. Struct.,2013,1034:276.
[13]马学兵,傅相锴,王强,王宁.含羟基、膦酸根水溶性膦配体的合成[J].应用化学,2002,19(12):1154.Ma X B,Fu X K,Wang Q,Wang N. Synthesis of water-soluble phosphine ligands containing hydroxyl and phosphonic acid groups[J]. Chinese Journal of Applied Chemistry,2002,19(12):1154.
[14] Murphy P J. Organophos Phorus Reagents[M]. Oxford:Oxford University Press,2004.
[15]谢远武.摩尔比法测定配合物组成和稳定常数的理论探讨[J].化学通报,1988,(2):41.Xie Y W. Theoretical discussion on molar ratio method for determination of composition and stability constant of complexes[J]. Chemistry(Huaxue Tongbao),1988,(2):41.
[16]陈连山,刘玉国,冯春亮,赵国良.应用摩尔比法和连续变化法研究混合溶液中形成沉淀的组成[J].辽宁师范大学学报:自然科学版, 1993, 16(2):135.Chen L S,Liu Y G,Feng C L,Zhao G L. Study of the composition of the precipitate from mixed solutions by using mole ratio method and asmus method[J]. Journal of Liaoning University(Natural Science),1993,16(2):135.
[17] Liu W,Li X H,Huo L N,Yang T L. Synthesis,luminescence and DNA-binding properties of Eu(Ⅲ)and Tb(Ⅲ)complexes with amide-based 2, 3-dihydroxynaphthalene derivative[J]. Asian. J. Chem.,2013,25(18):10465.
[18] Ding Y T,Wang Q X,Gao F,Gao F. Highly sensitive and selective DNA biosensor using a dumbbell-shaped bis-groove binder of bi-acetylferrocene ethylenediamine complex as electrochemical indicator[J]. Electrochim.Acta,2013,106:35.
[19] Rajendiran V,Karthik R,Palaniandavar M,StoeckliEvans H,Periasamy V S,Akbarsha M A,Srinag B S,Krishnamurthy H. Mixed-ligand copper(II)-phenolate complexes:Effect of coligand on enhanced DNA and protein binding, DNA cleavage, and anticancer activity[J]. Inorg. Chem.,2007,46(20):8208.
[20] Tarushi A,Karaflou Z,Kljun J,Turel L,Psomas G,Papadopoulos A N,Kessissoglou D P. Antioxidant capacity and DNA-interaction studies of zinc complexes with a non-steroidal anti-inflammatory drug,mefenamic acid[J]. J. Inorg. Biochem.,2013,128:85.
[21]杨频,高飞.生物无机化学原理[M].北京:科学出版社,2002. 329.Yang P,Gao F. Principles of Bioinorganic Chemistry[M]. Beijing:Science Press,2002. 329.
[22] Hu Y J,Liu Y,Zhang L X. Studies of interaction between colchicine and bovine serum albumin by fluores-cence quenching method[J]. J. Mol. Struct.,2005,750(1/3):174.
[23] Jayabharathi J,Thanikachalam V,Sathishkumar R,Jayamoorthy K. Fluorescence investigation of the interaction of 2-(4-fluorophenyl)-1-phenyl-1H-phenanthro[9,10-d] imidazole with bovine serum albumin[J]. J.Photochem. Photobiol. B,2012,117:222.
[24] Zhang J,Li W X,Ao B Y,Feng S Y,Xin X D. Fluorescence enhancement of europium(III)perchlorate by benzoic acid on bis(benzylsulfinyl)methane complex and its binding characteristics with the bovine serum albumin(BSA)[J]. Spectrochim. Acta A. Mol. Biomol. Spectrosc.,2014,118:972.
[25]杨树平,韩立军,潘燕,王大奇,赵翠,王波.N,N'-双(4-氯苄基)-1,2-丙二胺合铜(Ⅱ)配合物的合成、晶体结构、抑菌活性及与BSA的相互作用[J].高等学校化学学报,2012,33(1):14.Yang S P,Han L J,Pan Y,Wang D Q,Zhao C,Wang B. Synthesis,crystal structure,antibacterial activity and interaction with BSA of copper(II)complex with ligand N,N'-Bis(4-chlorobenzyl)propane-1,2-diamine[J]. Chemical Journal of Chinese Universities,2012,33(1):14.
[26] Tang R R,Tang C H,Tang C Q. Synthesis,luminescence properties of a novel aromatic carboxylic acid(L)and corresponding Eu(III)and Tb(III)compounds as well as the binding characteristics of L with bovine serum albumin(BSA)[J]. J. Organomet. Chem.,2011,696(10):2040.
[27]高继红,杨天林.酰胺型开链冠醚类稀土配合物的合成及其与DNA的作用研究[J].中国稀土学报,2014,32(4):453.Gao J H,Yang T L. Synthesis of amide-type openchain crown ether rare earth complex and its interaction with DNA[J]. Journal of the Chinese Society of Rare Earths,2014,32(4):453.
[28] Guo Q,Li L Z,Dong J F,Liu H Y,Xu T,Li J H.Synthesis,crystal structure and interaction of L-valine schiff base divanadium(V)complex containing a V2O3core with DNA and BSA[J]. Spectrochim. Acta A.Mol. Biomol. Spectrosc.,2013,106:155.
[29] Kamatchi T S,Chitrapriya N,Ahamed J V S,Moon S S,Fronczek F R. Ruthenium(II)complexes of 2,2'-bipyridine-5,5'-dicarboxylic acid:Synthesis,structure,DNA binding,cytotoxicity and antioxidant activity[J].Inorg. Chim. Acta,2013,404:58.
[30] Sampath K,Sathiyaraj S,Raja G,Jayabalakrishna C.Mixed ligand ruthenium(III)complexes of benzaldehyde4-methyl-3-thiosemicarbazones with triphenylphosphine/triphenylarsine co-ligands:Synthesis, DNA binding,DNA cleavage,antioxidative and cytotoxic activity[J].J. Mol. Struct.,2013,1046:82.
[31] Hu H,Chen Y F,Zhou H,Pan Z Q. Synthesis,crystal structure,and DNA cleavage activity of a dinuclear nickel(II)complex with a macrocyclic ligand[J].Trans. Met. Chem.,2011,36(4):395.
[32]丁应涛,王立衡,郑成凤,蒋淑恋,黄立漳,高飞,汪庆祥.一种席夫碱钴(Ⅱ)配合物的合成及其与DNA的相互作用[J].化学试剂,2013,35(4):313.Ding Y T,Wang L H,Zheng C F,Jiang S L,Huang L Z,Gao F,Wang Q X. Synthesis of a schiff base cobalt(Ⅱ)complex and its interaction with DNA[J]. Chemical Reagents,2013,35(4):313.
[33]夏洪齐,顾婷婷.杂交型DNA电化学生物传感器研究进展[J].辽宁科技大学学报,2012,35(1):9.Xia H Q,Gu T T. Development of electrochemical DNA hybridization biosensor[J]. Journal of University of Science and Technology Liaoning,2012,35(1):9.
[34]尹娟. DNA生物传感器的应用及展望[J].科学之友,2012,(4):3.Yin J. Application and prospect of DNA biosensor[J]. Friend of Science Amateurs,2012,(4):3.