苦味酸稀土配合物的合成及其与BSA/DNA的键合作用研究
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摘要
合成以N为中心的具有三脚架形结构的配体L及其稀土配合物。用元素分析、核磁共振波谱、紫外吸收光谱、红外光谱、热分析、计算化学等方法对它们的结构进行表征,通过光谱学、电化学等方法研究稀土配合物与BSA,ct-DNA的键合方式和结合位点。结果表明:1个L中2个羰基上的O、磷酰基上的1个O及磷酸根上的1个O与稀土离子配位,L与苦味酸盐以1∶1的形式结合。配合物对BSA的内源荧光以静态猝灭方式猝灭,293 K下二者之间的K_(sv)=5.97×10~5L·mol~(-1),K_q=10~(13)L·mol~(-1)·s,K=1.0×10~5L·mol~(-1),n=1,存在的作用力主要是氢键和范德华力。加入Fe~(3+),Cu~(2+)后,二者之间的作用点不变、结合常数增大,说明Fe~(3+),Cu~(2+)参与了反应且起到增强的作用。Eu(Ⅲ)配合物与ct-DNA以较强的插入作用结合,在测定电位区间内为电化学活性物质。可为该类稀土配合物与蛋白质之间的作用,有效药物在生物体内的药效发挥,新型DNA杂交指示剂的研究提供参考。
Ligand L and its rare earth complex with tripod structured ligand which concentrated on N were synthesited. Their structure was characterized with elemental analysis,nuclear magnetic resonance spectrum,ultraviolet absorption spectrum,infrared spectroscopy,thermal analysis and calculational chemistry. The bonding mode and bonding site of rare earth complex and BSA,ct-DNA with optical spectroscopy,electrochemistry,etc were studied. The result showed that two carbonyl O atoms,one phosphoryl O and one phosphate radical O within one L coordinated with rare earth ion,and L combined with picrate at the form of ratio 1∶ 1. The complex quenches BSA intrinsic fluorescence in static mode,K_(sv)= 5. 97 × 10~5 L·mol~(-1),K_q= 10~(13) L·mol~(-1)·s,K =1. 0 ×10~5 L·mol~(-1),n =1 between the two complexes under 293 K,and the acting forces are mainly hydrogen bond and Van der Waals' force. The application point between the two remains unchanged,and association constant magnifies after addition of Fe~(3+),Cu~(2+),which shows that,Fe~(3+),Cu~(2+) are involved in the reaction and play an enhanced role. Eu( Ⅲ)combines with ct-DNA by strong intercalation,appearing as electrochemical active substance within the potentiometric range. The reaction between this rare earth complex and protein and the effect of effective drug in living organisms can provide reference for study of new DNA hybridization indicator.
Ligand L and its rare earth complex with tripod structured ligand which concentrated on N were synthesited. Their structure was characterized with elemental analysis,nuclear magnetic resonance spectrum,ultraviolet absorption spectrum,infrared spectroscopy,thermal analysis and calculational chemistry. The bonding mode and bonding site of rare earth complex and BSA,ct-DNA with optical spectroscopy,electrochemistry,etc were studied. The result showed that two carbonyl O atoms,one phosphoryl O and one phosphate radical O within one L coordinated with rare earth ion,and L combined with picrate at the form of ratio 1∶ 1. The complex quenches BSA intrinsic fluorescence in static mode,K_(sv)= 5. 97 × 10~5 L·mol~(-1),K_q= 10~(13) L·mol~(-1)·s,K =1. 0 ×10~5 L·mol~(-1),n =1 between the two complexes under 293 K,and the acting forces are mainly hydrogen bond and Van der Waals' force. The application point between the two remains unchanged,and association constant magnifies after addition of Fe~(3+),Cu~(2+),which shows that,Fe~(3+),Cu~(2+) are involved in the reaction and play an enhanced role. Eu( Ⅲ)combines with ct-DNA by strong intercalation,appearing as electrochemical active substance within the potentiometric range. The reaction between this rare earth complex and protein and the effect of effective drug in living organisms can provide reference for study of new DNA hybridization indicator.
引文
[1] Benhamou L,Jaafar H,Thibon A,Lachkar M,Mandon D. Asymmetry and steric hindrance in tripodal ligands:Reaching the limit for octahedral geometry with the newly synthesized[(6-bromo 2-pyridylmethyl)(6-fluoro2-pyridylmethyl)(2-pyridylmethyl)] amine tripod in Fe Cl2complexes[J]. Inorg. Chim. Acta, 2011, 373(1):195.
[2] Chen J L,Yao Y M,Luo Y J,Zhou L Y,Zhang Y,Shen Q. Synthesis,characterization of homoleptic lanthanide amidinate complexes and their catalytic activity for the ring-opening polymerization ofε-caprolactone[J]. Organomet. Chem.,2004,662(1):144.
[3] Gribkov D V,Hultzsch K C,Hampel F. 3,3'-Bis(trisarylsilyl)-substituted binaphtholate rare earth metal catalysts for asymmetric hydroaminatuon[J]. J. Am.Chem. Soc.,2006,128(11):3748.
[4] Wan Y,Xu H,Su Y,Song S P,Fan C H. A surfaceinitiated enzymatic polymerization strategy for electrochemical DNA sensors[J]. Biosens. Bioelectron.,2013,41:526.
[5]丁杨,任祥祥,庄楚雄,乐学义.甘缬二肽-铜(Ⅱ)-多吡啶配合物合成、表征及与DNA的作用[J].无机化学学报,2009,25(4):656.Ding Y,Ren X X,Zhuang C X,Le X Y. Synthesis,characterization of ternary gly-L-Vval-copper(Ⅱ)-polypyridyl complexes and their interaction with DNA[J].Chinese Journal of Inorganic Chemistry, 2009, 25(4):656.
[6]刘晶莹,王国清,王鸿刚.金属配合物抗癌活性的研究进展[J].化学试剂,2003,25(5):274.Liu J Y,Wang G Q,Wang H G. Research progress in antitumor activities of coordination compounds[J].Chemical Reagents,2003,25(5):274.
[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] Ma L,Evans O R,Foxman B M,Li W B. Luminescent lanthanide coordination polymers[J]. Inorg.Chem.,1999,38(25):5837.
[9]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.
[10] Komiyama M,Takeda N,Shigekawa H. Hydrolysis of DNA and RNA by lanthanide ions:mechanistic studies leading to new applications[J]. Chem. Comm.,1999,(16):1443.
[11] Lakowicz J R,Webber G. Quenching of fluorescence by oxygen. A Probe for structural fluctuations in macromolecules[J]. Biochemistry,1973,12(21):4161.
[12]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.
[13] Villemin E,Elias B,Marchand-Brynaert J. Europium(III)coordination complex with a novel phosphonated ligand[J]. J. Mol. Struct.,2013,1034:276.
[14]陈连山,刘玉国,冯春良,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(Nature Science),1993,16(2):135.
[15] 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.
[16] Liu W,Li X H,Huo L N,Yang T L. Synthesis,luminescenceand 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.
[17] 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.
[18] Zampakou M,Akrivou M,Andreadou E G,Raptopoulou C P,Psycharis V,Pantazaki A A,Psomas G. Structure,antimicrobial activity,DNA-and albumin-binding of manganese(II)complexes with the quinolone antimicrobial agents oxolinic acid and enrofloxacin[J]. J. Inorg. Biochem.,2013,121:88.
[19] Wang Y,Jiang X H,Zhou L M,Yang L J,Xia G Q,Chen Z J,Duan M. Synthesis and binding with BSA of a new gemini surfactant[J]. Physicochem. Eng. Aspects,2013,436:1159.
[20]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.
[21] 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.
[22] 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, Part A, 2013,118:972.
[23]杨树平,韩立军,潘燕,王大奇,赵翠,汪波.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.
[24]宋盼,杨水兰,周通,杨天林,纳鹏军,倪刚.甘氨酸-N,N-双(亚甲基磷酸)及其Eu(Ⅲ)配合物与BSA的作用机制[J].中国稀土学报,2016,34(5):566.Song P,Yang S L,Zhou T,Yang T L,Na P J,Ni G.Mechanism of interaction between glycine-N,N-dimethyl phosphonate and its europium(Ⅲ)complex and bovine serum albumin(BSA)[J]. Journal of the Chinese Society of Rare Earths,2016,34(5):566.
[25]刘伟,杨水兰,宋盼,杨天林.一种含磷三足体衍生物及其铕配合物的合成及性能表征[J].应用化学,2015,32(7):777.Liu W,Yang S L,Song P,Yang T L. Synthesis and characterization of a phosphorus-containing tripod ligand and its europium complex[J]. Chinese Journal of Applied Chemistry,2015,32(7):777.
[26]王安萍,张国文,潘军辉,龚毅.金属离子对次野鸢尾黄素与牛血清白蛋白相互作用的影响[J].分析科学学报,2008,24(4):389.Wang A P,Zhang G W,Pan J H,Gong Y. Effect of metal ions on the interaction between bovine serum albumin and irisflorentin[J]. Journal of Analytical Science,2008,24(4):389.
[27]郭明,王炜,周建钟,郭晓琴.金属离子介导下的紫杉醇与血清蛋白结合反应机制的研究[J].化学研究与应用,2008,20(4):457.Guo M,Wang W,Zhou J Z,Guo X Q. Study on the interaction between paclitaxel-iron(Ⅲ)and bovine ser-um albumin[J]. Chemical Research and Application,2008,20(4):457.
[28] Kamatchi T S,Chitrapriya N,Ahamed J V S,Moon S S,Fronczek F R,Natarajan K. 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.
[29] Purcell M,Neault J F,Tajmir-Riahi H A. Interaction of taxol with human serum albumin[J]. Biochim. Biophys. Acta,2000,1478(1):61.
[30] 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].Transition. Met. Chem.,2011,36(4):395.
[31]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.
[32]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.
[2] Chen J L,Yao Y M,Luo Y J,Zhou L Y,Zhang Y,Shen Q. Synthesis,characterization of homoleptic lanthanide amidinate complexes and their catalytic activity for the ring-opening polymerization ofε-caprolactone[J]. Organomet. Chem.,2004,662(1):144.
[3] Gribkov D V,Hultzsch K C,Hampel F. 3,3'-Bis(trisarylsilyl)-substituted binaphtholate rare earth metal catalysts for asymmetric hydroaminatuon[J]. J. Am.Chem. Soc.,2006,128(11):3748.
[4] Wan Y,Xu H,Su Y,Song S P,Fan C H. A surfaceinitiated enzymatic polymerization strategy for electrochemical DNA sensors[J]. Biosens. Bioelectron.,2013,41:526.
[5]丁杨,任祥祥,庄楚雄,乐学义.甘缬二肽-铜(Ⅱ)-多吡啶配合物合成、表征及与DNA的作用[J].无机化学学报,2009,25(4):656.Ding Y,Ren X X,Zhuang C X,Le X Y. Synthesis,characterization of ternary gly-L-Vval-copper(Ⅱ)-polypyridyl complexes and their interaction with DNA[J].Chinese Journal of Inorganic Chemistry, 2009, 25(4):656.
[6]刘晶莹,王国清,王鸿刚.金属配合物抗癌活性的研究进展[J].化学试剂,2003,25(5):274.Liu J Y,Wang G Q,Wang H G. Research progress in antitumor activities of coordination compounds[J].Chemical Reagents,2003,25(5):274.
[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] Ma L,Evans O R,Foxman B M,Li W B. Luminescent lanthanide coordination polymers[J]. Inorg.Chem.,1999,38(25):5837.
[9]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.
[10] Komiyama M,Takeda N,Shigekawa H. Hydrolysis of DNA and RNA by lanthanide ions:mechanistic studies leading to new applications[J]. Chem. Comm.,1999,(16):1443.
[11] Lakowicz J R,Webber G. Quenching of fluorescence by oxygen. A Probe for structural fluctuations in macromolecules[J]. Biochemistry,1973,12(21):4161.
[12]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.
[13] Villemin E,Elias B,Marchand-Brynaert J. Europium(III)coordination complex with a novel phosphonated ligand[J]. J. Mol. Struct.,2013,1034:276.
[14]陈连山,刘玉国,冯春良,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(Nature Science),1993,16(2):135.
[15] 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.
[16] Liu W,Li X H,Huo L N,Yang T L. Synthesis,luminescenceand 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.
[17] 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.
[18] Zampakou M,Akrivou M,Andreadou E G,Raptopoulou C P,Psycharis V,Pantazaki A A,Psomas G. Structure,antimicrobial activity,DNA-and albumin-binding of manganese(II)complexes with the quinolone antimicrobial agents oxolinic acid and enrofloxacin[J]. J. Inorg. Biochem.,2013,121:88.
[19] Wang Y,Jiang X H,Zhou L M,Yang L J,Xia G Q,Chen Z J,Duan M. Synthesis and binding with BSA of a new gemini surfactant[J]. Physicochem. Eng. Aspects,2013,436:1159.
[20]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.
[21] 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.
[22] 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, Part A, 2013,118:972.
[23]杨树平,韩立军,潘燕,王大奇,赵翠,汪波.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.
[24]宋盼,杨水兰,周通,杨天林,纳鹏军,倪刚.甘氨酸-N,N-双(亚甲基磷酸)及其Eu(Ⅲ)配合物与BSA的作用机制[J].中国稀土学报,2016,34(5):566.Song P,Yang S L,Zhou T,Yang T L,Na P J,Ni G.Mechanism of interaction between glycine-N,N-dimethyl phosphonate and its europium(Ⅲ)complex and bovine serum albumin(BSA)[J]. Journal of the Chinese Society of Rare Earths,2016,34(5):566.
[25]刘伟,杨水兰,宋盼,杨天林.一种含磷三足体衍生物及其铕配合物的合成及性能表征[J].应用化学,2015,32(7):777.Liu W,Yang S L,Song P,Yang T L. Synthesis and characterization of a phosphorus-containing tripod ligand and its europium complex[J]. Chinese Journal of Applied Chemistry,2015,32(7):777.
[26]王安萍,张国文,潘军辉,龚毅.金属离子对次野鸢尾黄素与牛血清白蛋白相互作用的影响[J].分析科学学报,2008,24(4):389.Wang A P,Zhang G W,Pan J H,Gong Y. Effect of metal ions on the interaction between bovine serum albumin and irisflorentin[J]. Journal of Analytical Science,2008,24(4):389.
[27]郭明,王炜,周建钟,郭晓琴.金属离子介导下的紫杉醇与血清蛋白结合反应机制的研究[J].化学研究与应用,2008,20(4):457.Guo M,Wang W,Zhou J Z,Guo X Q. Study on the interaction between paclitaxel-iron(Ⅲ)and bovine ser-um albumin[J]. Chemical Research and Application,2008,20(4):457.
[28] Kamatchi T S,Chitrapriya N,Ahamed J V S,Moon S S,Fronczek F R,Natarajan K. 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.
[29] Purcell M,Neault J F,Tajmir-Riahi H A. Interaction of taxol with human serum albumin[J]. Biochim. Biophys. Acta,2000,1478(1):61.
[30] 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].Transition. Met. Chem.,2011,36(4):395.
[31]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.
[32]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.