一种含磷三足体衍生物及其铕配合物的合成及性能表征

doi:10.11944/j.issn.1000-0518.2015.07.140408

摘要/Abstract

摘要：

设计合成了一种新型含磷的水溶性三足体衍生物[L:N-二(吡啶-二氨基乙酰基)甲基磷酸]及其Eu(Ⅲ)的配合物,用红外吸收光谱、元素分析、差热-热重和紫外光谱法等技术手段对该配合物进行了表征,用荧光光谱法研究了室温下该配合物和牛血清白蛋白(BSA)的相互作用。结果表明,配体与苦味酸铕形成1:1型配合物Eu(pic)₃L;配合物与BSA之间有很强的结合作用;配合物对BSA内源荧光的猝灭方式为静态猝灭;配合物与BSA的作用力为分子间氢键和范德华力。分别考察了Fe³⁺和Cu²⁺对配合物与BSA结合作用的影响,证明Fe³⁺和Cu²⁺能够以金属离子桥键与配合物结合使配合物-BSA的稳定性增强。根据Foster型偶极-偶极无辐射能量转移机理可知,配合物可以和BSA以偶极-偶极无辐射进行能量传递。

关键词: 含膦三脚架配体, 铕配合物, 牛血清白蛋白

Abstract:

A novel water-soluble phosphorus-containing tripod ligand [L:N-bis(pyridine-aminoacetyl) methyl phosphate] and its europium complexes was synthesized and characterized by elemental analysis, TG-DSC, IR spectroscopy, UV spectroscopy and molar conductance analysis. In addition, the interaction between bovine serum albumin (BSA) and complexes was investigated with fluorescence spectra at room temperature. The experimental results show that the ligand forms the 1:1 complex Eu(pic)₃L with europium picrate. There exists a strong combination action between complexes and BSA. The acting forces between the complexes and BSA are hydrogen bonding and van der Waals interaction. The quenching of BSA by complexes follows the static quenching mechanism. The influence of Fe³⁺ and Cu²⁺ on the combination process of the complexes with BSA was investigated. It is found that Fe³⁺ and Cu²⁺ can strengthen the interaction of the complex with BSA through the formation a metal bridge bond with the complex. According to Foster type dipole-dipole nonradiative energy transfer mechanism, there is no radiation energy transfer between complexes and BSA by dipole-dipole.

Key words: tripod phosphorus ligands, europium complexes, bovine serum albumin

中图分类号:

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): 777-787.

LIU Wei, YANG Shuilan, SONG Pan, YANG Tianlin. Synthesis and Characterization of a Phosphorus-containing Tripod Ligand and Its Europium Comphex[J]. Chinese Journal of Applied Chemistry, 2015, 32(7): 777-787.

参考文献

[1]	WU Mingxu,ZHAO Zhi,ZHOU Jing,et al.Influences of Organophosphorus Pesticide on the Growth and Physiological Characteristics of Bacillus subtilis[J]. Anim Husbandry Feed Sci,2013,34(3):10-13(in Chinese). 吴明旭,赵治,周晶,等. 有机磷农药对枯草芽胞杆菌生长和生理特征的影响[J]. 畜牧与调料科学,2013,34(3):10-13.
[2]	Vitha T,Kubicek V,Kotek J,et al.Gd(Ⅲ) Complex of a Monophosphinate-bis(phosphonate) DOTA Analogue with a High Relaxivity; Lanthanide(Ⅲ) Complexes for Imaging and Radiotherapy of Calcified Tissues[J]. Dalton Trans,2009,(17):3204-3214.
[3]	Xu H,Wang L H,Zhu X H,et al.Application of Chelate Phosphine Oxide Ligand in EuⅢ Complex with Mezzo Triplet Energy Level, Highly Efficient Photoluminescent, and Electroluminescent Performances[J]. J Phys Chem B,2006,110(7):3023-3029.
[4]	Kiefer G E,Woods M. Solid State and Solution Dynamics of Pyridine Based Tetraaza-Macrocyclic Lanthanide Chelates Possessing Phosphonate Ligating Functionality(Ln-PCTMB):Effect on Relaxometry and Optical Properties[J]. Inorg Chem,2009,48(24):11767-11778.
[5]	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,2010,696(2011):2040-2046.
[6]	Xu X W,Li X J,Zhan S H. Synthesis and Structure of a New Tetracopper(II) Complex Bridged both by Oxamido and Phenolato Groups: Cytotoxic Activity, and Reactivity Towards DNA and BSA[J]. J Mol Struct,2013,1039:28-36.
[7]	HUO Lina,LIU Wei,YANG Tianlin,et al.Synthesis,Characterization and Interaction of a Novel Ce(Ⅲ) Picorate Complex with HAS,BSA and VOA[J]. Chinese Rare Earth,2014,35(2):37-43(in Chinese). 霍丽娜,刘伟,杨天林,等. 新型铈苦味酸配合物的合成、表征及其与白蛋白相互作用[J]. 稀土,2014,35(2):37-43.
[8]	ZHAO Long,LU Jixin,XIANG Zhenling,et al.Study on the Interaction of Adriamycin Rare Earth Complexes with Human Serum Albumin[J]. J Anal Sci,2011,27(5):581-585(in Chinese). 赵龙,卢继新,项振玲,等. 多柔比星稀土配合物与人血清白蛋白相互作用的研究[J]. 分析科学学报,2011,27(5):581-585.
[9]	Helmut Sigel,Bruce Martin R. Coordinating Properties of the Amide Bond. Stability and Structure of Metal Ion Complexes of Peptides and Related Ligands[J]. Chem Rev,1982,82:385-426.
[10]	Nakamoto K. Infrared and Raman Spectra of Inorganic and Coordination Compounds[M]. Beijing:Chemical Industry Press(CIP),1986(in Chinese). 中本一雄. 无机和配位化合物的红外的拉曼光谱[M]. 北京:化学工业出版社,1986.
[11]	MA Xuebing,FU Xiangkai,WANG Qiang,et al.Synthesis of Water-soluble Phospgine Ligands Containing Hydroxyl and Phosphonic Acid Groups[J]. Chinese J Appl Chem,2002,19(12):1154-1157(in Chinese). 马学兵,傅相锴,王强,等. 含羟基、磷酸根水溶性膦配体的合成[J]. 应用化学,2002,19(12):1154-1157.
[12]	Organophosphorus Reagents:A Practical Approach in Chemistry[M]. Oxford University Press,2004.
[13]	GAO Jihong,YANG Tianlin,WU Genliang. Synthesizing,Charaterizing and Flourescence Properties of 2,2,2-Amine Tri-Acetly-Benzylamine and Its Rare Earth Complexes[J]. Rare Met Lett,2013,26(7):29-33(in Chinese). 高继红,杨天林,吴根良. 2,2,2-胺三乙酰-苯胺及其稀土配合物的合成、表征与荧光性质[J]. 稀有金属快报,2013,26(7):29-33.
[14]	XIE Yuanwu. The Molar Ratio Determinates Composition of Complex and Study Its Theory of Stability Constant[J]. Chem Online,1988,2:39-42(in Chinese). 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,1988,2:39-42.
[15]	CHEN Lianshan,LIU Yuguo,FENG Chunliang,et al.Study of the Composition of the Precipitate from Method and Asmus Method[J]. J Liaoning Normal Univ,1993,16(2):135-140(in Chinese). 陈连山,刘玉国,冯春亮,等. 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,1993,16(2):135-140.
[16]	Liu W,Li X H,Huo L N,et al.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):10465-10469.
[17]	Vicente-Sancheza C,Egidoa J,Sanchez-Gonzaleza P D,et al. Effect of the Flavonoid Quercetin on Cadmium-induced Hepatotoxicity[J]. Food Chem Toxicol,2008,46(6):2279-2287.
[18]	YANG Meiling,YANG Peiju,SONG Yumin. Synthesis, Characterization and Interaction of Metal Complexes of Rutin with HAS and BSA[J]. Chinese J Inorg Chem,2005,21(4):483-489(in Chinese). 杨美玲,杨培菊,宋玉民. 芦丁金属配合物的合成,表征及与血清白蛋白的相互作用[J]. 无机化学学报,2005,21(4):483-489.
[19]	TIAN Lunfu,LIU Zhongfang,HU Xiaoli,et al.Proteins Fluorescence Quenching by and Its Analytical [Hg (SCN)4]2-Application[J]. Chem J Chinese Univ,2012,33(1):59-65(in Chinese). 田伦富,刘忠芳,胡小莉,等. [Hg(SCN)4]2-对蛋白质的荧光猝灭反应及其分析应用[J]. 高等学校化学学报,2012,33(1): 59-65.
[20]	LIN Haibin,ZHEN Lin,LIN Yuqin,et al.Study of Interaction Between Bovine Serum Albumin and Colbalt Complexes of Phenanthroline and Nitrilotriacetate by Fluorescence Spectrometry[J]. Chem J Chinese Univ,2013,34(8):1818-1825(in Chinese). 林海彬,郑琳,林玉琴,等. 邻菲啰啉和氨三乙酸钴配合物与牛血清白蛋白相互作用的荧光分析[J]. 高等学校化学学报,2013,34(8):1818-1825.
[21]	YANG Manman,XI Xiaoli,YANG Pin. Studies on Interaction of New Medicine of Quinolone Class with HSA and BSA by Using Fluorescence Enhancement and Fluorescence Quenching Theory[J]. Chem J Chinese Univ,2006,27(4):687-691(in Chinese). 杨曼曼,席小莉,杨频. 用荧光猝灭和荧光加强两种理论研究喹诺酮类新药与白蛋白的作用[J]. 高等学校化学学报,2006,27(4):687-691.
[22]	HUANG Ying,WANG Juan,GUO Gaiying,et al.Interaction of 6-Thioguanine with Cucurbit[7]uril and Bovine Serum Albumin by Spectroscopic Method[J]. Chem J Chinese Univ,2013,34(2):375-380(in Chinese). 黄英,王娟,郭改英,等. 光谱法研究硫鸟嘌呤与七元瓜环及牛血清白蛋白的超分子相互作用[J]. 高等学校化学学报,2013,34(2):375-380.
[23]	Peng L,Wei R R,Li K,et al.A Ratiometric Fluorescent Probe for Hydrophobic Proteins in Aqueous Solution Based on Aggregation-induced Emission[J]. Analyst,2013,138(7):2068-2072.
[24]	SUN Qilong,WANG Zhaoyang,REN Biye,et al.Effect of Added Salts on Intra-and Inter-molecular Fluorescence NRET of Sulfonate Polyelectrolytes[J]. Chem J Chinese Univ,2003,24(9):1695-1699(in Chinese). 孙启龙,王朝阳,任碧野,等. 添加盐对磺酸基聚电解质分子内及分子间荧光非辐射能量转移的影响[J]. 高等学校化学学报,2003,24(9):1695-1699.
[25]	Guo X Q,Castellano F N,Li L,et al.Use of a Long-lifetime Re(Ⅰ) Complex in Fluorescence Polarization Immunoassays of High-molecular-weight Analytes[J]. Anal Chem,1998,70(3):632-637.
[26]	SUN Changfeng,GUO Na. Trace Element Iron Effects on Human Health[J]. Stud Trace Elem Health,2011,28(2):64-66(in Chinese). 孙长峰,郭娜. 微量元素铁对人体健康的影响[J]. 微量元素与健康研究,2011,28(2):64-66.
[27]	SHANG Yonghui,LI Hua,SUN Jiajuan,et al.Study on the Interaction of Bovine Serum Albumin with Riboflavin by Fluorescence Spectroscopy[J]. J Anal Sci,2010,26(1):67-70(in Chinese). 尚永辉,李华,孙家娟,等. 核黄素与牛血清白蛋白相互作用的荧光光谱研究[J]. 分析科学学报,2010,26(1):67-70.
[28]	XIAO Jianbo. Structure-Affinity RelationshiP,Theory Model and Application of Interaction between Polyphenols and Serum Albumin[D]. Changsha:Zhongnan University,2009(in Chinese). 肖建波. 多酚类化合物与血清白蛋白相互作用的结构-结合力关系,理论模型和应用研究 [D]. 长沙:中南大学,2009.