以黄酮冠醚金属配合物为基体的阴离子化学敏感器

高等学校化学学报 ›› 2004, Vol. 25 ›› Issue (8): 1525.

以黄酮冠醚金属配合物为基体的阴离子化学敏感器

周丽丽, 李华平, 王辉, 冯琳, 张晓宏, 吴世康

中国科学院理化技术研究所, 北京100101

收稿日期:2003-07-14 出版日期:2004-08-24 发布日期:2004-08-24
基金资助:
国家重点基础研究发展规划署(批准号:G2000078100)资助

An Anion Chemosensor Based on Flavone Quasi-crown Ether Metal Complex

ZHOU Li-Li, LI Hua-Ping, WANG Hui, FENG Lin, ZHANG Xiao-Hong, WU Shi-Kang

Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100101, China

Received:2003-07-14 Online:2004-08-24 Published:2004-08-24

摘要/Abstract

摘要： 合成了两种以新型黄酮类冠醚化合物(L)为配体的金属配合物[Ca(L)]²⁺(1)或[Mg(L)]²⁺(2).对其在乙腈溶液中与阴离子间的相互作用进行了研究.当这种化学敏感器和HSO₄^-或H₂PO₄^-阴离子相互作用时,可观察到强烈的颜色变化.UV光谱滴定实验表明,配合物1(或2)和HSO₄^-间形成了1:1的稳定配合物.配合物1(或2)对于HSO₄^-或H₂PO₄^-阴离子也可用荧光光谱法进行选择性检测,较UV方法有更高的灵敏度.还提出了配合物1(或2)与阴离子间通过两点结合方式,构成新的配合物可能结构的建议.通过色调变化和荧光测定的方法进行研究,结果表明,带有染料分子的金属配合物可用作为有效识别和检测阴离子的敏感器件.

关键词: 金属配合物, 阴离子检测, 比色法, 含氧酸阴离子

Abstract: A novel metal complex [Ca(L)] 2+ (1)[or [Mg(L)] 2+ (2)] based on the flavone derivative with a quasi-crown ether(4′-(dimethylamino)-3,6-(tetraethylene glycol)flavone) was synthesized and studied as anion-binding receptors. Remarkable color change of host 1 or 2 induced by the complex formation with HSO₄^-(or H₂PO₄^-) was observed. The UV-Vis spectroscopic titration experiments indicated the formation of 1:1 stable complexes between 1 or 2 and HSO₄^-. HSO₄^-(or H₂PO₄^-) can also be selectively detected by the fluorescence method,which is even more sensitive than the UV-Vis spectroscopic method. The binding manner using double binding sites and possible structures formed between complex 1 or 2 and selected anions were proposed. The results showed the dye-containing metal complexes could act as the efficient and selective chromogenic and fluorescent reagents for anion sensing.

Key words: Metal-complex, Anionic recognition, Colorimetry, Oxoanions

中图分类号:

O641.4

TrendMD:

周丽丽, 李华平, 王辉, 冯琳, 张晓宏, 吴世康. 以黄酮冠醚金属配合物为基体的阴离子化学敏感器. 高等学校化学学报, 2004, 25(8): 1525.

ZHOU Li-Li, LI Hua-Ping, WANG Hui, FENG Lin, ZHANG Xiao-Hong, WU Shi-Kang . An Anion Chemosensor Based on Flavone Quasi-crown Ether Metal Complex. Chem. J. Chinese Universities, 2004, 25(8): 1525.

参考文献

[1] 　N iiku ra K.,B isson A.P.,E.V.A n slyn..J.Chem.Soc.,Perk in T ran s.2.[J],1999:1 111—1 114 [2] 　M iyaji H.,Sato W.,Sessler J.L.et al..T etrahed ron L ett.[J],2000,41(9):1 369—1 371 [3] 　A nzenbacher J r.P.,T ry A.C.,M iyaji H.et al..J.Am.Chem.Soc.[J],2000,122(42):10 268—10 272 [4] 　M iyaji H.,Sato W.,Sessler J.L..A ngew.Chem.,In t.Ed.[J],2001,40(1):154—157 [5] 　L ee C.,L ee D.H.,Hong J.I..T etrahed ron L ett.[J],2001,42(49):8 665—8 668 [6] 　L ee K.H.,L ee H.Y.,Hong J.I..T etrahed ron L ett.[J],2001,42(32):5 447—5449 [7] 　L ee D.H.,L ee H.Y.,L ee K.H.et al..Chem.Comm un.[J],2001:1 188—1 189 [8] 　Kato R.,N ih izaw a S.,H ayash ita T.et al..T etrahed ron L ett.[J],2001,42(30):5 053—5 056 [9] 　Sancenon F.,D escalzo A.B.,M artinez-M anaez R.et al..A ngew.Chem.,In t.Ed.[J],2001,40(14):2 640—2 643 [10] 　Sancenón F.,Mãnez R.M.,So to J..A ngew Chem e.In t.Ed.[J].2002,41(8):1 416—1 419 [11] 　Schm id tchen F.P.,Berger M..Chem.R ew.[J],1997,97(5):1 609—1646 [12] 　Kubo Y.,Tok ita S.,Kubo M..N atu re[J],1996,382(6 591):522—524 [13] 　L ehn J.M..Sup ram o lecu lar Chem istry,Concep ts and Persp ectives[M],W einheim:W iley2vch,1995 [14] 　B lack C.B.,A nd rio letti B.,T ry A.C.et al..J.Am.Chem.Soc.[J],1999,121(44):10 438—10 439 [15] 　M iyaji H.,Sato W.,Sessler J.L..A ngew.Chem.,In t.Ed.[J],2000,39(10):1 777—1 780 [16] 　A nzenbacher P.,J u rsikova K.,Sessler J.L..J.Am.Chem.Soc.[J],2000,122(38):9 350—9 351 [17] 　L ee D.H.,L ee H.Y.,Hong J.I..T etrahed ron L ett.[J],2002,43(40):7 273—7 276 [18] 　Ho rn ing E.C..O rg.Syn.Co ll.[J],1955,3:280—452 [19] 　L I H ua-P ing(李华平),W AN G Peng-Fei(汪鹏飞),W U Sh i-Kang(吴世康).Chem.J.Ch inese U n iversities(高等学校化学学报)[J],1998,19(9):1 431—1435 [20] 　W ang Pengfei,W u Sh ikang.J.Pho tochem.Pho tob io l.A:Chem.[J],1993,76:27—32 [21] 　W ang Pengfei,W u Sh ikang.J.Pho tochem.Pho tob io .lA:Chem.[J],1994,77:127—131 [22] 　Bou rson J.,Pouget J.,V aleu r B..J.Phys.Chem.[J],1993,97:4 552—4 557