物理化学学报 >> 2007, Vol. 23 >> Issue (03): 394-398.doi: 10.3866/PKU.WHXB20070321

研究论文 上一篇    下一篇

一种新型芳香二胺桥联β-环糊精对染料的分子识别

赵焱;杨自明;朱洪友;顾娟;王宇飞   

  1. (云南师范大学化学化工学院, 昆明 650092; 云南大学化学科学与工程学院, 昆明 650091)
  • 收稿日期:2006-09-25 修回日期:2006-11-13 发布日期:2007-03-07
  • 通讯作者: 赵焱 E-mail:zhaooyann@eyou.com

Molecular Recognition of a Novel Bridged Bis(β-cyclodextrin) Tethered with Aromatic Diamine for Dyes

ZHAO Yan;YANG Zi-Ming;ZHU Hong-You;GU Juan;WANG Yu-Fei   

  1. (College of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650092, P. R. China; School of Chemical Science and Technology, Yunnan University, Kunming 650091, P. R. China)
  • Received:2006-09-25 Revised:2006-11-13 Published:2007-03-07
  • Contact: ZHAO Yan E-mail:zhaooyann@eyou.com

摘要:
以单-(6-对甲苯磺酰基)-β-环糊精和3,3′-亚甲基联苯胺为原料, 合成了一种新型刚性结构的芳香二胺桥联环糊精, 3,3′-亚甲基联苯胺桥联(6-氨基-6-脱氧-β-环糊精)2. 并用荧光光谱和紫外光谱技术分别测定了在25 ℃时, pH为7.20的磷酸缓冲溶液中β-环糊精(1)和新型桥联环糊精(2)与几种染料分子, 如吖定红(AR)、中性红(NR)、2-对甲苯胺基-6-萘磺酸钠(TNS)、1-苯胺基-8-萘磺酸铵(ANS)、罗丹明B(RhB)和亮绿(BG)形成超分子配合物的稳定常数KS. 化学计量比表明, 桥联环糊精2与客体形成了1∶1的超分子配合物, 其对客体的键合能力和分子选择性远远强于母体?茁-环糊精, 如桥联环糊精2对BG的键合能力可以达到母体环糊精的22.2倍. 从主-客体间的尺寸匹配关系和多重识别机理等方面探讨了桥联环糊精对客体分子的协同键合作用.

关键词: 桥联β-环糊精, 协同键合, 染料, 分子识别, 超分子化学

Abstract: A novel bridged bis(β-cyclodextrin) with rigid aromatic diamino tethers, 3,3′-methylenedianilino-briged-bis(6-aimino-6-deoxy-β-cyclodextrin) (2), was synthesized by the reaction of mono-[6-o-(p-tolysulfonyl)]-β-cyclodextrin with 3,3′-methylenedianiline. The inclusion complexation behaviors of native β-cyclodextrin (1) and the novel briged(β-cyclodextrin) (2) with some organic dyes, i.e., acridine red (AR), neutral red (NR), sodium 6-toluidino-2-naphthalenes- ulfonate (TNS), ammonium 8-anilino-1-naphthalenesulfonate (ANS), rhodamine B (RhB) and brilliant green (BG) were investigated at 25 ℃ in aqueous phosphate buffer solution (pH=7.20) by means of fluorescence and ultraviolet spectroscopy. The spectral titrations gave the complex stability constants (KS) and Gibbs free energy changes (ΔG0) for the stoichiometry 1∶1 inclusion complexation of hosts examined with dye molecules. The obtained results demonstrated that bis(β-cyclodextrin) 2 showed much higher binding ability and molecular selectivity toward these guest dyes than native β-cyclodextrin 1. Typically, dimmer 2 displayed the highest binding ability upon inclusion complexation with BG, affording 22.2 times higher KS value than native β-cyclodextrin. The cooperative binding ability of the bis(β-cyclodextrin) was discussed from the viewpoints of size/shape-fit interaction and multiple recognition mechanism.

Key words: Bridged bis(β-cyclodextrin), Cooperative binding, Dyes, Molecular recognition, Supramolecular chemistry