Premium
Synthesis of Novel Bis( β ‐cyclodextrin)s Linked with Glycol and Their Inclusion Complexation with Organic Dyes
Author(s) -
Zhao Yong,
Yang Yong Cun,
Shi Hao,
Zhu Hong You,
Huang Rong,
Chi Chao Ming,
Zhao Yan
Publication year - 2010
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.200900345
Subject(s) - chemistry , ethylene glycol , cyclodextrin , triethylene glycol , diethylene glycol , medicinal chemistry , molecule , hydrogen bond , rhodamine b , polymer chemistry , stereochemistry , organic chemistry , photocatalysis , catalysis
Three novel bis( β ‐cyclodextrin (CD))s with flexible glycol linkers, i.e. , ethylene glycol‐bridged bis(6‐hydroxy‐6‐deoxy‐ β ‐CD) ( 2 ), diethylene glycol‐bridged bis(6‐hydroxy‐6‐deoxy‐ β ‐CD) ( 3 ), and triethylene glycol‐bridged bis(6‐hydroxy‐6‐deoxy‐ β ‐CD) ( 4 ) have been synthesized by the reaction of mono[6‐ O ‐( p ‐toluenesulfonyl)]‐ β ‐CD with corresponding materials. The inclusion complexation behaviors of these compounds 2 – 4 with organic dyes; that is, acridine red (= N ‐[(3 Z )‐6‐(methylamino)‐3 H ‐xanthen‐3‐ylidene]methanaminium chloride; AR), neutral red (= N 8 , N 8 ,3‐trimethylphenazine‐2,8‐diamine hydrochloride; NR), ammonium 8‐anilinonaphthalene‐1‐sulfonate (ANS), sodium 6‐( p ‐toluidinyl)‐naphthalene‐2‐sulfonate (TNS), rhodamine B (RhB) and brilliant green (= N ‐(4‐{[4‐(diethylamino)cyclohexa‐2,5‐dien‐1‐yl](phenyl)methyl}cyclohex‐2‐en‐1‐ylidene)‐ N ‐ethyl‐ethanaminium hydrogen sulfate; BG), have been investigated at 25° in phosphate buffer (pH 7.20) by ultraviolet, fluorescence, and 2D‐NMR spectroscopy. The results indicate that the two linked CD units may cooperatively bind a guest, and the molecular binding ability toward dye guests, especially bent ANS, T‐shaped RhB, and triangular BG, can be extended. This cooperative binding mode is confirmed by Job 's experiments and 2D‐NMR investigations. Furthermore, the complex stability depends greatly on the linker length of these glycol‐bridged bis( β ‐CD)s and the size and shape of guest. The higher binding ability and selectivity of dye molecules by bis( β ‐CD)s 2 – 4 are discussed from the viewpoint of size/shape‐fit concept and multiple recognition mechanism.