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萘酰氨基修饰β环糊精对几种荧光染料的分子识别
http://www.100md.com 《分析化学》 2006年第7期
修饰环糊精,染料分子,分子识别,超分子配合物,热力学,,修饰环糊精,染料分子,分子识别,超分子配合物,热力学,摘要,关键词,1引言,2实验部分,3
     摘 要 用光谱滴定技术分别测定了β环糊精(1)、单\[6(1萘酰氨基)乙基氨基6脱氧\]β环糊精(2)、单\[6(1萘酰氨基)二乙基二氨基6脱氧\]β环糊精(3)在25℃时,pH为7.2 、2.0和10.1的缓冲溶液中与几种染料分子形成超分子配合物的稳定常数Ks,并考察了pH=7.2时识别过程的热力学参数ΔH0和TΔS0。结果表明,pH为2.0和10.1时,静电、疏水和氢键作用协同贡献于超分子配合物的形成,如主体2与AR在pH=10.1时形成的Ks=7085;而pH=2.0时的Ks=1034。当pH=7.2时主客体的尺寸/形状匹配、疏水作用和范德华力决定配合物的稳定性。主体2、3对AR、 TNS 和ANS的包结配位是放热过程,并给出较大的焓变(-ΔH0),对RhB主要表现为熵驱动过程。

    关键词 修饰环糊精,染料分子,分子识别,超分子配合物,热力学

    Molecular Recognition of Several Fluorescent Dyes

    by βCyclodextrins Modified with Naphthyloxamino

    Zhao Yan, Liu Xiaoqing, Zhao Yong, Liu Pin, Li Cong

    (College of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650092)

    Abstract The spectral titrations have been performed to give the stability constants Ks for the supermolecular systems formed by βcyclodextrin (1) , mono \[6(1naphthyloxamino)ethylenediamino)6 dexoy\]βcyclodextrin(2), mono \[6(1naphthyloxamino)diethylenediamino)6dexoy\] βcyclodextrin (3), with some dyes in aqueous buffers of pH 7.2, 2.0 and 10.1 at 25℃. Moreover, the thermodynamic parameters (ΔH and TΔS ) for the inclusion complexation were also calculated at pH 7.2. The results obtained indicated that electrostatic, hydrophobic and hydrogen bonding interactions cooperatively contributed to the formation of supramolecular complexes at pH 2.0 and pH 10.1 respectively. Typically, host 2 with acridine red (AR) displayed the binding ability (Ks=7085) at pH 10.1, but Ks=1034 at pH 2.0. On the other hand, the size/shapematching between host and guest, hydrophobic and van der Waals interactions determined the stability of inclusion complex at pH 7.2. The inclusion reactions of 2, 3 with AR, sodium2pmethyl phenylamino6naphthalene sulfonate (TNS) and ammoniumphenylaminonaphthalene sulfonate (ANS) were exothermic, giving the larger negative enthalpic gain (-ΔH ), but the inclusion complexation with RhB was mainly entropydriven contribution. ......

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