萘酰氨修饰β-环糊精及其铜配合物对萘衍生物的分子识别  

Molecular Recognition of β-CD Modified by Naphthyloxamino Groups and Their Complexes with Copper(II) to Naphthalene Derivatives

作　　者：赵焱[1] 杨自明[1] 李正宇[1] 李碧玉[1] 阿芳[1] 毕先钧[1] 

机构地区：[1]云南师范大学化学化工学院,昆明650092

出　　处：《无机化学学报》2006年第4期679-684,共6页Chinese Journal of Inorganic Chemistry

基　　金：云南省自然科学基金资助项目(2003B0014Q);云南省教育厅科研基金资助项目(03Y313A)。

摘　　要：用荧光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)及其相应的铜配合物(4、5)在25℃时,pH为7.20的缓冲溶液中与几种萘衍生物形成的超分子配合物的稳定常数。结果表明,化合物2、3与大部分β-萘衍生物形成超分子配合物的稳定性大于α-萘衍生物。铜键合修饰的环糊精4、5扩展了母体环糊精的键合能力,其中主体5与2-萘酚(2-NO)形成的稳定常数是母体环糊精的35倍,且引入铜(II)后,修饰环糊精的分子选择性提高。从主-客体的尺寸/形状匹配和多重识别等方面探讨了分子识别的机理。Two novel copper（Ⅱ） complexes of β-cyclodextrin modified by naphthyloxamino groups were synthesized. The spectrofluorometric titrations were performed to give the stability constants for the supramolecular 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） and their copper（R） complexes （4,5）, with several naphthalene derivatives in phosphate buffer solution （pH 7.2, 0.1 mol·L^-1） at 25 ℃. The results obtained indicate that the inclusion complexes of most β-naphthalene derivatives and hosts 2,3 are more stable than those of β-naphthalene derivatives. On the other hand, copper（R） complexes of β-CD modified by naphthyloxamino groups enhance the original binding ability of the parent β-CD. Typically, host 5 displays the highest binding ability upon inclusion complexation with 2-NO affording 35 times higher Ks value than unmodified β-CD. Additionally, the copper（R） ion introduced in the chain enhances the molecular selectivity of modified β-cyclodextrins. The molecular recognition mechanism is discussed from the viewpoint of the size/shape-fit concept and multiple recognition.

关 键 词：修饰环糊精 萘衍生物 分子识别 超分子配合物 

分 类 号：O614.121[理学—无机化学]