Fluorophore appended saccharide cyclophane: self-association, fluorescent properties, heterodimers with cyclodextrins, and cross-linking behavior with peanut agglutinin of dansyl-modified saccharide cyclophane.
Fluorophore appended saccharide cyclophane: self-association, fluorescent properties, heterodimers with cyclodextrins, and cross-linking behavior with peanut agglutinin of dansyl-modified saccharide cyclophane.
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荧光团附加的糖环芳烷：自缔合、荧光特性、与环糊精的异二聚体以及丹酰基修饰的糖环芳烷与花生凝集素的交联行为。
DOI：
10.1021/jo0496852
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发表时间：
2004
期刊：
影响因子：
--
通讯作者：
I. Hamachi
中科院分区：
文献类型：
--
作者：
O. Hayashida;I. Hamachi
通过在四氮杂对环蕃骨架中引入三个末端半乳糖残基的支链和一个丹磺酰基部分的支链，制备了带有环境敏感荧光团的糖环蕃（1）。6.1.6.1通过荧光光谱和动态光散射研究了丹磺酰基修饰的糖环番在水溶液中的自缔合行为。至少在低于1.0 × 10（-5）M的浓度下，糖环番1以单体状态存在，而在较高浓度下，它倾向于形成自聚集复合物。通过荧光光谱法研究了溶剂极性对1的发射光谱的依赖性。随着二氧六环/水溶剂中二氧六环含量的增加，源自1的丹磺酰基部分的荧光强度随着荧光最大值（λ（em））的伴随蓝移而沿着增加。在1在水中的单体状态下，1的丹磺酰基部分不完全包括在其环蕃腔中，而是部分暴露于本体水相。然而，在较高的浓度范围内的聚集状态，丹磺酰基基团1位于非极性的环番腔，其微环境相当于1-丁醇的极性评价的基础上的λ（EM）和溶剂极性之间的相关性。这表明丹磺酰基部分在环蕃内的分子间包含。当环糊精（CD）与1混合时，1的丹磺酰基结合到CD的内腔，例如γ-CD、β-CD、6-O-alpha-葡糖基-β-CD和6-O-alpha-麦芽糖基-β-CD，结合常数分别为7.5 × 10（2）、7.8 × 10（2）、7.7 × 10（2）和6.0 × 10（2）M（-1）。这种超分子组装的丹磺酰基修饰的环番1和CD引起的荧光光谱的变化，以及诱导CD带在水介质中的外观。此外，糖cyclophane 1选择性地结合到花生凝集素（PNA），半乳糖苷结合凝集素，这是很容易监测的可见浊度的解决方案，由于这些组件的交联凝集，以及通过荧光光谱。
A saccharide cyclophane bearing an environment-sensitive fluorophore (1) was prepared by introducing not only three branches with a terminal galactose residue but also one with a dansyl moiety into a tetraaza[6.1.6.1]paracyclophane skeleton. Self-association behavior of the dansyl-appended saccharide cyclophane was characterized in aqueous media by fluorescence spectroscopy and dynamic light scattering measurements. At least in the concentrations below 1.0 x 10(-5) M, saccharide cyclophane 1 existed in a monomeric state, whereas it tended to form self-aggregated complexes in the higher concentration. Solvent polarity dependency on the emission spectra of 1 was examined by fluorescence spectroscopy. With increasing dioxane contents in dioxane/water solvents, the fluorescence intensity originating from the dansyl moiety of 1 increased along with a concomitant blue shift of the fluorescence maximum (lambda(em)). In the monomeric state of 1 in water, the dansyl moiety of 1 was not fully included into its cyclophane cavity but partially exposed to the bulk aqueous phase. In the higher concentration ranges in an aggregate state, however, the dansyl group of 1 was located in the apolar cyclophane cavity whose microenvironment was equivalent to the polarity of 1-butanol evaluated on the basis of a correlation between lambda(em) and solvent polarity. This indicates an intermolecular inclusion of the dansyl moiety within the cyclophane. When cyclodextrin (CD) was mixed with 1, the dansyl group of 1 was bound to an internal cavity of CD such as gamma-CD, beta-CD, 6-O-alpha-glucosyl-beta-CD, and 6-O-alpha-maltosyl-beta-CD with binding constants of 7.5 x 10(2), 7.8 x 10(2), 7.7 x 10(2), and 6.0 x 10(2) M(-1), respectively. Such a supramolecular assembling of dansyl-modified cyclophane 1 and CDs caused changes of the fluorescence spectra as well as appearance of induced CD bands in aqueous media. Furthermore, saccharide cyclophane 1 was selectively bound to peanut agglutinin (PNA), galactoside-binding lectin, which was readily monitored by a visible turbidity of the solution due to a cross-linking agglutination of these components, as well as by fluorescence spectroscopy.