Ozawa Rimiko, Hashimoto Takeshi, Yamauchi Akiyo, Suzuki Iwao, Smith Bradley D, Hayashita Takashi
Department of Chemistry, Faculty of Science and Technology, Sophia University, Chiyoda, Tokyo, Japan.
Anal Sci. 2008 Feb;24(2):207-12. doi: 10.2116/analsci.24.207.
An inclusion complex consisting of a fluorescent phenylboronic acid (C1-APB) and beta-cyclodextrin (beta-CD) acts as a supramolecular saccharide sensor whose response mechanism is based on photoinduced electron transfer (PET). This study evaluated four kinds of cyclodextrins (alpha-CD, beta-CD, gamma-CD, and NH(2)-beta-CD) by comparing their pH profiles, and confirmed that beta-CD was the best host for C1-APB because the C1-APB/beta-CD complex exhibited high affinity for saccharides as well as high fluorescent recovery upon saccharide binding. An investigation of the beta-CD concentration effect revealed the formation of a 1:1 inclusion complex of C1-APB with beta-CD. The observed saccharide selectivity of the C1-APB/beta-CD complex is in the following order: D-fructose (4039 +/- 69 M(-1)) > D-ribose (1083 +/- 26 M(-1)) > L-arabinose (474 +/- 11 M(-1)) > D-galactose (318 +/- 3 M(-1)) > maltotoriose (135 +/- 5 M(-1)) > D-glucose (114 +/- 2 M(-1)) > maltose (81 +/- 2 M(-1)). In addition to monomer emission, dimer emission from pyrene dimers was observed in the spectra for the C1-APB/gamma-CD complex, which allowed a ratiometric analysis. This study shows that the combination of a simple fluorescent probe, C1-APB, with various CDs diversifies the response systems for saccharide recognition.
由荧光苯基硼酸（C1 - APB）和β - 环糊精（β - CD）组成的包合物作为一种超分子糖类传感器，其响应机制基于光致电子转移（PET）。本研究通过比较四种环糊精（α - CD、β - CD、γ - CD和NH₂ - β - CD）的pH谱，证实β - CD是C1 - APB的最佳主体，因为C1 - APB/β - CD复合物对糖类具有高亲和力，并且在结合糖类后荧光恢复程度高。对β - CD浓度效应的研究揭示了C1 - APB与β - CD形成了1:1的包合物。观察到的C1 - APB/β - CD复合物对糖类的选择性顺序如下：D - 果糖（4039 ± 69 M⁻¹）＞D - 核糖（1083 ± 26 M⁻¹）＞L - 阿拉伯糖（474 ± 11 M⁻¹）＞D - 半乳糖（318 ± 3 M⁻¹）＞麦芽三糖（135 ± 5 M⁻¹）＞D - 葡萄糖（114 ± 2 M⁻¹）＞麦芽糖（81 ± 2 M⁻¹）。除了单体发射外，在C1 - APB/γ - CD复合物的光谱中还观察到芘二聚体的二聚体发射，这使得能够进行比率分析。本研究表明，简单的荧光探针C1 - APB与各种环糊精的组合使糖类识别的响应系统多样化。
