Development of Fluorescent Reagents for Chirality Recognition Based on π-Electron Interaction

寡肽链末端含芘基团的试剂的研制以氨基酸[1]作为分子识别的目标客体。进行了如下分子设计：将L-苯丙氨酸或相关分子通过酰胺键引入到1，4-丁二胺上。在此化合物中，还引入了萘或芘部分。该试剂与客体分子通过氢键作用形成复合物，复合物形成时荧光发生变化，而与L-或D-苯丙氨酸酯形成复合物时荧光变化不大，另一方面，该试剂对L-或D-苯丙氨酸酯具有手性识别.环糊精基础试剂的研制选用环糊精作为分子识别基团，通过多个碳原子的亚甲基链在环糊精上引入萘基，该化合物（试剂）的荧光强度随水溶液pH值的变化而变化，该试剂在与客体分子如（-）β-氨基丁酸或1-金刚烷醇形成络合物时也显示荧光变化。客体分子诱导该试剂的圆二色性表明了其对手性识别的有效性。

Development of the reagent with pyrene moieties in the terminal of oligopeptide chain Amino acid[ was selected as a target guest of molecular recognition. A molecular design was carried out as follows: L-Phenylalanine or related molecules were introduced on 1,4-diaminobutane by amide bond. To this compound, naphthalene or pyrene moieties were also introduced. This reagent was expected to form a complex with guest molecule by the hydrogen bonds, and to show a fluorescence change was observed at the complex formation.However, a little fluorescence change was observed at the complex formation with L- or D- phenylalanine esters.On the other hand, the ^1H NMR spectra showed the chirality recognition for L- or D- phenylalanine esters.2. Development of cyclodextrin base reagentsCyclodextrin was selected as a molecular recognizing moiety, and naphthalene group was introduced on the cyclodextrin via methylene chain with several carbon atoms.This compound (reagent) exhibits a change of fluorescence intensity depending on pH off the aqueous solution, and can be used for a pH sensor.This reagent also shows a fluorescence change at the complex formation with guest molecules such as (-)borneol or 1-adamentanol. Induced circular Dichroism of this reagent by the guest molecules shows the usefulness for the chirality recognition.