|Budget Amount *help
¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 2005: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2004: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2003: ¥2,000,000 (Direct Cost: ¥2,000,000)
1.Porphyrin, pyrromethene-dye, and other functional compounds with highly-conjugated systems were prepared from 2-acenaphtho[1,2-c]pyrrole which showed strong stacking ability. The UV spectrum of the resulting porphyrin exhibits large red shifts with the Soret-band (556 nm), besides the unexpected strong absorption of Q-band. Octa-carboxylbenzoporphyrin was also prepare using retro Diels-Alder reaction. The stacking ability of this porphyrin varies depending on the pH.
2.Four tripeptides (Z-AA_1-2Dpy-AA_3-OMe ; AA_1, AA_3 = Gly, Aib) containing a novel amino acid, α,α-di(2-pyridyl)glycine (2Dpy), were synthesized by the modified Ugi reaction. NMR analysis clearly indicated that the 2Dpy-containing tripeptides except the peptide in which AA_1, AA_3 = Aib, adopt a unique conformation with two intramolecular hydrogen bonds between 2Dpy-NH and a pyridine nitrogen and between AA_3-NH and another pyridine nitrogen. This conformation has so far not been reported. On the other hand, the peptide Z-Aib-2Dpy-Aib-OMe probably adopts a β-turn structure which is stabilized by two intramolecular hydrogen bonds between 2Dpy-NH and a pyridine nitrogen and between AA_3-NH and the C=O of the Z group.
3.The novel ferrocene-based ditopic receptor was synthesized. This receptor bears two oligoethylene glycol arms with pendant 2,2'-bipyridine unit at the identical cyclopentadienyl rings, Cu(I) cation binds to the receptor to form 1:1 complex with the cavity consisting of polyether, and the resulting complex acts as a receptor for amino acid ester salts to give the ditopic complex. The ^1H NMR spectrum of the ditopic complex exhibits strong broadening at the bipyridine region, and the ESR spectrum of the same sample gives the signals assigned as Cu(II) species. With these data, the binding of Cu(I) complex towards AAOMe-HCl leads to the conformational change, and the Cu(I) complex is simultaneously oxidized to Cu(II) complex.