Intramolecular charge transfer and electron transfer in N-(1-naphthyl) aminoacetic acid in aqueous solution

摘要

pH titration of the fluorescence of N-(1-naphthyl)aminoacetic acid(NAA) was performed in aqueous solution over pH range of 1.5-12.5. Despite no shift in the fluorescence maximum wavelength, the titration curve showed an Omega -shaped profile with increasing pH with two inflection points at pH 4.1 and pH 11.5, respectively. These values correspond to the excited-state pK(a)*'s of carboxylic group and ammonium cation, respectively, which are both higher than those of the corresponding ground-state PKa' s of 2.64 and 11.83, of which the former changes more. The substantial weakening of the proton dissociation of carboxylic group in the excited state should be indicative of the decrease in the inductive + I-effect of the ammonium cation at the beta -position due to the excited-state intramolecular charge transfer from naphthalene moiety to ammonium. The latter was also confirmed by the slight increase in the exited-state pK(a2)*. The fact that the increase in pK(s1)* is larger than that in pK(a2)* suggests that the effect of the intramolecular charge transfer on the involved moiety be weaker than that on a remote moiety in the same species. This could be taken into consideration for designing means of tuning the structures and properties of peptide and protein via photo-excitation, It was identified that the NAA zwitterion( Il) was the emissive species. The fluorescence quenching at high pH was assumed to be due to the photo-induced intramolecular electron transfer between carboxylate anion and the excited naphthalene moiety. The present cask represents an example in which both intramolecular charge transfer and electron transfer occur to shape the pH titration profile.