A ratiometric TICT-type dual fluorescent sensor for an amino acid.
A novel ratiometric fluorescent sensor 1 having the 4-(N,N-dimethylamino)benzoate (DMAB) group as a twisted intramolecular charge transfer (TICT) dual fluorescence site and the guanidinium group as a binding site for an amino acid at the 12- and 3-positions of cholic acid, respectively, was designed and synthesized. The sensor 1 showed characteristic dual fluorescence and it was shown that the guanidinium group in the proximity of the DMAB group influenced largely the TICT formation process in 1. Liquid/liquid extraction experiments demonstrated that the intensity ratio of the TICT fluorescence to the locally-excited (LE) fluorescence (I(TICT)/I(LE)) observed from the organic layer decreased with an increase in the concentration of N-acetyl-d-phenylalanine (AcPhe) in the water phase. Such fluorescence titration experiments afforded the apparent binding constant between 1 and AcPhe to be 7.0 x 10(5) M(-1). Temperature dependence of the fluorescence spectrum of 1 in the absence and presence of AcPhe indicated that the primary origin of the change in the I(TICT)/I(LE) value upon recognition of the amino acid was the increase in the activation energy of the TICT formation process in 1.
Ito
Akitaka
A
Department of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan.
Ishizaka
Shoji
S
Kitamura
Noboru
N
D010129:4-Aminobenzoic Acid / Q000138:chemical synthesis / Q000737:chemistry*; D000596:Amino Acids / Q000737:chemistry*; D005456:Fluorescent Dyes / Q000737:chemistry*; D007700:Kinetics; D009570:Nitriles / Q000737:chemistry; D013050:Spectrometry, Fluorescence; D062366:para-Aminobenzoates
C115085:4-(n,n-dimethylamino)benzonitrile; D000596:Amino Acids; D005456:Fluorescent Dyes; D009570:Nitriles; D062366:para-Aminobenzoates; D010129:4-Aminobenzoic Acid