Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
9605546 | Journal of Photochemistry and Photobiology A: Chemistry | 2005 | 8 Pages |
Abstract
A hemicyanine dye, 4-[4-(dimethylamino)styryl]-1-methylpyridinium iodide (4-ASP) forms inclusion complexes with β-cyclodextrin (β-CD) and modified β-CDs having a sulfonaphthyl (β-CD-NS) or a pyrenyl group (β-CD-py) at the primary face. The complexation constants in water were determined by fluorescence titration and found to be 4.7 Ã 104 Mâ1 with β-CD-NS and 3.6 Ã 104 Mâ1 with β-CD-py, while it is 730 Mâ1 with β-CD. Compared to 4-ASP in water, the emission maximum of 4-ASP of the inclusion complexes is blue-shifted by about 20 nm, and emission intensity is higher by 6.4-fold for β-CD, 14-fold for β-CD-NS and as much as 56 fold for β-CD-py complexes. These are much greater than the 3 nm blue shift and 3.3-fold enhancement of emission intensity when the solvent medium is changed to CH3OH. Good overlap between the emission bands of β-CD-appended aromatic groups and absorption band of 4-ASP results in the excitation energy transfer from the excited aromatic groups to 4-ASP and the efficiency of the intra-complex transfer is near 100%. 1H NMR spectra and molecular modeling of the 4-ASP complexes with β-CD-NS and β-CD-py indicated that N-methyl-pyridinium moiety of 4-ASP is outside the primary face of β-CD cavity. The interaction between the N-methyl-pyridinium group and the appended aromatic groups appear to result in the high stability of the complexes. The high fluorescence intensity of 4-ASP in the complexes with β-CD-NS and β-CD-py was explained in terms of hindrance of the formation of the non-fluorescent twisted intramolecular charge transfer (TICT) states by the interaction and confinement in cavity.
Related Topics
Physical Sciences and Engineering
Chemical Engineering
Bioengineering
Authors
Joon Woo Park, Soo Yeon Lee, Soo Min Kim,