Fluorescence resonance energy transfer between the metal core and the ligand in Au 25 SG 18 (SG-glutathione thiolate) is demonstrated using dansyl chromophores attached to the cluster core through glutathione linkers. The dansyl chromophore functionalization of the cluster has been carried out by two different routes. Efficient energy transfer from the dansyl donor to the Au 25 core is manifested by way of the reduced lifetime of the excited state of the former and drastic quenching of its fluorescence. The donor-acceptor separation observed in the two synthetic routes reflects the asymmetry in the ligand binding on the cluster core, which is in agreement with the recent theoretical and experimental results on the structure of Au 25 .
In this paper, we report a detailed study of the fluorescence relaxation dynamics of a well-known fluorescent DNA intercalator, acridine orange (AO), in reverse micelles (RM), micelles, and DNA using picosecond resolved fluorescence spectroscopy. Solvation studies of AO in AOT reverse micelles (RM) containing water indicate the locations of AO close to the interface and those in RM containing NaOH; there are two types of AO--one in the nonpolar oil phase and the other at the interface. The bound water at the reverse micellar interface is found to be much more rigid than that at the micellar interface of sodium dodecyl sulfate (SDS) micelles. Dynamic light scattering (DLS) studies allow for the determination of the hydrodynamic radius and the overall tumbling motion of the macromolecules. Wobbling-in-cone data analysis of the temporal fluorescence anisotropy decay allows for determination of restriction on the motion of fluorophores attached to the macromolecules. This model further applied to AO-intercalated genomic DNA and synthetic oligonucleotides within their structural integrity (as confirmed through circular dichroism (CD) studies) shows that AO experiences less restriction in genomic salmon sperm DNA compared with that in synthetic oligonucleotides, and among the oligonucleotides, the ones with AT base pairs are much more rigid. This study would invoke further research on the dynamical nature of AO in restricted environments.
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