title: Time-resolved spectral observations of cadmium-enriched cadmium sulfide nanoparticles and the effects of DNA oligomer binding.
abstract: We measured the steady-state and time-resolved fluorescence spectral properties of cadmium-enriched nanoparticles (CdS-Cd2+). These particles displayed two emission maxima, at 460 and 580 nm. The emission spectra were independent of excitation wavelength. Surprisingly, the intensity decays were strongly dependent on the observation wavelength, with longer decay times being observed at longer wavelengths. The mean lifetime increased from 150 to 370 ns as the emission wavelength was increased from 460 to 650 nm. The wavelength-dependent lifetimes were used to construct the time-resolved emission spectra, which showed a growth of the long-wavelength emission at longer times, and decay-associated spectra, which showed the longer wavelength emission associated with the longer decay time. These nanoparticles displayed anisotropy values as high as 0.35, depending on the excitation and emission wavelengths. Such high anisotropies are unexpected for presumably spherical nanoparticles. The anisotropy decayed with two correlation times near 5 and 370 ns, with the larger value probably due to overall rotational diffusion of the nanoparticles. Addition of a 32-base pair oligomer selectively quenched the 460-nm emission, with less quenching being observed at longer wavelengths. The time-resolved intensity decays were minimally affected by the DNA, suggesting a static quenching mechanism. The wavelength-selected quenching shown by the nanoparticles may make them useful for DNA analysis.
authors.affiliation: Department of Biochemistry and Molecular Biology, University of Maryland School of Medicine, Baltimore 21201, USA.
authors.forename: J R
authors.initials: JR
authors.lastname: Lakowicz
authors.forename: I
authors.initials: I
authors.lastname: Gryczynski
authors.forename: Z
authors.initials: Z
authors.lastname: Gryczynski
authors.forename: K
authors.initials: K
authors.lastname: Nowaczyk
authors.forename: C J
authors.initials: CJ
authors.lastname: Murphy
mesh_terms: D001704:Biopolymers / Q000737:chemistry; D002104:Cadmium / Q000737:chemistry*; D019187:Cadmium Compounds / Q000737:chemistry*; D004247:DNA / Q000737:chemistry*; D017931:DNA Primers; D008854:Microscopy, Electron; D010316:Particle Size; D013057:Spectrum Analysis / Q000379:methods*; D013440:Sulfides / Q000737:chemistry*; D013995:Time
chemical_list: D001704:Biopolymers; D019187:Cadmium Compounds; D017931:DNA Primers; D013440:Sulfides; D002104:Cadmium; C034939:cadmium sulfide; D004247:DNA