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The spectral
properties of fluorophores can be well described by
Maxwell's equations for an oscillating dipole radiating
energy into free space. From this perspective a
fluorophore is like an antenna which oscillates at high
frequency and radiates at UV to NIR wavelengths. In
standard fluorescence experiments the effects of
surfaces or particles are not usually seen because of
the small size of fluorophores relative to the sample
holder. However, in the near-field around the
fluorophore the nearby conducting metal surfaces can
respond to the oscillating dipole, and modify the
absorption, modify the rate of emission, and modify the
spatial distribution of the radiated energy. Nanofabrication of Plasmonic Structures Quasi-two-dimensional, collective
electron oscillations known as localized surface
plasmons (LSP) can be excited in metal nanoparticles
(typically gold or silver) along a dielectric surface
resulting in strong amplification of the local
electromagnetic field and appearance of surface plasmon
absorption bands. These enhanced fields are evanescent
i.e. they are confined to a distance of within 300 nm
from the particles and decay significantly beyond it.
State-of-the-art lithographic techniques provide tools
for tailoring the interaction of nanosize structures
with light; they provide precise control of size and
spacing for the fabrication of a wide variety of complex
shapes. These nanoparticles can be used to control,
transmit, scatter, amplify, radiate and modify
electromagnetic field of the incident light for
applications in subwavelength optics, data storage,
biophotonics, detection and sensing. Single Molecule Spectroscopy near Plasmonic Structures The use of fluorophore-metal
interactions has the potential to dramatically increase
the detectability ofsingle fluorophores for both SMD and
FCS experiments. Our ensemble measurements have shown
increased quantum yields, decreased lifetimes and
increased photostabilities. Decreased lifetimes will
result in higher emission rates prior to saturation.
This is possible because the fluorophores can cycle
faster between the ground and excited states. Decreased
lifetimes should result in higher photostability because
there is less time for chemical reactions to occur in
the excited state. Decreased lifetimes should also
result in decrease blinking because there will be less
time for the fluorophores to go to the triplet state.
These effects will provide longer observation times
prior to photobleaching. We will use these effects to
create the next generation of probes, which could be
fluorophores in nanoshells, fluorophores bound to
colloids, or fluorophores trapped in small volumes.
These effects may also be used for increased
detectability of single molecules bound to surfaces
which contain metallic structures, for either
biophysical studies or high sensitivity assays. Surface Plasmon-coupled Emission Surface plasmon-coupled emission (SPCE)
is a phenomenon which occurs with excited fluorophores
near continuous metallic surfaces covered with thin 50
nm metal films. These films are visually almost
completely opaque. Excited fluorophores within about 100
nm of the surface result in strongly directional
emission through the metal film and into the substrate.
A large fraction of the total light energy is coupled
into the substrate. This remarkable phenomenon is the
result of near-field interactions of the excited
fluorophores with thin metal film, and is not a
reflective or transmissive phenomenon. Calculations on Metallic Nanostructures An understanding of MEF, SPCE and PCF
will ultimately be based on an understanding of the
interactions of incident light with plasmonic structures
and the interactions of excited state fluorophores with
electron oscillations in these structures. A complete
emphasis on such calculations would be diversion from
our efforts on nanofabrication and experimentation. Most
of these experiments measured light extinction or
transmission, not fluorescence. Many of the recently
discovered properties of plasmonic structures are based
on experimentation rather than theory. Our goal is to
use commercially available software and selective
calculations to allow comparison of our experimental
results with electrodynamics theory for a more complete
understanding of the underlying phenomena. |
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National Center for Research Resources |
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