an0c01544_si_001.pdf (13.92 MB)
Download fileImpact of Incoherent Coupling within Localized Surface Plasmon Resonance on Singlet Oxygen Production in Rose Bengal-Modified Silica-Coated Silver Nanoshells (SiO2@Ag@SiO2‑RB)
journal contribution
posted on 29.07.2020, 20:30 by Vladimir Kabanov, Belinda HeyneThe use of metal-containing
nanoparticles capable of localized
surface plasmon resonance (LSPR)-enhanced singlet oxygen (1O2) production, via photosensitization,
are currently promising candidates for cytotoxic medical purposes.
Despite the ongoing advances in fabricating plasmonic nanomaterials,
much of the insight into the fundamental mechanisms governing the
photosensitizer (PS)–plasmon interactions remain unexplored.
Silver nanoshells (SiO2@Ag) possess seemingly promising
optical properties to investigate the underlying LSPR effects on photosensitization,
while also raising questions about the nature of LSPR generation in
such dielectric-core metallic-shell nanostructures. In the present
study, we synthesize and use silica-coated hybrid SiO2@Ag
nanoparticles with an outer surface-conjugated PS, and Ag shell densities
ranging from ∼50 to >90%, to experimentally investigate
these
nanostructures’ LSPR-enhanced 1O2 generation
properties. Using both direct and indirect 1O2 detection approaches, and with rigorous consideration of 1O2 kinetics, we show that the SiO2@Ag-based
structures produce severe inner filter effects in bulk-solution measurements,
making them impractical for photodynamic applications. Furthermore,
we make a case for the SiO2@Ag nanoparticles’ poor
LSPR generation efficiency to be the consequence of the species’
incoherently coupled plasmonic field and resultant lack of enhancement
of the nearby chromophore’s photophysical properties.