Ceria
nanocrystals (nanoceria) are well known for their excellent
antioxidant activity providing effective scavenging of reactive oxygen
species (ROS) both in water solutions and biological systems. The
mechanism and dynamics of nanoceria action are determined by the features
of its defect structure. Our experimental results confirm that Ce3+–Vo–Ce3+ surface defect
complexes on the surface of nanoceria acting similar to active sites
in enzyme molecules actually provide nanoceria with enzyme-like activity.
In accordance with this supposition, the processes of hydrogen peroxide
(HP) decomposition by nanoceria can be well described using the Michaelis–Menten
equations usually used in the description of enzyme–substrate
interaction. The maximum rate of HP decomposition shows a clear dependence
on the size of nanoparticles, i.e., on the number of available surface
sites for binding of HP molecules. At HP concentrations, for which
almost all Ce3+–Vo–Ce3+ sites are involved in HP decomposition, the process of slow Ce3+ → Ce4+ oxidation turns into fast redox
cycling and Ce3+/Ce4+ oscillations are observed.
This effect can be explained by the combined action of fast synchronous
Ce3+/Ce4+ and pH change in nanoceria water solutions,
as well as by HP ability to act both as oxidative and reductive agents.
ROS decomposition by nanoceria in the oscillatory regime is a rather
unexpected effect that can provide deeper understanding of the redox
mechanisms of nanoceria action as a whole.
The
aggregation behavior of 1-methyl-1′-octadecyl-2,2′-cyanine
perchlorate (amphi-PIC) and 3,3′-dimethyl-9-(2-thienyl)-thiacarbocyanine
iodide (L-21) dyes in binary dimethylformamide (dimethylsulfoxide)/water
(1:9) solution containing CeO2 nanoparticles (NPs) has
been studied by optical absorption and fluorescent spectroscopy, as
well as dynamic light-scattering method. Formation of stable hybrid
complexes between NPs and dye J-aggregates due to Coulombic and stacking
interactions has been revealed. The arrangement of dye molecules in
aggregates (slipping angle θ, twisting angle α, the center-to-center
distance R, and the exciton splitting energy ΔE) was analyzed within the Kasha exciton model based on
oblique transition dipoles orientation. For amphi-PIC, formation of
twisted face-to-face and oblique head-to-tail J-aggregates has been
revealed depending on CeO2 NPs concentration, whereas L-21
dye forms aggregates of a twisted face-to-face fashion independently
on NPs concentration.
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