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Pellegrino Nanoletters 2004
Pellegrino Nanoletters 2004
LETTERS
2004
Vol. 4, No. 4
703-707
ABSTRACT
A general strategy is described which allows for transferring hydrophobically capped nanocrystals from organic to aqueous solution by
wrapping an amphiphilic polymer around the particles. In particular, high quality CoPt3, Au, CdSe/ZnS, and Fe2O3 nanocrystals have been
water-solubilized in this way. Analysis with transmission electron microscopy, gel electrophoresis, and fluorescence correlation spectroscopy
demonstrates that monodispersity of the particles is conserved upon phase transfer to aqueous solution.
Scheme 1.
Scheme of the polymer coating procedure. Several reports (e.g. ref 35) suggest that the surfactant chains for hydrophobically capped
nanocrystals are pointing away from the nanocrystal surface, in a brush-like arrangement. The following plausible configuration is then
assumed for the polymer coating process: The hydrophobic alkyl chains of the polymer intercalate with the surfactant coating. The anhydride
rings are located on the surface of the polymer-coated nanocrystal. The amino end groups of the cross-linker molecule open the rings and
link the individual polymer chains. The surface of the polymer shell becomes negatively charged, stabilizing the particles in water by
electrostatic repulsion. A structural analysis aimed at determining the detailed conformation of the cross-linked polymer shell is in progress.
Figure 1. TEM images of polymer-coated nanocrystals of four different core materials: Fe2O3 (9.2 nm average diameter), Au (4.0 nm),
CoPt3 (8.0 nm), and CdSe/ZnS (7.0 nm) nanocrystals.
precipitation occurred and the bands during gel electrophoresis kept their narrow shape).
Results and Discussions. In water the nanocrystals
retained their major physical properties (such as the fluorescence of CdSe/ZnS and the magnetic moment of CoPt3).
TEM analysis (Figure 1) showed no large aggregates of
particles, besides the formation of monolayers. Such patterns
are due to particle-particle interactions (van der Waals,
magnetic) and are also observed on grids prepared from
solutions of hydrophobic nanocrystals. However, the presence
of small aggregates, such as dimers and trimers, cannot be
distinguished from such monolayers and so it cannot be
excluded.
The polymer-coated nanocrystals were investigated with
agarose gel electrophoresis28 (Figure 2). The bands on the
gels are remarkably narrow, and since the particle mobility
on gels depends on both charge and size, we estimated that
our polymer-coated particles have a rather homogeneous
Nano Lett., Vol. 4, No. 4, 2004
Figure 2. Gel electrophoresis of polymer-coated nanocrystals corresponding to the samples of Figure 1. The bands were observed either
by their fluorescence (CdSe/ZnS) or by their absorption color. For each sample the left lane (lanes 1, 3, 5, 7) corresponds to particles as
obtained after the last column purification step. The right lanes (lanes 2, 4, 6, 8) correspond to an additional purification step where the
fastest migrating band of nanocrystals in a first gel run has been extracted.
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