Polymer molecules
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Some of the most prominent examples of the synthesis of 3D molecules
with a well-defined shape are spherical dendrimers, arborescent-graft
polymers, monodendron-jacketed linear chains, and cylindrical brushes
(Fig.1.). The shape of these molecules is controlled by the steric
repulsion of its branches and by the branching symmetry.
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| Height image of single star-like macromolecules
on mica. Scan size 300 nm. |
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The dense grafting of these molecules gives them a well-defined
shape. With a well-chosen monomer unit, the molecules can undergo
conformational changes with changes in their environment. This functional
behavior could be used to design stimuli-responsive objects that
could work as tiny springs or even motors.
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| (a) Height image obtained using regular
GP probe in tapping mode. Click to enlarge. |
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(b) Phase image reveals the molecules
in better contrast. Click to enlarge. |
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| Fig. 2. Height (left) and phase (right)
images of single macromolecules of polymer with minidendritic groups
obtained in the tapping mode.Scan size is 320 nm. Image courtesy of
S. Magonov. |
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Molecular visualization provides a unique opportunity for the
characterization of polymers. First, it gives direct evidence of
their architecture. Second, it allows for accurate measurements
of the number average molecular weight when combined with an appropriate
sample preparation technique. Third, it enables size measurements
of the individual branches separately from the size of the whole
molecule.
For example, you can see images of single polymer molecules with
minidendritic groups in Fig. 2. Due to the minidendritic groups,
the molecules become thicker (about 7 nm in diameter) so that they
can be visualized using regular GP probes (click image to enlarge).
Single polymer molecules above Tg are delicate samples that require
very gentle imaging conditions in tapping mode due to small size
and weak adhesion to the substrate. General shape and average dimensions
of the particles can be acquired using General Purpose tips with
curvature radius of 10 nm. Imaging of soft delicate samples requires
soft cantilevers.
When fine features need to be resolved, one should use Hi'RES probes
on the same cantilevers for the further reduction of tip-sample
interaction forces and geometrical dilation effects. When using
Hi'RES, "light tapping" conditions are preferable, which
implies low resonance amplitude (start at 0.2V up to 1.2V) and a
set point ratio about 0.9 to 1. Scan rate should start at below
1 Hz. Scan size should start out at 50 nm (250 nm maximum). See
high-resolution imaging page for details.
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