The angular dependence of dynamic light scattering from five
degraded potato starch samples
was studied. The study allowed the determination of internal modes
of motion in branched structures
that resemble hyperbranched polymers. The properties of the
investigated starches are dominated by
the large size of the amylopectin. Measurements were made at
infinite dilution (c = 0) and at
concentrations c > c* where c* is the overlap
concentration. The time correlation function (TCF) at
low
concentration was analyzed by its first cumulant at low values of
qR
g and in the asymptotic region of
qR
g
> 2. The first cumulant Γ describes the initial decay of the
TCF, g
1
(q,t). A double
logarithmic plot of
Γ/q
2 ≡
D
app
(q) against
qR
g gave a curve that lies between those for
hard spheres and flexible coils. In
contrast to linear chains, it showed an asymptotic slope of 0.80−0.85
instead of the theoretically expected
slope of 1.00. The reduced first cumulant Γ*(q)
≡
(Γ/q
3
)(η0/kT)
did not approach a constant plateau at
large q but decayed continuously below the experimentally
observed plateau value for linear chains. The
reason for this behavior is seen in the high branching density and a
loss of internal flexibility. In a
second part, the angular dependence of the first cumulant in the
semidilute regime, up to c/c* = 5,
was
measured. The data from the different concentrations could be
condensed to one common master curve
when an empirical scaling parameter
was used. A plot of the TCF's from the various
concentrations as a function of Γ(q,c,)t resulted in
q-independent shape functions
g
1
(Γt), which gradually
changed
from Zimm to Rouse behavior when the concentration was increased beyond
the overlap concentration
c*. This change is interpreted as a result of
hydrodynamic screening.