Dynamic Light Scattering (DLS) and Static Light Scattering (SLS) are well-established ensemble techniques for characterizing colloids and macromolecules, providing insights into their size, molecular weight, and interactions. Beyond traditional applications, these methods also offer the potential to probe anisotropy which can be a critical parameter of today¡¯s increasingly complex functional materials.
This presentation explores the principles and practical considerations of anisotropic particle characterization using modern goniometer-based DLS and SLS instrumentation. Several relevant applications to soft matter systems will be shared to highlight capabilities, advantages and limitations of the techniques.
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Shape Characterization Using Dynamic & Static Light Scattering
2. In SLS/DLS, a laser beam is sent through a colloidal sample, the average scattered intensity and the
auto/cross correlation of the resulting scattered light are computed.
Why choose DLS as a characterization method?
? Fast
? Simple measurements with easy sample preparation
? In-situ, non-destructive approach
Measuring particle size reliably
2
Static and Dynamic Light Scattering (SLS/DLS)
?
3. 3
SLS
The measured intensity can be divided up into
contributions from within particles (intraparticle) and
between particles (interparticle):
I(q) ¡Ö c ? Mw ? V? ? P(q) ? S(q)
The Radius of Gyration can be
determined from the so-called Guinier
Plot:
Slope =
Ln (I)
Guinier regime
??
7. 7
Depolarized Static and Dynamic Light Scattering (D-SLS/D-DLS)
? In D-SLS /D-DLS we add a polarizer at detection before the detector
? Depending on the orientation of the polarizer, vertical or horizontal we can
measure in two different configurations, VV and VH
? In D-SLS /D-DLS gives access to advanced shape and size information
8. Decorrelation for Anisotropic Particles
8
Diffusion
Translational
Diffusion
??
Rotational
Diffusion
??
For anisotropic particles, the diffusion mechanism
is more complex as it involves translations and
rotations
9. D-DLS in VV Configuration
9
Intensity
fluctuation
s
???
t
<I
>
Intensity
correlation function
(t)-1
¦Ó
Correlato
r
?? , ??
R. Nixon-Luke, G. Bryant, Part. Part. Syst. Charact. 2019, 36, 1800388.
10. D-DLS in VV Configuration: The Tobacco Mosaic Virus
10
For small scattering angles, :
??
??
?1? ??0 (? ) exp(? ?? ?2
? )
log
??
??
?1
?
? ?? ?? ?
2
?
log
?
?
??
?1
?
?
For small scattering angles, the logarithmic plot of
the correlation function is linear and yields the
translational diffusion coefficient,
? ?? ?2
Wada A. et al., J. Chem. Phys. 55, 1798 (1971)
Tobacco Virus
11. D-DLS in VV Configuration: The Tobacco Mosaic Virus
11
log
?
?
??
?1
?
?
For large :
??
??
?1 ? ?2 exp (?( ?? ?
2
+6 ? ?)? )
log
??
??
?1
?
? ? ?(?? ?
2
+6 ? ?)?
?(?? ?
2
+6 ??)
For large the logarithmic plot of the correlation
function is linear and yields the rotational diffusion
coefficient,
Wada A. et al., J. Chem. Phys. 55, 1798 (1971)
12. Shape and Size from Diffusion Coefficients
For an axisymmetric particle of major size, , minor size, ,
and anisotropy factor
?? , ??
Microhydrodynami
cs
?,?,?
For rodlike particles, such as Tobacco Mosaic Virus:
? ?=
1
3
?? (ln ? ? ?)
? ?0 ?
3
?? =
1
3
?? (ln ? ?? )
? ?0 ?
?? =0.312+
0.565
?
+
0.100
?
?
??=?0.662+
0.917
?
?
0.050
?
?
Ortega A.; Garc a
?? de la Torre J., J. Chem. Phys. 119, 9914¨C9919 (2003)
Shape and Size
?
?
13. Takeaways
? In VV Configuration at low angles DLS provides access to the
translational diffusion of anisotropic particles
? At large angles and large lag times, knowing the
translational diffusion coefficient, we can obtain the
rotational diffusion coefficient
? From translational and rotational diffusion coefficients we
can obtain size and shape parameters of anisotropic
particles
? The procedure is complicated by the fact that in general
correlation functions display an angle-dependent double
decay
14. D-DLS in VH Configuration
14
Intensity
fluctuation
s
?? ?
t
<I
>
Intensity
correlation function
(t)-1
¦Ó
Correlato
r
?? , ??
?2
? ?
=1+ ? exp (?2 (?? ?
2
+ 6 ?? )?)
Simpler single exponential
decay
R. Nixon-Luke, G. Bryant, Part. Part. Syst. Charact. 2019, 36, 1800388.
Decay Rate
15. D-DLS in VH Configuration
15
? ¡Ô ?2
?? +6 ? ?
? In VH configuration we obtain a simpler
single exponential decay
? Plotting the decay rate vs we obtain the
translational diffusion coefficient from
the slope and the rotational diffusion
coefficient from the intercept of the
linear plot
? The procedure is simpler than in the VV
configuration case
Decay Rate:
? ??
??
??
?
16. D-DLS in VH Configuration: Magnetic Nanoparticles with Tunable
Shape Anisotropy
16
? Anisotropic Magnetic NPs
characterized by TEM and D-
DLS
? The two techniques agree thus
confirming the validity of D-
DLS
Martchenko I. et al., J. Chem. Phys. B 115(49), 14838-14845 (2011)