Table Of ContentAdvances in Polymer Science 255
Martin Müller Editor
Polyelectrolyte
Complexes
in the Dispersed
and Solid State I
Principles and Theory
255
Advances in Polymer Science
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Martin Müller
Editor
Polyelectrolyte Complexes
in the Dispersed and
Solid State I
Principles and Theory
With contributions by
(cid:1) (cid:1) (cid:1)
A.G. Cherstvy M.A. Cohen Stuart C. Cramer
N.I. Lebovka (cid:1) S. Lindhoud (cid:1) A.H.E. Mu¨ller (cid:1)
D.V. Pergushov (cid:1) M. Scho¨nhoff (cid:1) R.G. Winkler (cid:1)
(cid:1)
A.A. Zezin A.B. Zezin
Editor
MartinMu¨ller
LeibnizInstituteofPolymerResearchDresden
DepartmentofPolyelectrolytesandDispersions
HoheStraße6
D-01069Dresden
Germany
ISSN0065-3195 ISSN1436-5030(electronic)
ISBN978-3-642-40733-8 ISBN978-3-642-40734-5(eBook)
DOI10.1007/978-3-642-40734-5
SpringerHeidelbergNewYorkDordrechtLondon
#Springer-VerlagBerlinHeidelberg2014
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Preface
Nearly one decade ago, a two volume edition “Polyelectrolytes with Defined
MolecularArchitecture”editedbyM.SchmidtappearedintheseriesAdvancesin
PolymerScienceandsummarizedprogressinthefieldatthatdate.Withinthetotal
of 11 chapters, one was dedicated to polyelectrolyte complexes, which addressed
interpolyelectrolyteandpolyelectrolyte/surfactantcomplexesaswellastheoretical
aspectsofpolyelectrolyte(PEL)complexation.
This new two-volume edition “Polyelectrolyte Complexes in the Dispersed and
Solid State: Principles and Applications” is intended to extend the content of
this former chapter by bringing together selected state-of-the-art contributions on
principlesandtheory(VolumeI)aswellasoncurrentapplicationaspects(VolumeII)
of polyelectrolyte complex (PEC)-based particles and soft matter. In Volume I,
progress and new knowledge on theoretical aspects of electrosorption phenomena
betweenPELandoppositelychargedsurfaces(A.G.CherstvyandR.G.Winkler)and
of the practically always apparent aggregation and clustering tendency of PEC
particles (N.I. Lebovka) are reviewed. Recently identified important dynamic
aspects of ion conductivity (C. Cramer and M. Scho¨nhoff) within PEC soft
matter and relaxation phenomena within PEL/protein PEC particles (S. Lindhoud
and M.A. Cohen-Stuart) as well as structural aspects of interpolyelectrolyte com-
plexes of novel synthetic polyionic species with nonlinear topology and polymer–
inorganic hybrids (D.V. Pergushov, A.A. Zezin, A.B. Zezin, A.H.E. Mu¨ller) are
reviewed.InVolumeII,prominentrecentapplicationsofPECparticlesarereviewed
togetherwithanoutlineofrelevantkeypropertiesconcerningcolloidalstability,size,
shape, compactness, surface, and biointeraction. The use and tailoring of PEC
particle-modifiedrelevantsurfacesforpapermaking(C.AnkerforsandL.Wagberg),
solid–liquid separation and water treatment (G. Petzold and S. Schwarz) are
addressed.ThelastthreecontributionsreviewPECapplicationsinthelifesciences,
including the role of PEL/protein complex assemblies in food (S. Bouhallab and
v
vi Preface
T.Croguennec),theuseofDNA/polycationcomplexesforgenedeliveryandprotec-
tion(A.Bertin),andthepotentialofsizableandshapablenanosizedPECparticlesin
pharmaceuticalapplicationssuchascontrolleddrugrelease(M.Mu¨ller).
Dresden,Germany MartinMu¨ller
Contents
StrongandWeakPolyelectrolyteAdsorptionontoOppositely
ChargedCurvedSurfaces ..................................................... 1
RolandG.WinklerandAndreyG.Cherstvy
AggregationofChargedColloidalParticles ................................ 57
NikolaiI.Lebovka
IonConductioninSolidPolyelectrolyteComplexMaterials .............. 97
CorneliaCramerandMonikaScho¨nhoff
RelaxationPhenomenaDuringPolyelectrolyteComplexFormation .... 139
SaskiaLindhoudandMartienA.CohenStuart
AdvancedFunctionalStructuresBasedonInterpolyelectrolyte
Complexes .................................................................... 173
DmitryV.Pergushov,AlexeyA.Zezin,AlexanderB.Zezin,
andAxelH.E.Mu¨ller
Index .......................................................................... 227
vii
AdvPolymSci(2014)255:1–56
DOI:10.1007/12_2012_183
#Springer-VerlagBerlinHeidelberg2013
Publishedonline:15March2013
Strong and Weak Polyelectrolyte Adsorption
onto Oppositely Charged Curved Surfaces
RolandG.WinklerandAndreyG.Cherstvy
Abstract Polyelectrolytesaremacromoleculescomposedofchargedmonomersand
exhibit unique properties due to the interplay of their flexibility and electrostatic
interactions.Insolution,theyareattractedtooppositelychargedsurfacesandinterfaces
andexhibitatransitiontoanadsorbedstatewhencertainconditionsaremetconcerning
thechargedensitiesofthepolymerandsurfaceandthepropertiesofthesolution.In
thisreview,wediscusstwolimitingcasesforadsorptionofflexiblepolyelectrolyteson
curved surfaces: weak and strong adsorption. In the first case, adsorption is strongly
influencedbytheentropicdegreesoffreedomofaflexiblepolyelectrolyte.Bycontrast,
in the strong adsorption limit, electrostatic interactions dominate, which leads to
particular adsorption patterns, specifically on spherical surfaces. We discuss the
correspondingtheoreticalapproaches,applyingamean-fielddescriptionforthepoly-
merandthepolymer–surfaceinteraction.Forweakadsorption,wediscussthecritical
adsorption behavior by exactly solvable models for planar and spherical geometries
and a generic approximation scheme, which is additionally applied to cylindrical
surfaces. For strong adsorption, we investigate various polyelectrolyte patterns on
cylinders and spheres and evaluate their stability. The results are discussed in the
lightofexperimentalresults,mostlyofDNAadsorptionexperiments.
Contents
1 Introduction.................................................................................... 2
2 WeakAdsorption:TheoreticalModel........................................................ 6
2.1 EquationfortheGreenFunction........................................................ 7
2.2 DensityDistributionFunction........................................................... 8
R.G.Winkler(*)
TheoreticalSoftMatterandBiophysics,InstituteforAdvancedSimulation,
ForschungszentrumJu¨lich,52425Ju¨lich,Germany
e-mail:[email protected]
A.G.Cherstvy(*)
InstituteforPhysicsandAstronomy,UniversityofPotsdam,14476Potsdam,Germany
e-mail:[email protected]
2 R.G.WinklerandA.G.Cherstvy
3 WeakAdsorption:ExactlySolvableModels................................................ 8
3.1 PlanarSurface.......................................................................... 8
3.2 SphericalSurface....................................................................... 10
4 WeakAdsorption:WKBApproximation.................................................... 21
4.1 WKBApproximationScheme......................................................... 21
4.2 PlanarSurface.......................................................................... 22
4.3 CylindricalSurface..................................................................... 23
4.4 SphericalSurface....................................................................... 25
4.5 ConformationalPropertiesofAdsorbedPolyelectrolytes............................ 26
5 WeakAdsorption:Discussion............................................................... 27
5.1 ComparingGeometries................................................................. 27
5.2 ComparisonBetweenTheoryandExperiment........................................ 28
6 StrongAdsorption:TheoreticalModel...................................................... 30
6.1 AdsorptionataCylindricalSurface................................................... 31
6.2 AdsorptionataSphericalSurface..................................................... 40
7 LimitationsandFurtherStudies............................................................. 47
8 Conclusions................................................................................... 50
References........................................................................................ 52
1 Introduction
Adsorption of charged macromolecules, and polyelectrolytes in particular, onto
charged surfaces is of paramount importance in a wide range of technological
applications [1, 2], such as surface coating [3], colloid stabilization [4], and paper
making[5–7]andforavarietyofbiologicalsystems[8–12].Becauseoftheircharges,
mostchargedpolymersarewater-soluble,whichmakestheminterestingcandidates
for water-based, environmentally friendly technology. This aspect is even more
important for a number ofbiologicalsystems.Here, examplesinclude wrappingof
double-stranded DNA in nucleosomes [13–20], adsorption of single-stranded RNA
ontotheinteriorofviralcapsides[21–29],andpolyelectrolytemultilayeredvesicles
[30,31].Correspondingly,polyelectrolyteadsorptionhasreceivedsubstantialatten-
tion for many decades. There are several valuable books and review articles on
the subject [8, 9, 32–34]. However, electrostatically driven polymer adsorption
shows a broad range of facets, not all of which have been addressed adequately in
theliterature.
A fundamental step in polyelectrolyte adsorption is the transition from a free
state in solution to a bound polymer on an interface. Figure 1 illustrates such a
transition for the adsorption of a polyelectrolyte onto spherical colloidal particles
[35]. In the unbound state, the polymer chain explores the entropic degrees of
freedom, whereas in the bound state the attractive polymer–surface electrostatic
interactions dominate [8, 33, 36–39]. These two antagonistic trends dictate the
propertiesofadsorption.Theoreticalstudiesoftheadsorptionbehaviorofpolyelec-
trolytes onto planar and curved surfaces suggest a phase-transition-like behavior,
i.e., a bound polymer state appears at certain critical conditions, which depend
upon, e.g., the temperature, the charge density and curvature of the surface, the
polyelectrolyte linear charge density and its mechanical persistence [40–44]. An
importantaspectofthisreviewistodiscussrecentadvancesonthisissue.
