The authors report dynamic and coagulation properties of a dispersion of polyelectrolyte multilayer microcapsules filled with solutions of a strong polyelectrolyte. Microcapsules are shown to take a charge of the sign of encapsulated polyions and are characterized by a nonuniform distribution of inner polyions, which indicates a semipermeability of the shell and a leakage of counterions. The capsule self-diffusion coefficient in the vicinity of the similarly charged wall is measured using a particle tracking procedure from confocal images of the dispersion. The diffusion of capsules in the force field suggests that the effective interaction potential contains an electrostatic barrier, so that we deal with the same types of interaction forces as for solid particles. The theoretical estimates of the authors show that when microcapsules are in close proximity, their interaction should even be quantitatively the same as that of colloids with the same surface potential. However, due to the mobility of inner polyions they might repel stronger at large distances. The authors thus conclude that the encapsulation of charged polymers is an important factor in determining the adhesion and interaction properties of multilayer microcapsules.

1.
E.
Donath
,
G. B.
Sukhorukov
,
F.
Caruso
,
S. A.
Davis
, and
H.
Möhwald
,
Angew. Chem., Int. Ed.
42
,
2202
(
1998
).
2.
F.
Caruso
,
R. A.
Caruso
, and
H.
Möhwald
,
Science
282
,
1111
(
1998
).
3.
I. L.
Radtchenko
,
G. B.
Sukhorukov
,
S.
Leporatti
,
G. B.
Khomutov
,
E.
Donath
, and
H.
Möhwald
,
J. Colloid Interface Sci.
230
,
272
(
2000
).
4.
G. B.
Sukhorukov
,
A. A.
Antipov
,
A.
Voigt
,
E.
Donath
, and
H.
Möhwald
,
Macromol. Rapid Commun.
22
,
44
(
2001
).
5.
L.
Dähne
,
S.
Leporatti
,
E.
Donath
, and
H.
Möhwald
,
J. Am. Chem. Soc.
123
,
5431
(
2001
).
6.
V. V.
Lulevich
,
I. L.
Radtchenko
,
G. B.
Sukhorukov
, and
O. I.
Vinogradova
,
J. Phys. Chem. B
107
,
2735
(
2003
).
7.
O. I.
Vinogradova
,
D.
Andrienko
,
V. V.
Lulevich
,
S.
Nordschild
, and
G. B.
Sukhorukov
,
Macromolecules
37
,
1113
(
2004
).
8.
G. B.
Sukhorukov
,
D. G.
Shchukin
,
W. F.
Dong
,
H.
Möhwald
,
V. V.
Lulevich
, and
O. I.
Vinogradova
,
Macromol. Chem. Phys.
205
,
530
(
2004
).
9.
B. S.
Kim
and
O. I.
Vinogradova
,
J. Phys. Chem. B
108
,
8161
(
2004
).
10.
O. V.
Lebedeva
,
B. S.
Kim
, and
O. I.
Vinogradova
,
Langmuir
20
,
10685
(
2004
).
11.
B. S.
Kim
,
T. H.
Fan
,
O. V.
Lebedeva
, and
O. I.
Vinogradova
,
Macromolecules
38
,
8066
(
2005
).
12.
C.
Gao
,
E.
Donath
,
S.
Moya
,
V.
Dudnik
, and
H.
Möhwald
,
Eur. Phys. J. E
5
,
21
(
2001
).
13.
V. V.
Lulevich
,
I. L.
Radtchenko
,
G. B.
Sukhorukov
, and
O. I.
Vinogradova
,
Macromolecules
36
,
2832
(
2003
).
14.
N.
Elsner
,
F.
Dubreuil
, and
A.
Fery
,
Phys. Rev. E
69
,
031802
(
2004
).
15.
O. I.
Vinogradova
,
O. V.
Lebedeva
, and
B. S.
Kim
,
Annu. Rev. Mater. Res.
36
,
143
(
2006
).
16.
O. I.
Vinogradova
,
J. Phys.: Condens. Matter
16
,
R1105
(
2004
).
17.
D. G.
Shchukin
,
G. B.
Sukhorukov
, and
H.
Möhwald
,
Angew. Chem.
42
,
4472
(
2003
).
18.
B. S.
Kim
,
O. V.
Lebedeva
,
D. H.
Kim
,
A. M.
Caminade
,
J. P.
Majoral
,
W.
Knoll
, and
O. I.
Vinogradova
,
Langmuir
21
,
7200
(
2005
).
19.
O. I.
Vinogradova
,
O. V.
Lebedeva
,
K.
Vasilev
,
H.
Gong
,
J.
Garcia-Turiel
, and
B. S.
Kim
,
Biomacromolecules
6
,
1495
(
2005
).
20.
B. S.
Kim
,
O. V.
Lebedeva
,
K.
Koynov
,
H.
Gong
,
A. M.
Caminade
,
J. P.
Majoral
, and
O. I.
Vinogradova
,
Macromolecules
39
,
5479
(
2006
).
21.
J. N.
Israelachvili
and
G. E.
Adams
,
J. Chem. Soc., Faraday Trans. 1
74
,
975
(
1978
).
22.
J. N.
Connor
and
R. G.
Horn
,
Langmuir
17
,
7194
(
2001
).
23.
W. A.
Ducker
,
T. J.
Senden
, and
R. M.
Pashley
,
Nature (London)
353
,
239
(
1991
).
24.
M.
Brunner
,
J.
Dobnikar
,
H. H.
von Grunberg
, and
C.
Bechinger
,
Phys. Rev. Lett.
92
,
078301
(
2004
).
25.
D. C.
Prieve
and
N. A.
Frej
,
Langmuir
6
,
396
(
1990
).
26.
G. M.
Kepler
and
S.
Fraden
,
Phys. Rev. Lett.
73
,
356
(
1994
).
27.
S. H.
Behrens
and
D.
Grier
,
Phys. Rev. E
64
,
050401
(
2001
).
28.
M.
Brunner
,
C.
Bechinger
,
W.
Strepp
,
V.
Lobaskin
, and
H. H.
von Grünberg
,
Europhys. Lett.
58
,
926
(
2002
).
29.
V.
Lobaskin
,
M.
Brunner
,
C.
Bechinger
, and
H. H.
von Grünberg
,
J. Phys.: Condens. Matter
15
,
6693
(
2003
).
30.
G. B.
Sukhorukov
,
E.
Donath
,
H.
Lichtenfeld
,
E.
Knippel
,
M.
Knippel
,
A.
Budde
, and
H.
Möhwald
,
Colloids Surf., A
137
,
253
(
1998
).
31.
W. F.
Dong
,
J. K.
Ferri
,
T.
Adalsteinsson
,
M.
Schönhoff
,
G. B.
Sukhorukov
, and
H.
Möhwald
,
Chem. Mater.
17
,
2603
(
2005
).
32.

Note that there have been several recent attempts to assemble multilayers on other templates (for a recent review, see Ref. 15). This might lead to some minor changes in properties of capsules (due to a different adsorption of shell-forming polyelectrolytes and a different treatment of the shell during the core dissolution) as compared with that obtained with the method (Refs. 30 and 31) we are using here.

33.
J. C.
Crocker
and
D. G.
Grier
,
J. Colloid Interface Sci.
179
,
298
(
1996
).
34.
D. V.
Volodkin
,
A. I.
Petrov
,
M.
Prevot
, and
G. B.
Sukhorukov
,
Langmuir
20
,
3398
(
2004
).
35.
D. G.
Shchukin
,
G. B.
Sukhorukov
, and
H.
Möhwald
,
J. Phys. Chem. B
108
,
19109
(
2004
).
36.
37.
A. J.
Goldman
,
R. G.
Cox
, and
H.
Brenner
,
Chem. Eng. Sci.
22
,
637
(
1967
).
38.
B. S.
Kim
,
O. V.
Lebedeva
,
K.
Koynov
,
H.
Gong
,
G.
Glasser
,
I.
Lieberwith
, and
O. I.
Vinogradova
,
Macromolecules
38
,
5214
(
2005
).
39.
V. V.
Lulevich
,
S.
Nordschild
, and
O. I.
Vinogradova
,
Macromolecules
37
,
7736
(
2004
).
40.
C. Y.
Gao
,
S.
Moya
,
H.
Lichtenfeld
,
A.
Casoli
,
H.
Fiedler
,
E.
Donath
, and
H.
Mohwald
,
Macromol. Mater. Eng.
286
,
355
(
2001
).
41.

Beside that varying the concentration of salt could induce structure changes of the shell (Ref. 56), its permeability for high Mw polymers (Ref. 57) affect the multilayer stability (Refs. 58 and 59) and morphology (Ref. 60) and change the size of the capsules (Ref. 56), the state of the inner polyelectrolyte (Ref. 61), and other, still poorly understood phenomena, absent for solid particles.

42.
B. V.
Derjaguin
and
L. D.
Landau
,
Acta Phys.-Chim.
14
,
633
(
1941
).
43.

Moreover, this structure of the potential can be inferred from an analysis of capsule distributions in the focal plane. The radial distribution function has a main maximum at a distance of 8μm, for the 1day old sample, which is reduced to about 6μm, for the 4day sample. The distant peak clearly indicates the presence of a long-range repulsion. The effective pair potential obtained by the inversion of pair correlation function, with an inverse Monte Carlo procedure (Ref. 62) decays exponentially at large distances with a characteristic length of 300nm, which can only be associated with the Debye length in water (Ref. 54). The peak at shorter distance reflects the particle aggregation due to the short-range attraction. However, as we mentioned in the Introduction, it is hardly possible to quantify short-range forces in the capsule system with this approach.

44.
V.
Bosio
,
F.
Dubreuil
,
G.
Bogdanovic
, and
A.
Fery
,
Colloids Surf., A
243
,
147
(
2004
).
45.
H.
Gong
,
J.
Garcia-Turiel
,
K.
Vasilev
, and
O. I.
Vinogradova
,
Langmuir
21
,
7545
(
2005
).
46.
M. R.
Stukan
,
V.
Lobaskin
,
C.
Holm
, and
O. I.
Vinogradova
,
Phys. Rev. E
73
,
021801
(
2006
).
47.
R.
Tsekov
and
O. I.
Vinogradova
,
J. Chem. Phys.
126
,
094901
(
2007
).
48.
B. W.
Stanton
,
J. J.
Harris
,
M. D.
Miller
, and
M. L.
Bruening
,
Langmuir
19
,
7038
(
2003
).
49.
X.
Liu
and
M. L.
Bruening
,
Chem. Mater.
16
,
351
(
2004
).
50.
M. D.
Miller
and
M. L.
Bruening
,
Chem. Mater.
17
,
5375
(
2005
).
51.
R.
Tadmor
,
J. Phys.: Condens. Matter
13
,
L195
(
2001
).
52.
H. C.
Hamaker
,
Physica (Amsterdam)
4
,
1058
(
1937
).
53.
H.
Faxen
,
Ark. Mat., Astron. Fys.
17
,
1
(
1922
).
54.
O. I.
Vinogradova
,
G. E.
Yakubov
, and
H. J.
Butt
,
J. Chem. Phys.
114
,
8124
(
2001
).
55.
J.
Viser
,
Surf. Colloid Sci.
8
,
3
(
1976
).
56.
O. V.
Lebedeva
,
B. S.
Kim
,
K.
Vasilev
, and
O. I.
Vinogradova
,
J. Colloid Interface Sci.
284
,
455
(
2005
).
57.
G.
Ibarz
,
L.
Dähne
,
E.
Donath
, and
H.
Möhwald
,
Adv. Mater. (Weinheim, Ger.)
13
,
1324
(
2001
).
58.
N. G.
Hoogeven
,
M. A.
Cohen Stuart
, and
G. J.
Fleer
,
Langmuir
12
,
3675
(
1996
).
59.
V. V.
Lulevich
and
O. I.
Vinogradova
,
Langmuir
20
,
2874
(
2004
).
60.
R. A.
McAloney
,
V.
Dudnik
, and
M. C.
Goh
,
Langmuir
19
,
3947
(
2003
).
61.
M. N.
Spiteri
,
F.
Boué
,
A.
Lapp
, and
J. P.
Cotton
,
Phys. Rev. Lett.
77
,
5218
(
1996
).
62.
V.
Lobaskin
,
A.
Lyubartsev
, and
P.
Linse
,
Phys. Rev. E
63
,
020401
(
2001
).
You do not currently have access to this content.