Abstract.
We use molecular dynamics simulations to investigate centipede-like polymers with stiff charged side chains, end-grafted to a planar wall. The effect of the grafting density and the Bjerrum length on the conformational behaviour of the brush is examined in detail. In addition, we make a comparison of centipede-like polyelectrolyte (CPE) brushes with neutral centipede-like polymer (NCP) and linear polyelectrolyte (LPE) brushes. At weak electrostatic interaction, the main chains of the CPE chains adopt a strongly stretched conformation, and the monomer density profiles of side chains exhibit a clear oscillatory behaviour. With increasing Bjerrum length, the CPE brush undergoes a collapse transition. Compared to the CPE brushes, the counterion condensation effect is stronger for the LPE brushes, regardless of whether the electrostatic interaction is weak or strong and of whether the grafting density is low or high. Additionally, it is shown that the architecture of the grafted chains makes a weak contribution to the counterion condensation at strong electrostatic interaction. We also find that the electrostatic repulsion between charged side chains can enhance the stiffness of the main chains and thus limit the range of movement of the free-end monomers.
Similar content being viewed by others
References
J. Rühe et al., Adv. Polym. Sci. 165, 79 (2004)
M. Ballauff, O. Borisov, Curr. Opin. Colloid Interface Sci. 11, 316 (2006)
F. Zhou, W.T.S. Huck, Phys. Chem. Chem. Phys. 8, 3815 (2006)
M. Ballauff, Prog. Polym. Sci. 32, 1135 (2007)
L. Samokhina, M. Schrinner, M. Ballauff, Langmuir 23, 3615 (2007)
U. Raviv, S. Giasson, N. Kampf, J.-F. Gohy, R. Jerome, J. Klein, Nature 425, 163 (2003)
F. Zhou, W.M. Shu, M.E. Welland, W.T.S. Huck, J. Am. Chem. Soc. 128, 5326 (2006)
E.B. Zhulina, O.V. Borisov, J. Chem. Phys. 107, 5952 (1997)
E.B. Zhulina, J.K. Wolterink, O.V. Borisov, Macromolecules 33, 4945 (2000)
R. Israels, F.A.M. Leermakers, G.J. Fleer, E.B. Zhulina, Macromolecules 27, 3249 (1994)
O.V. Borisov, F.A.M. Leermakers, G.J. Fleer, E.B. Zhulina, J. Chem. Phys. 114, 7700 (2001)
E.B. Zhulina, O.V. Borisov, J. van Male, F.A.M. Leermakers, Langmuir 17, 1277 (2001)
A.A. Mercurieva, T.M. Birshtein, E.B. Zhulina, P. Iakovlev, J. van Male, F.A.M. Leermakers, Macromolecules 35, 4739 (2002)
P. Pincus, Macromolecules 24, 2912 (1991)
F.S. Csajka, R.R. Netz, C. Seidel, J.F. Joanny, Eur. Phys. J. E 4, 505 (2001)
P.M. Biesheuvel, J. Colloid Interface Sci. 275, 97 (2004)
R. Nap, P. Gong, I. Szleifer, J. Polym. Sci., Part B: Polym. Phys. 44, 2638 (2006)
P. Gong, J. Genzer, I. Szleifer, Phys. Rev. Lett. 98, 018302 (2007)
P. Gong, T. Wu, J. Genzer, I. Szleifer, Macromolecules 40, 8765 (2007)
O.J. Hehmeyer, G. Arya, A.Z. Panagiotopoulos, I. Szleifer, J. Chem. Phys. 126, 244902 (2007)
O.V. Borisov, E.B. Zhulina, T.M. Birshtein, Macromolecules 27, 4795 (1994)
T. Wu, P. Gong, I. Szleifer, P. Vlcek, V. Subr, J. Genzer, Macromolecules 40, 8756 (2007)
R. Barbey, L. Lavanant, D. Paripovic, N. Schuwer, C. Sugnaux, S. Tugulu, H.A. Klok, Chem. Rev. 109, 5437 (2009)
F.S. Csajka, C. Seidel, Macromolecules 33, 2728 (2000)
C. Seidel, Macromolecules 36, 2536 (2003)
N.A. Kumar, C. Seidel, Macromolecules 38, 9341 (2005)
N.A. Kumar, C. Seidel, Phys. Rev. E 76, 020801 (2007)
H. Fazli, R. Golestanian, P.L. Hansen, M.R. Kolahchi, Europhys. Lett. 73, 429 (2006)
M. Sirchabesan, S. Giasson, Langmuir 23, 9713 (2007)
Y. Mei, M. Hoffmann, M. Ballauff, A. Jusufi, Phys. Rev. E 77, 031805 (2008)
Q. Cao, C. Zuo, H. He, L. Li, Macromol. Theory Simul. 18, 441 (2009)
O.J. Hehmeyer, M.J. Stevens, J. Chem. Phys. 122, 134909 (2005)
J.M.Y. Carrillo, A.V. Dobrynin, Langmuir 25, 13158 (2009)
A. Naji, R.R. Netz, C. Seidel, Eur. Phys. J. E 12, 223 (2003)
H. Ahrens, S. Forster, C.A. Helm, N.A. Kumar, A. Naji, R.R. Netz, C. Seidel, J. Phys. Chem. B 108, 16870 (2004)
G. Romet-Lemonne, J. Daillant, P. Guenoun, J. Yang, J.W. Mays, Phys. Rev. Lett. 93, 148301 (2004)
A. Wynveen, C.N. Likos, Phys. Rev. E 80, 010801 (2009)
M. Baratlo, H. Fazli, Eur. Phys. J. E 29, 131 (2009)
X. Gao, W. Feng, S.P. Zhu, H. Sheardown, J.L. Brash, Langmuir 24, 8303 (2008)
S.S. Sheiko, B.S. Sumerlin, K. Matyjaszewski, Prog. Polym. Sci. 33, 759 (2008)
N. Hadjichristidis, M. Pitsikalis, H. Iatrou, S. Pispas, Macromol. Rapid Commun. 24, 979 (2003)
G. Ten Brinke, O. Ikkala, Chem. Rec. 4, 219 (2004)
R.J. Nap, I. Szleifer, Biophys. J. 95, 4570 (2008)
L. Feuz, F.A.M. Leermakers, M. Textor, O. Borisov, Macromolecules 38, 8891 (2005)
R. Stepanyan, A. Subbotin, G. ten Brinke, Macromolecules 35, 5640 (2002)
A. Subbotin, M. Saariaho, O. Ikkala, G. ten Brinke, Macromolecules 33, 3447 (2000)
G.A. van Ekenstein, E. Polushkin, H. Nijland, O. Ikkala, G. ten Brinke, Macromolecules 36, 3684 (2003)
K. Fischer, M. Schmidt, Macromol. Rapid Commun. 22, 787 (2001)
C.M. Li, N. Gunari, K. Fischer, A. Janshoff, M. Schmidt, Angew. Chem., Int. Ed. 43, 1101 (2004)
M. Kikuchi, L.T.N. Lien, A. Narumi, Y. Jinbo, Y. Izumi, K. Nagai, S. Kawaguchi, Macromolecules 41, 6564 (2008)
K. Lienkamp, L. Noe, M.H. Breniaux, I. Lieberwirth, F. Groehn, G. Wegner, Macromolecules 40, 2486 (2007)
A. Papagiannopoulos, C.M. Fernyhough, T.A. Waigh, A. Radulescu, Macromol. Chem. Phys. 209, 2475 (2008)
T. Pettersson, A. Naderi, R. Makuska, P.M. Claesson, Langmuir 24, 3336 (2008)
Y.Y. Xu, S. Bolisetty, M. Drechsler, B. Fang, J.Y. Yuan, M. Ballauff, A.H.E. Muller, Polymer 49, 3957 (2008)
Y.Y. Xu, S. Bolisetty, M. Drechsler, B. Fang, J.Y. Yuan, L. Harnau, M. Ballauff, A.H.E. Muller, Soft Matter 5, 379 (2009)
L.-T. Yan, Y. Xu, M. Ballauff, A.H.E. Muller, A. Boker, J. Phys. Chem. B 113, 5104 (2009)
L.-T. Yan, X. Zhang, Langmuir 25, 3808 (2009)
K. Kremer, G.S. Grest, J. Chem. Phys. 92, 5057 (1990)
S.W. Sides, G.S. Grest, M.J.K. Stevens, Macromolecules 35, 566 (2002)
R.W. Hockney, J.W. Eastwood, Computer Simulation Using Particles (Adam Hilger, Bristol, 1988)
I.C. Yeh, M.L. Berkowitz, J. Chem. Phys. 111, 3155 (1999)
G.S. Manning, J. Chem. Phys. 51, 924 (1969)
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Cao, Q.Q., Zuo, C.C. & Li, L.J. Molecular dynamics simulations of end-grafted centipede-like polymers with stiff charged side chains. Eur. Phys. J. E 32, 1–12 (2010). https://doi.org/10.1140/epje/i2010-10585-3
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1140/epje/i2010-10585-3