Abstract
Rod-like polyelectrolytes represent ideal model systems for a comprehensive comparison of theory and experiment because their conformation is independent of the ionic strength in the system. Hence, the correlation of the counterions to the highly charged macroion can be studied without the interference of conformational effects. In this chapter the synthesis and the solution behavior of rigid, rod-like cationic polyelectrolytes having poly(p-phenylene) (PPP) backbones is reviewed. These polymers can be characterized precisely and possess degrees of polymerization of up to P n ≈ 70. The analysis of the uncharged precursor polymer demonstrated that the PPP backbone has a high persistence length (ca. 22 nm) and hence may be regarded in an excellent approximation as rod-like macromolecules. The solution properties of the PPP-polyelectrolytes were analyzed using electric birefringence , small-angle X-ray scattering (SAXS) and osmometry. Measurements of the electric birefringence demonstrate that these systems form molecularly disperse systems in aqueous solution. The dependence of electric birefringence on the concentration of added salt indicates that an increase of ionic strength leads to stronger binding of counterions to the polyion. Data obtained from osmometry and small-angle X-ray scattering can directly be compared to the prediction of the Poisson-Boltzmann theory and simulations of the restricted primitive model. Semi-quantitative agreement is achieved.
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Abbreviations
- a :
-
radius of macroion
- f :
-
scattering factor (SAXS)
- f’ :
-
real part of scattering factor f
- f″ :
-
imaginary part of scattering factor f
- I(q) :
-
scattering intensity of solution
- I 0 (q) :
-
scattering intensity of isolated molecule
- L :
-
length of rod-like molecule
- n(r) :
-
radial distribution of counterions around rod
- q :
-
magnitude of scattering vector
- R M :
-
Manning radius (Eq. (5))
- R 0 :
-
cell radius
- RPM :
-
restricted primitive model
- S(q) :
-
structure factor describing interaction between solute molecules
- α:
-
cosin of angle between long axis of rod-like molecule and scattering vector q
- β :
-
integration constant of cell model (Eq. (4))
- ϕ :
-
osmotic coefficient
- ϕ ∞ :
-
osmotic coefficient in Manning limit
- κ :
-
screening constant
- λ B :
-
Bjerrum length (Eq. (2))
- Π :
-
osmotic pressure
- ξ :
-
charge parameter (Eq. (1))
References
Förster S, Schmidt M (1995) Adv Polym Sci 120:51
Schmitz KS (1993) Macroions in Solution and Colloid Suspension. VCH, New York
Förster S, Schmidt M, Antonietti M (1990) Polymer 31:781
MacCallum MJ, Vincent CA (1987) Polymer Electrolyte Reviews, Elsevier, London
Barrat J-L, Joanny J-F (1996) Theory of polyelectrolyte solutions. In: Prigogine I, Rice SA (eds) Advances on Chemical Physics 94, Wiley, p 1
Kassapidou K, Jesse W, Kuil ME, Lapp A, Egelhaaf S, van der Maarel JRC (1997) Macromolecules 30:2671
Raspaud E, da Conceicao M, Livolant F (2000) Phys Rev Lett 84:2533
Lee CC, Chu S-G, Berry GC (1983) J Polym Sci Polym Phys Ed 21:1573
Metzger Cotts P, Berry GC (1983) J Polym Sci Polym Phys Ed 21:1255
Rau IU, Rehahn M (1993) Makromol Chem Phys 194:2225
Rau IU, Rehahn M (1993) Polymer 34:2889
Rau IU, Rehahn M (1994) Acta Polym 45:3
Brodowski G, Horvath A, Ballauff M, Rehahn M (1996) Macromolecules 29:6962
Wittemann M, Rehahn M (1998) J Chem Soc Chem Commun 623
Rulkens R, Schulze M, Wegner G (1994) Macromol Rapid Commun 15:669
Vanhee S, Rulkens R, Lehmann U, Rosenauer C, Schulze M, Köhler W, Wegner G (1996) Macromolecules 29:5136
Ballauff M (1993) Mater Sci Tech 12:213
Ballauff M (1989) Angew Chem 101:261
Rehahn M, Schlüter A-D, Wegner G, Feast WJ (1989) Polymer 30:1060
Rehahn M, Schlüter A-D, Wegner G (1990) Makromol Chem Phys 191:1991
Schlüter A-D, Wegner G (1993) Acta Polym 44:59
Manning GS (1969) J Chem Phys 51:924, 934,3249
Oosawa F (1971) Polyelectrolytes, Marcel Dekker, New York
Katchalsky A (1971) Pure Appl. Chem. 26:327
Deserno, M, Ph.D. thesis, Universität Mainz, 2000, http://archimed.uni-mainz.de/pub/2000/0018/;
Deserno, M, Holm C (2001) Cell model and Poisson-Boltzmann theory: a brief introduction. In: Holm C, Kekicheff P, Podgornik R (eds) Electrostatic Effects in Soft Matter and Biophysics. Kluwer, Dordrecht, p 27
Deserno, M, Holm C, Kremer K (2000) Molecular dynamics simulations of the cylindrical cell model. In: Radeva T (ed) Physical Chemistry of Polyelectrolytes. Marcel Dekker, New York, pp 26
Fuoss RM, Katchalsky A, Lifson S (1951) Proc Natl Acad Sci USA 37:579; Alfrey T, Berg PW, Morawetz H (1951) J Polym Sci 7:543
Le Bret M, Zimm BH (1984) Biopolymers 23:287
Deserno M, May S, Holm C (2000) Macromolecules 33:199
Marcus RA (1955) J Chem Phys 23:1057
Barbosa MC, Deserno M, Holm C (2000) Europhys Lett 52:80
Borukhov I, Andelman D, Orland H (1997) Phys Rev Lett 79:435
Lue L, Zoeller N, Blankschtein D (1999) Langmuir 15:3726
Nordholm S (1984) Chem Phys Lett 105:302; Penfold R, Nordholm S, Jönsson B, Woodward CE (1990) J Chem Phys 92:1915
Groot R (1990) J Chem Phys 95:9191; Diel A, Barbosa MC, Tamashiro MN, Levin Y (1999) Physica A 274:433
Gonzales-Tovar E, Lozada-Cassou M, Henderson D (1985) J Chem Phys 83:361; Das T, Bratko D, Bhuyan LB, Outhwaite CW (1997) J Chem Phys 107:9197; Kjellander R (2001) Distribution function theory of electrolytes and electrical double layers. In: Holm C, Kekicheff P, Podgornik R (eds) Electrostatic Effects in Soft Matter and Biophysics. Kluwer, Dordrecht, p. 317
Deserno M, Jimenez-Angeles F, Holm C, Lozada-Cassou M (2001) J Phys Chem B, 105:10983; Messina R, Gonzalez Tovar E, Lozada-Cassou M, Holm C (2002) Europhys Lett 60:383
Kuhn P, Levin Y, Barbosa MC (1998) Macromolecules 31:8347;Levin Y, Barbosa MC (1997) J Phys II France 7:37
Nyquist RM, Ha B-Y, Liu A (1999) Macromolecules 32:3481
O’Konski CT ed (1978) Molecular Electro-Optics, part 2. Marcel Dekker, New York
Jennings BR (ed) (1979) Electro-Optics and Dielectrics of Macromolecules and Colloids. Plenum Press, New York
Krause S (ed) (1981) Molecular Electro-Optics. Plenum Press, New York
Fredericq E, Houssier C (1973) Electric Dichroism and Electric Birefringence. Clarendon Press, Oxford
Yamaoka K, Ueda K (1980) J Phys Chem 84:1422.
Schwarz G (1959) Z Phys 145:563; Z Phys Chem 19:286
Mandel M (1961) Mol Phys 4:489.
Oosawa F (1970) Biopolymers 9:677
Lachenmayer K (2000) PhD. Thesis, Stuttgart.
Lachenmayer K, Oppermann W (2002) J Chem Phys 116:392.
O’Konski CT, Krause S (1970) J Phys Chem 74:3243.
van Dijk W, van der Touw F, Mandel M (1981) Macromolecules 14:792.
Hogan M, Dattagupta N, Crothers DM (1978) Biochemistry 75:195
Rau DC, Bloomfield VA (1979) Biopolymers 18:2783
Fixman M, Jagannathan S (1981) J Chem Phys 75:4048
Yoshida M, Kikuchi K, Maekawa T, Watanabe H (1992) J Phys Chem 96:2365
Oppermann W (1988) Macromol Chem 189:927; 189:2125
Wandrey Ch, Hunkeler D, Wendler U, Jaeger W (2000) Macromolecules 33:7136
Blaul J, Wittemann M, Ballauff M, Rehahn M (2000) J Phys Chem B 104:7077
Deserno M, Holm C, Blaul J, Ballauff M, Rehahn M (2001) Eur Phys J E 5:97
Deserno M, Holm C (2002) Molecular Physics 100:2941
Neu J (1999) Phys Rev Lett 82:1072
Sader J, Chan DY (1999) J Colloid Interface Sci 213:268
Trizac E, Raimbault JL (1999) Phys Rev E 60:6530
Nilsson LG, Guldbrand L, Nordenskiöld L (1991) Mol Phys 72:177
Lyubartsev AP, Nordenskiöld L (1997) J Phys Chem 101:4335
Gronbech-Jensen N, Mashl RJ, Bruinsma RF, Gelbart WM (1997) Phys Rev Lett 78:2477
Lyubartsev AP, Tang JX, Janmey PA, Nordenskiöld L (1998) Phys Rev Lett 81:5465
Auer H, Alexandrowicz Z (1969) Biopolymers 8:1
Oppermann W, Wagner M (1999) Langmuir 15:4089
Wandrey C (1997) Polyelektrolyte—Makromolekulare Parameter und Elektrolytverhalten. Cuvillier, Göttingen
Guilleaume B, Blaul J, Wittemann M, Rehahn M, Ballauff M (2002) Eur Phys J E 8:299; Guilleaume B, Ballauff M, Goerigk G, Wittemann M, Rehahn M (2001) Colloid Polym Sci 279:829
Stuhrmann HB Adv Polym Sci (1985) 67:123
Kassapidou K, Jesse W, Kuil M E, Lapp A, Egelhaaf S, van der Maarel JRC (1997) Macromolecules 30:2671
van der Maarel JRC, Kassapidou K (1998) Macromolecules 31:5734
van der Maarel JRC, Groot LCA, Mandel M, Jesse W, Jannink G, Rodriguez V (1992) J Phys II France 2:109
Zakharova SS, Engelhaaf SU, Bhuiyan LB, Outhwaite CW, Bratko D., van der Maarel, JRC (1999) J Chem Phys 111:10706
Wu CF, Chen SH, Shih LB, Lin JS (1988) Phys Rev Lett 61:645
Chang SL, Chen SH, Rill RL, Lin JS (1990) J Phys Chem 94:8025
Maier EE, Krause R, Deggelmann M, Hagenbüchle MM, Weber R, Fraden S (1992) Macromolecules 25:1125
Acknowledgment
The authors are indebted to the Deutsche Forschungsgemeinschaft for generous support within the Schwerpunkt “Polyelektrolyte”. C. Holm acknowledges M. Deserno for intensive collaboration on the presented material.
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Holm, C., Rehahn, M., Oppermann, W., Ballauff, M. Stiff-Chain Polyelectrolytes. In: Schmidt, M. (eds) Polyelectrolytes with Defined Molecular Architecture II. Advances in Polymer Science, vol 166. Springer, Berlin, Heidelberg. https://doi.org/10.1007/b11347
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DOI: https://doi.org/10.1007/b11347
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