Polyelectrolyte Gels-Fundamentals and Applications
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Polymer Journal, Vol. 38, No. 12, pp. 1211–1219 (2006) #2006 The Society of Polymer Science, Japan AWARD ACCOUNTS: SPSJ AWARD (2005) Polyelectrolyte Gels-Fundamentals and Applications y Hyuck Joon KWON,1 Yoshihito OSADA,1 and Jian Ping GONG1;2; 1Department of Biological Science, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan 2SORST, JST, Sapporo 060-0810, Japan (Received October 3, 2006; Accepted October 12, 2006; Published November 10, 2006) ABSTRACT: Polyelectrolyte gels are charged polymer networks with macro-ions fixed on polymer chains. This present paper introduces fundamental aspects, properties and application of negatively charged polyelectrolyte gels, focusing on the electrical properties of polyelectrolyte gels, diffusion of proteins in polyelectrolyte gels, interactions between polyelectrolyte gels and oppositely charged molecules, and mechanical strength of polyelectrolyte based gels. These characteristic properties of polyelectrolyte gels have considerable potential for applications, such as soft and wet scaffolds of cells, soft actuators and replacement of biological tissues. [doi:10.1295/polymj.PJ2006125] KEY WORDS Polyelectrolyte Gel / Electrostatic Potential / Protein Diffusion / Oppositely Charged Surfactant / Double Network (DN) Gel / Cell Scaffold / A polymer gel consists of an elastic cross-linked largely made of gels, in which water content ranges network and a fluid filling the interstitial spaces of up to 90%, except for bones, teeth, nails, and the outer the network. The network of long polymer molecules layers of skin, and this enables the organism to trans- holds the liquid in place to give the gel solidity. Gels port ions and molecules more easily and effectively are wet and soft and look like solid material but are while keeping its solidity. Especially, biological tis- capable of undergoing large deformation in response sues consist of polyelectrolytes such as polysaccharide to environmental change, in contrast with most indus- and charged filamentous proteins and their properties trial materials such as metal, ceramics, and plastics, originate from the polyelectroyte nature. Articular which are dry and hard. cartilage, containing anionic proteoglycan-rich extrac- A polyelectrolyte gel is a charged polymer network ellular matrix (ECM), has remarkable elasticity, low with macro-ions fixed on the polymer chains and mi- surface friction, and ability to withstand enormous cro-counter ions are localized in the network frame. physical forces.4 These features are directly related Polyelectrolyte gels exhibit the ability to absorb a to the high water content of cartilage, which is tightly significant amount (up to 2000 times the polymer held within the matrix of negatively charged macro- weight) of water within its network structure, but do molecular aggrecan/hyaluronic acid complexes stabi- not dissolve in water.1 When a polyelectrolyte gel is lized by link proteins. This negatively charged poly- interposed between a pair of plate electrodes and a electrolyte gels draw great attention despite consid- DC current is applied, it undergoes electrically- erable theoretical difficulties in analysis. induced chemomechanical contraction and concomi- This article describes fundamental aspects, proper- tant water exudation in the air.2 Polyelectrolyte gels ties, and application of negatively charged polyelec- exhibit various unique electrical responses different trolyte gels. from those of linear polyelectrolyte solutions. For ex- ample, a repetitive current oscillation occurs when a ELECTRICAL PROPERTIES OF DC voltage is applied to a water-swollen polyelectro- POLYELECTROLYTE GELS lyte gel through a pair of needle electrodes.3 Shape change and motion of polyelectrolyte gels are similar Electrostatic Potential Distribution to biological motion such as muscle, flagellar, and The properties and behavior of polyelectrolyte gels, ciliary movement in terms of the molecular level such as high swelling, phase transition, and elasticity deformation, and this gel actuator has been studied have been mostly investigated. However, little study for construction of biomimetic system and further has been made of local electric potential distribution application to creation of artificial organs.1 in the charged network because of difficulty of the Living organisms such as mammalian tissues are analysis. Numerical calculation of electrostatic poten- yTo whom correspondence should be addressed (Tel/Fax: +81-11-706-2774, E-mail: [email protected]). 1211 H. J. KWON,Y.OSADA, and J. P. GONG havior of the polyelectrolyte gel can be expected such as enhanced counter-ion ‘‘binding’’ which should in- crease with the increase in the cross-linking density.6,7 Previous calculations revealed the presence of the deep electrostatic potential wells at cross-linking point. These potential wells should strongly localize or ‘‘condense’’ counter-ions through strong electro- static interactions and should affect the conductive behaviors of the gel. Another effect is decreased con- tribution of ion transportation from the ‘‘giga’’ macro- molecular network. The macroions also make a contribution to the electrical conduction of polymer solution.8,9 This contribution is expected to be de- pressed in the case of the networked gel. The equivalent (molar) conductance of the strong polyelectrolyte gel, poly(2-acrylamido-2-methylpro- Figure 1. Spatial profile of electrostatic potential energy for panesulfonic acid) (PAMPS) gel was investigated at the plane within the mesh-like network. X and Y axes are in unit various monomeric concentrations.10 Figure 2c shows of r (¼ 0:6 nm). Reproduced with permission from (5), Gong, i the concentration dependency of the equivalent con- J. P., et al., Chem. Lett. 449 (1995) #1995, The Chemical Society of Japan. ductance of the PAMPS gels with various counterions. The equivalent conductance of solutions of corre- sponding monomers (AMPS) and linear polymers tial distribution in the charged polymer network has (PAMPS) are shown in Figure 2a, 2b. This shows that been made basing the Poisson-Boltzmann equation.5 a polyelectrolyte gel has equivalent conductance ap- Figure 1 shows a spatial profile of electrostatic po- proximately equal to that of the corresponding linear tential energy in the unit of kT on the planes of mesh- polymer solution which showed slightly increase in like networks. The figure shows potential energy wells the equivalent conductance with concentration. Con- at every cross-linking points and valleys along the siderable coiling of the polymer chain at such high polymer chains. concentrations may be responsible for the decreas- Counter-ion distribution in the gel is determined by ing in the fraction of counter-ions condensed on the the Boltzmann distribution. Counter ions are mostly polyions, leading to higher counter-ion mobility and localized around the network knots as well as polymer equivalent conductance. chains due to the deep potential wells and valleys. However, the gels showed almost no distinct con- Charge density of counter ions decreased very sharply centration dependency of equivalent conductance, with an increase in the distance from the polymer which was somewhat smaller than that of linear poly- chain. Counter ions located in the deep potential val- mer solutions at concentrations higher than 0.25 M. ley ( kBT) should strongly be bound to macro-ions. The polymer chain coiling effect at higher concentra- The number of bound counter ions would increase tions for polymer solutions may be canceled out by with cross-linking density. the increasing cross-linking points which condense The deep potential wells and high counter ion den- counter-ions to decreases counter-ion mobility and sities at cross-linking points may bring about an insta- equivalent conductance of gels. bility to result in counter ion condensation as predict- ed by Oosawa and Manning for the linear polyelec- Low Frequency Dielectric Relaxation trolyte solution.6,7 When the complex dielectric constant of the anion- The presence of deep electrostatic potential valleys ic poly(sodium 2-acrylamido-2-methylpropanesulfo- should strongly confine the motion of water molecules nate) (PNaAMPS) gels and their corresponding anion- which fill interfacial spaces of the network and restrict ic polymer solutions were measured, the gels showed the configuration favorable to form crystal structure. low-frequency dielectric relaxation in a frequency This may decrease entropy and enthalpy changes of region lower than that of linear polymer solutions.11 solvent molecules at crystallization, due to enhanced Mean relaxation time of the gel decreased with cross- polarization and should decrease the melting temper- linking density or the concentration, which is different ature of water. from the behavior of the linear polymer solution that showed constant of relaxation time on changing poly- Electrical Conductance mer concentration (Figure 3). The low-frequency re- Some effects of cross-linkage on the conductive be- laxation observed on the gels has been explained as 1212 Polym. J., Vol. 38, No. 12, 2006 Properties and Application of Polyelectrolyte Gels Figure 3. Concentration dependence of the mean relaxation time o of PNaAMPS gels their corresponding linear polymer solu- tions: ( ): polyelectrolyte gels; ( ): linear polymer solutions. Re- produced with permission from (11), Mitsumata, T., et al., J. Phys. Chem. B, 102, 5246 (1998) #1998, American Chemical Society. Figure 2. Equivalent conductance à of monomer AMPS solu- tion (a), linear polymer