ABSTRACT
Electrophoretic behavior was studied for N-isopropylacrylamide (NIPA) microgels, into which different amounts of poly(acrylic acid) (PAAc) were physically entrapped. Copolymer microgels of NIPA with acrylic acid (AAc) were also studied as a control. Electrophoretic mobility was measured in 0.1 M NaCl solution at 25 °C as a function of pH, using an electrophoretic light scattering technique. The mobility of the copolymer microgel whose COOH groups are fully ionized agreed with that of PAAc when its ionization degree (α(n)) is close to the mole fraction (f(AAc)) of the AAc unit in the copolymer gel. There was good agreement between the mobility values of the copolymer microgel and the linear NIPA/AAc copolymer when their AAc contents are very close to each other. However, the mobility of the microgel with immobilized PAAc was higher than that of the copolymer microgel, even when there was no difference in the AAc content for both microgels. Moreover, the immobilized PAAc showed a higher mobility than the free PAAc when its α(n) is equal to f(AAc) in the immobilized system. No correlation was observed between the mobility and the hydrodynamic radius. These results were discussed in terms of the free draining model (FDM) for the electrophoresis of polyelectrolytes. It became apparent that the mobility difference depending upon whether (i) the PAAc ions are in the cage of the NIPA network or (ii) the AAc units are copolymerized with the network chain is due to the structural difference of the segments considered in the FDM.
ABSTRACT
We synthesized the glutaraldehyde cross-linked hydrogels using four kinds of poly(lysine)s (PLs) and measured the equilibrium swelling ratio (Q) as a function of pH. Also measured was the temperature change of Q at a fixed pH (11.6) in the absence and presence of additives (LiBr, methanol and urea) that affect the secondary structure of PLs. The swelling data were examined using a force balance approach in which the repulsive and attractive interactions among the cross-linked PL chains were considered based on the conformational properties of PLs in aqueous solutions. It was found that the formation of the helical segments in the cross-linked chain has little effect in the gel collapse, but their association acts as the attractive interaction causing the gel to shrink. The formation of the beta-sheet structure within the network also acts as the attractive interaction. These attractive interactions are mainly due to the hydrogen bonding, but hydrophobic interactions between the lysine side chains should be considered. In addition, in the swelling behavior of all the PL gels the polyampholyte nature appears due to electrostatic interactions of the basic groups with the C-terminal carboxyl group.
