pH and temperature-sensitive N-isopropylacrylamide ampholytic networks incorporating L-lysine

Langmuir. 2006 Aug 29;22(18):7843-7. doi: 10.1021/la060334n.

Abstract

Ampholytic polymer gels based on N-isopropylacrylamide (NIPA) and natural amino acid L-lysine were prepared by free radical polymerization in aqueous solutions. To make amino acids attachable to the polymer chain, the acrylic group was added to the epsilon-amino group of lysine to obtain N-epsilon-acrylic-lysine (Z). Finally, a new temperature- and pH-sensitive (NIPA-Z) hydrogel was obtained. The presence of amino and carboxylic groups of amino acids gave us a possibility to control the amount and sign of the excessive charge on the polymeric network with respect to pH. The swelling behavior of the NIPA-Z hydrogels with respect to the amount of Z (0-4%), temperature, and pH was investigated. Temperature and pH were changed in the ranges of 20-50 degrees C and 2-12, respectively. To eliminate the influence of ionic strength on the swelling behavior, this parameter was kept constant in all experiments. It was found that the pH dependence of the degree of swelling for the NIPA-Z gels, measured at constant temperature, exhibits a minimum. Such a minimum was seen for the ampholyte networks with independent acidic and basic groups attached to the polymer chains. For the NIPA-Z gels, the minimum was wide, and the pH range over which it was spread corresponded well to the pH distribution of the zwitterions. The way the gel volume changed with an increase in temperature depends on the amino acid amount. It is initially discontinuous and turns to the continuous one for the higher percentage of amino acid. The temperature dependence of the swelling process obtained for different pH values clearly shows that for the pH region where the zwitterions dominate, the polymer networks collapse more efficiently.