Synthesis, characterisation and solution behaviour of thermo- and pH-responsive polymers bearing L-leucine residues in the side chains

Polymers capable of responding to both temperature and pH changes were synthesised by radical copolymerisation of N-isopropylacrylamide (NIPAAm) and N-methacryloyl-l-leucine (MALEU) in different NIPAAm/MALEU molar ratios (15:1, 10:1, 2:1 and 1:1). The polymers were characterised by Size Exclusion Chromatography, acid–base titrations, FT-IR and 1H-NMR analyses. Their solution behaviour was studied in 0.1 M NaCl and in citrate buffers (pH 4.0, 4.5, 5.0 and 6.0). At pH 4.0 and 4.5 the cloud point temperature (TCP) of copolymers was depressed proportionally to their MALEU content. In contrast, at pH 5.0 and 6.0 the phase transition temperature increased linearly. The behaviour of the copolymers with NIPAAm/MALEU ratios 15:1 and 10:1 was investigated also between pH 3 and 11 in 0.1 M
NaCl. In both cases a sharp increase in TCP was observed around pH 4–5. The TCP vs. pH curve was linearised and the acidity constants were determined by the linearisation procedure. Furthermore, it was possible to demonstrate that the phase transition temperature increases linearly with the ionic content of the polymers.