The self-association of copolymers of N-isopropylacrylamide and N-n-oc
tadecylacrylamide (Pnipam-C18) in aqueous solutions was studied by mea
ns of time-resolved fluorescence quenching. The discrete domains consi
st of several polymer chains interacting through their hydrophobic sid
e chains, since the number of aliphatic side chains involved in the mi
crodomain formation (aggregation number) is larger than the number of
aliphatic side chains per polymer. By means of titration microcalorime
try, the interaction of the copolymer with surfactants was studied. St
rong association between the copolymer and the cationic surfactants N-
cetylpyridinium chloride (C1GPyCl) and cetyltrimethylammonium bromide
(CTAB) occurs by partitioning of the surfactants in a noncooperative m
echanism. Prior to mixed-micelle formation, individual surfactant mole
cules adsorb to collapsed polymer coils as can be seen from the large
exothermal contribution in the enthalpy curves which result from micro
calorimetric titration of surfactant into aqueous Pnipam-C18 solutions
.