The rotational mobility of spin probes of different shape and size in low m
olecular and polymer micelles has been studied. Several probes having nitro
xide fragment localized either in the vicinity of micelle interface or in t
he hydrocarbon core have been used. Upon increasing the number of carbon at
oms in hydrocarbon chain of detergent from 7 to 13 (sodium alkyl sulfate mi
celles) or from 12 to 16 (alkyltrimethylammonium bromide micelles) the rota
tional mobility of spin probes is decreased by the factor 1.5-2.0. The spin
probe rotational mobility in polymer micelles (the complexes of alkyltrime
thylammonium bromides and polymethacrylic or polyacrylic acids) is less tha
n mobility in free micelles of the same surfactants. The study of EPR-spect
ra of spin labeled polymethacrylic acid (PMA) indicated that formation of w
ater soluble complexes of polymer and alkyltrimethylammonium bromides in al
kaline solutions (pH 9) does not affect the polymer segmental mobility. On
the other hand, the polymer complexes formation in slightly acidic water so
lution (pH 6) breaks down the compact PMA conformation, thus increasing the
polymer segmental mobility. Possible structures of polymer micelles are di
scussed. (C) 1998 Elsevier Science B.V. All rights reserved.