A series of copolymers of methacrylic acid and benzyl methacrylate (up to 1
5 mole %) was prepared by reaction of the sodium salt of poly(methacrylic a
cid) (PMA) and benzyl chloride. The effect of increasing the amount of hydr
ophobic groups on the hypercoil conformation of PMA was studied by potentio
metry, viscosimetry, solubility and fluorescence measurements, using pyrene
as a probe. The hypercoil conformation is stabilized by benzyl groups in w
ater but in the presence of sodium perchlorate or urea, the opposite effect
is observed due to drastic changes of the entropy change accompanying the
conformational transition. Measurements of the intrinsic fluorescence of be
nzyl groups revealed that it is sensitive to the conformational transition.
Using pyrene as a probe indicates that, in acid conditions, the increase o
f the hydrophobic nature of the polymers makes the hypercoil progressively
tighter, and prevents the probe dissolving inside the polymer coil. In thes
e conditions, pyrene is located at the interface between the polymer and so
lvent in a medium of relatively high polarity. On the contrary, in basic me
dium, for the extended conformation, increasing the hydrophobicity of the p
olymer decreases the polarity of the medium surrounding pyrene. (C) 1998 El
sevier Science Ltd. All rights reserved.