Dansyl fluorescent labels with two different spacer
lengths (D2 and D8) were pendently
attached to unmodified and 30 mol % n-octyl-modified
copoly(sodium maleate-alt-ethyl vinyl ether).
The
time-resolved fluorescence anisotropy (TRFA) measurements of these
labels were obtained in aqueous
media as a function of pH and analyzed using impulse reconvolution
analysis (IRA). At pH values below
6.7, the hydrophobically modified copolymers exist as compact globules,
as evidenced by the long
fluorescence emission lifetimes of the labels. At these pH values,
two rotational correlation times (RCTs)
corresponding to two distinct molecular motions within associating
hydrophobic microdomains are seen:
one associated with the motion of the chromophore coupled to the
copolymer backbone and the other
associated with the rotational motion of the chromophore. Above pH
6.7, the copolymer is progressively
extended with increasing pH, as indicated by the short emission
lifetime of the labels and the observation
of only one rotational correlation time corresponding to the rotational
motion of the labels in an aqueous
environment. Local rotational diffusion coefficients and local
viscosities for the dansyl labels have also
been estimated as a function of pH. The observed fluorescence data
are consistent with the classic model
proposed for pH-induced transition from a polysoap to an extended
polyelectrolyte in dilute aqueous
solution.