Ky. Lee et al., STRUCTURAL DETERMINATION AND INTERIOR POLARITY OF SELF-AGGREGATES PREPARED FROM DEOXYCHOLIC ACID-MODIFIED CHITOSAN IN WATER, Macromolecules, 31(2), 1998, pp. 378-383
Hydrophobically modified chitosan derivatives containing 0.6-5.1 deoxy
cholic acid groups per 100 anhydroglucose units of chitosan were synth
esized by an EDC-mediated coupling reaction. Self-aggregates of the ch
itosan derivatives in aqueous media were formed by sonication with a P
robe-type sonifier. The mean diameter of self-aggregates determined by
dynamic light scattering decreased slightly with an increasing degree
of substitution (DS) by hydrophobic groups. Photophysical and photoch
emical characteristics of self-aggregates were examined by fluorescenc
e probe techniques. Measurement of the binding equilibrium constant (K
-v), for pyrene and lifetime (tau) for 1,6-diphenyl-1,3,5-hexatriene (
BPH) showed that the interior of self-aggregates became nonpolar as th
e DS was increased, Microviscosity of the interior of self-aggregates
determined by measuring an anisotropy value for DPH was not significan
tly affected by the DS of hydrophobic groups. The aggregation number o
f deoxycholic acid groups per one hydrophobic microdomain !(n(DCA)) wa
s estimated by the steady-state fluorescence quenching method with 1-d
odecylpyridinium chloride and was almost independent-of the DS. From t
he re suits of the fluorescence quenching experiment, it was conjectur
ed that there may be multiple (rather than one) hydrophobic microdomai
ns in a self-aggregate.