The interfacial behavior of surface localized,
poly(ethylene glycol) (PEG) esterified fatty acid
amphiphiles
was comparatively studied at microparticle surfaces via phase partition
and at flat surfaces via in situ
null ellipsometry. Ellipsometry was performed on methylsilane
(MeSi), phosphatidic acid (PA), and
phosphatidylcholine (PC) coated silica slides, while human erythrocyte
and PC liposomes were subjected
to partition in aqueous PEG, dextran two-phase systems. Analogous
results from both methods suggest
that PEG−amphiphile adsorption can be relatively independent of the
underlying surface. Ellipsometry
indicated that members of a series of PEG-fatty acid esters of the type
C
i
:
j
−EO151
(16 ≤ i ≤ 18, 0 ≤ j ≤
2) adsorb similarly at MeSi-, PC-, and PA-coated surfaces, reaching a
plateau (≈0.1 PEG
chains·nm-2)
independent of micelle formation. When normalized for acyl tail
hydrophobicity, PEG−amphiphile
adsorption is relatively noncooperative and independent of the acyl
tail; saturation is largely determined
by repulsive PEG interchain interactions. At saturation,
EO151−ester layers were 10−15 nm thick,
suggesting close packed PEG molecules unfolded normal to the target
surface. Ellipsometry also indicated
the average PEG concentration in the layer was ≈0.07
g·cm-3, and greater than in the
PEG-enriched phase
of many two-phase systems. This suggests that the partition of
PEG-coated colloids reflects interfacial
free energy differences between solution- and surface-localized,
polymer-enriched phases. PEG−ester
adsorption (mg·m-2) isotherms determined on
flat slides via ellipsometry correlate directly with those
reflected by the partition of analogous microparticles. These
results help explain previous observations
that changes in partition induced by surface-localized PEG mirror the
effects of such localization on the
physiological behavior of bioactive colloids.