Electrokinetic surface characterization is sensitive to both charge gr
oups (pK and surface density) and neutral polymer coatings (molecular
weight, surface density, grafting chemistry). It allows nondestructive
semiquantitative evaluation of coating stability, as regards alterati
on of the above parameters in relation to various environments. Charac
terization of surface electroosmosis versus pH (2 to 11) was used to e
valuate poly(ethylene glycol) (PEG) coatings of biotechnical significa
nce following a 3-week 22 degrees C exposure to 0.5 M sodium phosphate
solutions of pH 4-11. The coatings involved epoxide-functionalized PE
Gs of M(r)3400 (E-PEG 3400) covalently grafted to aminosilane-modified
fused quartz capillaries. Coatings made from PEGs with an epoxide gro
up at one end (mE-PEG 5000) were stable at pH 4-11 whereas those made
from PEGs with epoxide groups at both ends (diE-PEG 3400) were only st
able at pH 4-9. During storage at pH 11 the latter exhibited time-depe
ndent generation of surface negative charge groups of pK approximate t
o 5.3 and surface density (approximate to 0.1/nm(2)) similar to the PE
G grafting density. The effect was significantly reduced by N-2 purgin
g of storage solutions to remove dissolved O-2 and was mimicked by fre
sh, carboxyl difunctionalized PEG 3400 (diSPA-PEG 3400) coatings of si
milar surface density. The mE-, diE-, and diSPA-based coatings studied
appeared to exhibit similar grafting densities (approximate to 0.1/nm
(2)) and coating thicknesses (7 nm), suggesting grafting at only one e
nd group. The factors responsible for limiting surface reaction by bot
h end groups aided the ability of the diE-PEG coatings to secondarily
tether (approximate to 0.04/nm(2)) a model amine-containing compound (
n-propylamine) at the diE-PEG-coated quartz surface. Results are discu
ssed in relation to practical applications.