L. Gutman et Ak. Chakraborty, A FIELD-THEORY OF RANDOM HETEROPOLYMERS NEAR SOLID-SURFACES - ANALYSIS OF INTERFACIAL ORGANIZATION AND ADSORPTION-DESORPTION PHASE-DIAGRAM, The Journal of chemical physics, 103(24), 1995, pp. 10733-10750
Understanding the interfacial organization of heteropolymers near soli
d surfaces is an issue of fundamental interest that is relevant for ma
ny technological and biological applications. In this paper we address
several questions pertaining to the surface-induced ordering and the
adsorption-desorption phase behavior of a dilute solution of two-lette
r random heteropolymers interacting with a solid surface. Our analysis
is based on a statistical field theoretic formulation of the propagat
or for the problem of interest. We employ the replica trick to allevia
te analytical difficulties which arise when considering averaging over
the sequence distribution of the A and the B units. In order to highl
ight the effects of the surface, we consider the situation wherein the
intersegment interactions are of the excluded volume type while the s
egment-surface interactions of the A and B segments are arbitrarily di
fferent. Within the replica symmetric solution, we show that proper co
arse-graining of the interaction potentials leads to exact analytical
expressions for the self-consistent propagator of the heteropolymer at
theta conditions and for the case where excluded volume interactions
prevail. One of our interesting findings is that heteropolymers underg
o an adsorption-desorption transition in the vicinity of a surface tha
t interacts with the different types of segments in arbitrarily differ
ent ways. This is consistent with our previous numerical findings for
much more restricted circumstances. We explicitly analyze the influenc
e of the fluctuations in the sequence distribution on the conformation
al organization of the adsorbed chains and obtain the scaling behavior
of properties of interest in the vicinity of the adsorption-desorptio
n threshold with respect to the disorder strength and other polymer in
teraction parameters. Specifically, invoking the Ehrenfest theorem we
find that the adsorption-desorption transition at theta conditions is
a second-order phase transition while in the case where excluded volum
e interaction prevails the transition becomes first order. We also obt
ain exact analytical expressions for the adsorption-desorption thresho
ld. The threshold exhibits quite an unusual dependence on the strength
of the disorder. Finally, we compute the point of onset of repulsive
forces between plates that confine a random copolymer solution as a fu
nction of chain sequence distribution. We suggest specific experiments
employing the surface force apparatus that could directly test our pr
edictions. (C) 1995 American Institute of Physics.