Macromolecules, Vol.44, No.11, 4520-4529, 2011
Bond Tension in Tethered Macromolecules
The paper presents scaling analysis of mechanical tension generated in densely branched macromolecules tethered to a solid substrate with a short linker. Steric repulsion between branches results in z-fold amplification of tension in the linker, where z is the number of chain-like arms. At large z similar to 100-1000, the generated tension may exceed the strength of covalent bonds and sever the linker. Two types of molecular architectures were considered: polymer stars and polymer "bottlebrushes" tethered to a solid substrate. Depending on the grafting density, one distinguishes the so-called mushroom, loose grafting, and dense grafting regimes. In isolated (mushroom) and loosely tethered bottlebrushes, the linker tension is by a factor of root z smaller than the tension in a tethered star with the same number of arms z. In densely tethered stars, the effect of interchain distance (d) and number of arms (z) on the magnitude of linker tension is given by f congruent to f(o)z(3/2) (b/d) for stars in a solvent environment and f congruent to f(o)z(2)(b/d)(2) for dry stars, where b is the Kuhn length and f(o) congruent to k(B)T/b is intrinsic bond tension. These relations are also valid for tethered bottlebrushes with long side chains. However, unlike molecular stars, bottlebrushes demonstrate variation of tension along the backbone f congruent to f(o)z(1/2)/d as a function of distance s from the free end of the backbone. In dense brushes (d congruent to Vi) with z congruent to m 1000, the backbone tension increases from f congruent to f(o) congruent to 1 pN at the free end of the backbone (s congruent to b) to its maximum f congruent to zfo congruent to 1 nN at the linker to the substrate (s congruent to zb).