Thermal Degradation of Adsorbed Bottle-Brush Macromolecules: Molecular Dynamics Simulation

The scission kinetics of bottle-brush molecules in solution and on an adhesive substrate is modeled by means of Molecular Dynamics simulation with Langevin thermostat. Our macromolecules comprise a long flexible polymer backbone with $L$ segments, consisting of breakable bonds, along with two side chains of length $N$, tethered to each segment of the backbone. In agreement with recent experiments and theoretical predictions, we find that bond cleavage is significantly enhanced on a strongly attractive substrate even though the chemical nature of the bonds remains thereby unchanged. We find that the mean bond life time $<tau>$ decreases upon adsorption by more than an order of magnitude even for brush molecules with comparatively short side chains $N=1 div 4$. The distribution of scission probability along the bonds of the backbone is found to be rather sensitive regarding the interplay between length and grafting density of side chains. The life time $<tau>$ declines with growing contour length $L$ as $<tau>propto L^{-0.17}$, and with side chain length as $<tau>propto N^{-0.53}$. The probability distribution of fragment lengths at different times agrees well with experimental observations. The variation of the mean length $L(t)$ of the fragments with elapsed time confirms the notion of the thermal degradation process as a first order reaction.

Applications of a generalization of the nonlinear sigma model with O(d) group of symmetry to the dynamics of a constrained chain

Subject of this work are the applications of a field theoretical model, called here generalized nonlinear sigma model or simply GNLSM,to the dynamics of a chain subjected to constraints. Chains with similar properties and constraints have been discussed in a seminal paper of Edwards and Goodyear using an approach based on the Langevin equation. The GNLSM has been proposed in a previous publication in order to describe the dynamics of a two dimensional chain. In this paper the model is extended to d dimensions and a bending energy term is added to its action. As an application, two observables are computed in the case of a very stiff chain. The first observable is the dynamical form factor of a ring shaped chain. The second observable is a straightforward generalization to dynamics of the static form factor. This observable is relevant in order to estimate the average distance between two arbitrary points of the chain. Finally, a variant of the GNLNM is presented, in which the topological conditions which constrain the motion of two linked chains are imposed with the help of the Gauss linking invariant.