Extensive computer simulation was performed using the bond‐fluctuation model and cellular‐automaton (CA)‐based simulation technique to probe the equilibrium structure and dynamical behavior of comb‐branched polymers in which the flexible side chains of a given length are placed regularly along the backbone and the number of branches increases linearly with total molecular weight. By applying very efficient CA algorithm – the “lattice molecular dynamics” (LMD) method – we have been able to study the properties of sufficiently large structures (up to 5880 monomeric units). Depending on the length of main and side chains as well as on interbranch spacing, we have calculated mean chain dimensions, local fractal dimensionalities, particle scattering functions, time autocorrelation functions, etc. The following main conclusions may be drawn from the results presented in our study: (i) The critical exponent, governing the mean size of the main chain, remains unchanged from its value known for a 3d self‐avoiding walk (SAW). On the other hand, two‐dimensional branched macromolecules with one‐sided branches are effectively in a collapsed state even under conditions of a good solvent, forming specific helical superstructures. (ii) Comparison of the simulated data with the predictions of the scaling model indicates that the latter is valid in describing the mean dimensions of the backbone as a function of side‐chain length and interbranch spacing. (iii) The excluded volume interaction between side chains dramatically slows down the relaxation of the backbone chain.

Conformational properties of comb-like polymers strongly adsorbed on a flat solid surface were investigated using computer simulation and scanning force microscopy. The computer simulation showed that the macromolecules with asymmetric distribution of the side chains relatively to the backbone are effectively in a collapsed state even under conditions of a good solvent. They formed peculiar helical superstructures which could be observed by scanning force microscopy of cylindrical brushes of polymethylmethacrylate on mica.

A new approach to synthesis of copolymers with long-range correlations is proposed. Using Monte Carlo simulations and the lattice bond-fluctuation model, we perform the computer-aided sequence design of a two-letter (AB) copolymer with quenched primary structure near a chemically homogeneous impenetrable surface. We simulate an irreversible radical copolymerization of selectively adsorbed A and B monomers with different affinity to the surface, allowing for a strong short-range monomer-(A-) surface attraction. To describe the chain growth analytically, we introduce and investigate a simple theoretical model based on stochastic processes and probabilistic statistics. We find that this model provides a close approximation to the simulation data and explains a number of statistical properties of copolymer sequences. It is shown that, under certain conditions, the chain propagation near the adsorbing surface proceeds as a randomly alternating growth, leading to a copolymer with a specific quasi-gradient primary structure and power-law long-range correlations in distribution of different monomer units along the chain. The gradient extends along the entire chain for any chain length. We find that the statistical properties of the copolymer sequences correspond to those of a one-dimensional fractal object with scaleinvariant correlations. Thus, just by radical copolymerization of two monomers with different affinity to a certain plane surface, it is possible to obtain copolymers with a gradient primary structure.