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We review various methods to investigate the statics and the dynamics of collective composition fluctuations in dense polymer mixtures within fluctuating-field approaches. The central idea of fluctuating-field theories is to rewrite the partition function of the interacting multi-chain systems in terms of integrals over auxiliary, often complex, fields, which are introduced by means of appropriate Hubbard--Stratonovich transformations. Thermodynamic averages such as the average composition and the structure factor can be expressed exactly as averages of these fields. We discuss different analytical and numerical approaches to studying such a theory: The self-consistent field approach solves the integrals over the fluctuating fields in saddle-point approximation. Generalized random phase approximations allow one to incorporate Gaussian fluctuations around the saddle point. Field theoretical polymer simulations are used to study the statistical mechanics of the full system with Complex Langevin or Monte Carlo methods. Unfortunately, they are hampered by the presence of a sign problem. In a dense system, the latter can be avoided without losing essential physics by invoking a saddle point approximation for the complex field that couples to the total density. This leads to the external potential theory. We investigate the conditions under which this approximation is accurate. Finally, we discuss recent approaches to formulate realistic time evolution equations for such models. The methods are illustrated by two examples: A study of the fluctuation-induced formation of a polymeric microemulsion in a polymer-copolymer mixture and a study of early-stage spinodal decomposition in a binary blend. [ABSTRACT FROM AUTHOR]

Compression and interpenetration of two opposing polymer brushes formed by end-grafted adsorption-active chains are studied by the numerical self-consistent field approach and by analytical theory. For sufficiently strong polymer–surface attraction, a fraction of chains in the adsorption-active brush condenses into a near-surface layer, while the remaining ones form the outer brush with reduced effective grafting density. Analysis shows that the normal pressure in adsorption-active brushes can be understood in terms of the effective grafting density concept although the pressure at small separations is affected by the presence of the dense adsorbed phase. We propose a simple theory modification that accounts for this effect. We also formulate a procedure for extracting the value of the effective grafting density directly from the pressure vs separation curves by inverting the equation of state. In contrast to the normal pressure, the interpenetration of the two opposing adsorption-active brushes demonstrates a much more intricate behavior. At weak to moderate compressions, the effective grafting density concept works well but fails spectacularly at small interbrush separations. We identify two interpenetration regimes for adsorption-active brushes: (i) at separations larger than the ideal Gaussian coil size N1/2, the overlap of the two brushes is concentrated in the mid-plane region, in the same way as in brushes grafted onto non-attractive surfaces; (ii) at separations less than N1/2, the brush overlap is strongly enhanced in the wall regions where the attractive interaction plays an important role both in generating the dense layer for the "proper" brush and in attracting the "foreign" chains. [ABSTRACT FROM AUTHOR]

A combination of atomistic molecular dynamics (aMD) simulations and circular dichroism (CD) analysis is used to explore supramolecular structures of amphiphilic ABA‐type triblock polymer peptide conjugates (PPC). Using the example of a recently introduced PPC with pH‐ and temperature responsive self‐assembling behavior [Otter et al., Macromolecular Rapid Communications 2018, 39, 1800459], this study shows how molecular dynamics simulations of simplified fragment molecules can add crucial information to CD data, which helps to correctly identify the self‐assembled structures and monitor the folding/unfolding pathways of the molecules. The findings offer insights into the nature of structural transitions induced by external stimuli, thus contributing to the understanding of the connection of microscopic structures with macroscopic properties. [ABSTRACT FROM AUTHOR]