Structure and position-dependent properties of inhomogeneous suspensions of responsive colloids


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Responsive particles, such as biomacromolecules or hydrogels, display a broad and polymodal distribution of conformations and have thus the ability to change their properties (e.g, size, shape, charge density, etc.) substantially in response to external fields or to their local environment (e.g., mediated by cosolutes or pH). Here, we discuss the basic statistical mechanics for a model of responsive colloids (RCs) by introducing an additional property degree of freedom as a collective variable in a formal coarse-graining procedure. The latter leads to an additional one-body term in the coarse-grained (CG) free energy, defining a single-particle property distribution for an individual polydisperse RC. We argue that in the equilibrium thermodynamic limit such a CG system of RCs behaves like a conventional polydisperse system of non-responsive particles. We then illustrate the action of external fields, which impose local (position-dependent) property distributions leading to non-trivial effects on the spatial one-body property and density profiles, even for an ideal (non-interacting) gas of RCs. We finally apply density functional theory in the local density approximation (LDA-DFT) to discuss the effects of particle interactions for specific examples of i) a suspension of RCs in an external field linear in both position and property, ii) a suspension of RCs with highly localized properties (sizes) confined between two walls, and iii) a two-component suspension where an inhomogeneously distributed (non-responsive) cosolute component, as found, e.g., in the studies of osmolyte- or salt-induced collapse/swelling transitions of thermosensitive polymers, modifies the local properties and density of the RC liquid.

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