Controlling the bulk and surface properties of materials is a real challenge for bioengineers working in the fields of biomaterials, tissue engineering and biophysics. The layer-by-layer (LbL) deposition method, introduced 20 years ago, consists in the alternate adsorption of polyelectrolytes that self-organize on the material's surface, leading to the formation of polyelectrolyte multilayer (PEM) films. 1 Because of its simplicity and versatility, the procedure has led to considerable developments of biological applications within the past 5 years. In this review, we focus our attention on the design of PEM films as surface coatings for applications in the field of physical properties that have emerged as being key points in relation to biological processes. The numerous possibilities for adjusting the chemical, physical, and mechanical properties of PEM films have fostered studies on the influence of these parameters on cellular behaviors. Importantly, PEM have emerged as a powerful tool for the immobilization of biomolecules with preserved bioactivity.

Specific targeting is common in biology and is a key challenge in nanomedicine. It was recently demonstrated that multivalent probes can selectively target surfaces with a defined density of surface binding sites. Here we show, using a combination of experiments and simulations on multivalent polymers, that such "superselective" binding can be tuned through the design of the multivalent probe, to target a desired density of binding sites. We develop an analytical model that provides simple yet quantitative predictions to tune the polymer's superselective binding properties by its molecular characteristics such as size, valency, and affinity. This work opens up a route toward the rational design of multivalent probes with defined superselective targeting properties for practical applications, and provides mechanistic insight into the regulation of multivalent interactions in biology. To illustrate this, we show how the superselective targeting of the extracellular matrix polysaccharide hyaluronan to its main cell surface receptor CD44 is controlled by the affinity of individual CD44-hyaluronan interactions.tunability | superselectivity | host-guest multivalent interactions | hyaluronan