Quasi‐3D‐Structured Interfaces by Polymer Brushes

Abstract

The fabrication of polymer brushes via surface-initiated controlled radical polymerizations has progressively developed beyond a simple surface functionalization technique, enabling the design of complex polymer interfaces with a quasi-3D molecular organization. The modulation of polymer brush structure has led to an extremely broad tuning potential for technologically relevant interfacial, physicochemical properties, allowing one to precisely tune swelling, nanomechanical, and nanotribological characteristics of polymer films. In addition, the synthesis of multilayer brush interfaces with hierarchical architecture has been exploited to control biological phenomena on modified platforms, such as cell adhesion and settlement, or to fully prevent biological contamination from bacteria. In this feature article, the most recent developments in the synthesis and application of quasi-3D structured polymer brushes are summarized, placing particular attention on how the tuning of grafted-polymer architecture could translate into a variation of interfacial characteristics.

Conformational Distributions near and on the Substrate during Surface-Initiated Living Polymerization: A Lattice-Based Kinetic Monte Carlo Approach

“…a height of 20 nm and the maximal height is ca . 30 nm, highlighting the physical relevance of the kMC study with experimental studies, also putting forward such typical heights. ,,,,, …”

“…30 nm, highlighting the physical relevance of the kMC study with experimental studies, also putting forward such typical heights. 9,16,25,26,65,66 From the explicit visualization of individual polymer chains on the surface in Figure 6, important characteristics of the macromolecular size and shape per chain such as the squared end-to-end distance (R e,surf 2 ) and the squared radius of gyration (R g,surf 2) can be determined in a next stage at any synthesis time, being the core novelty of the present work. In this context, Figure 7a shows the ratio of the mean-squared end-to-end distance to the mean-squared radius of gyration (⟨R e,surf 2 ⟩/ ⟨R g,surf 2 ⟩) as a function of chain length.…”

“…The tailoring of the physicochemical properties of organic and inorganic substrates through the in situ formation of polymer layers has attracted great attention in recent decades. − Specific focus has been on designing polymer chains tethered by at least one chain-end to flat or curved surfaces for corrosion-protection coatings, adhesives, protein-resistant biosurfaces, chemical lubricants, and polymeric vehicles for controlled release of active compounds. − Hence, the synthesis of well-defined surface-tethered polymer structures constitutes the molecular basis for the development of advanced functional surfaces.…”

Self-Adaptive Antibacterial Coating for Universal Polymeric Substrates Based on a Micrometer-Scale Hierarchical Polymer Brush System

“…Previous attempts based on polymer brushes surface modification have been made to integrate the strength of both antiadhesive and bactericidal mechanisms into a single platform. , The most common strategy for dual-function polymer brush design is based on random copolymer or binary mixed brushes. However, the resulting brushes share the single-layer architecture essentially, which generally compromises one performance when pursuing the other due to the random arrangement and spatial interference of different functional units. − Another common strategy involves multilayered polymer brushes with the unique hierarchical architecture, which have been exploited for many biological applications such as antigen detection, − cell adhesion, , and protein adsorption. − Lately, our group has devised many types of multimodal antibacterial surfaces based on hierarchical polymer brushes, in which different functional blocks possessed the well-defined spatial distribution and exerted the antiadhesive and bactericidal properties separately but complementarily. The hierarchical polymer brushes serve as a modular platform to facilely tune each functionality through architectural and compositional changes and, more importantly, to implement functions in a collaborative manner.…”

Sculpting Enzyme-Generated Giant Polymer Brushes

“…Three-dimensional nanostructured polymer brushes are finding increasing applications in materials science, chemistry, and the biosciences. − Polymer brush gradients and other topographies have been used in combinatorial studies of a broad range of physiochemical phenomena, − enable the directed transport of soft materials like nanoparticles and cells, , facilitate the screening of design strategies for protein and cell–substrate interactions, , and are useful tools in expediently exploring the fundamental behavior of the brushes. ,,, Sculpted brushes can also be used to tune the local environment ( e.g ., porosity, stiffness, roughness) , or orchestrate the organization of complex materials such as structured nanoparticle-polymer film composites. − …”