Carbohydrate‐Based Polymer Brushes Prevent Viral Adsorption on Electrostatically Heterogeneous Interfaces

Abstract

Chemical heterogeneity on biomaterial surfaces can transform its interfacial properties, rendering nanoscale heterogeneity profoundly consequential during bioadhesion. To examine the role played by chemical heterogeneity in the adsorption of viruses on synthetic surfaces, a range of novel coatings is developed wherein a tunable mixture of electrostatic tethers for viral binding, and carbohydrate brushes, bearing pendant α‐mannose, β‐galactose, or β‐glucose groups, is incorporated. The effects of binding site density, brush composition, and brush architecture on viral adsorption, with the goal of formulating design specifications for virus‐resistant coatings are experimentally evaluated. It is concluded that virus‐coating interactions are shaped by the interplay between brush architecture and binding site density, after quantifying the adsorption of adenoviruses, influenza, and fibrinogen on a library of carbohydrate brushes co‐immobilized with different ratios of binding sites. These insights will be of utility in guiding the design of polymer coatings in realistic settings where they will be populated with defects.

Glycopolymer Brushes by Reversible Deactivation Radical Polymerization: Preparation, Applications, and Future Challenges

“…Surface modification with thin polymer films forming polymeric brushes is considered one of the most promising ways to obtain “smart” surfaces, which can change some of their physicochemical properties (e.g., solubility) as a response to external stimuli (e.g., pH) or present desired functionality for targeted applications (e.g., carbohydrate-recognition ability by lectins) [ 17 ]. On this matter, both SI-ATRP and SI-RAFT polymerization are very robust and versatile techniques to prepare such materials, as they allow the control of different polymer features, like degree of polymerization, brush grafting density, surface geometry, and film thickness at the nanoscale level [ 17 , 18 , 19 ]. However, the high grafting density can cause steric hindrance problems that are worsen by the brushes restricted mobility imposed by the attachment to surfaces, that in turn can negatively influence the performance of these materials, like their ability to be recognized by lectins [ 28 ].…”

“…Preliminary studies also releveled that mannose can interact with the FimH (mannose specific bacterial lectin) receptors, thus preventing or diminishing the adhesion of bacteria on mannose-containing surfaces [ 86 ]. In this vein, mannose-based polymer brushes have been also proposed for the preparation of antiviral surfaces [ 18 , 69 ]. Chemical vapor deposition polymerization was used to synthesize bromine-functionalized coatings, from which mannose-based glycopolymer brushes were grafted by SI-ATRP [ 18 ].…”

“…In this vein, mannose-based polymer brushes have been also proposed for the preparation of antiviral surfaces [ 18 , 69 ]. Chemical vapor deposition polymerization was used to synthesize bromine-functionalized coatings, from which mannose-based glycopolymer brushes were grafted by SI-ATRP [ 18 ]. Aminomethyl (AM) groups were also introduced in the coating to evaluate the influence of the heterogeneity of the surface on its performance, mimicking the positively charged regions that sometimes are created during the synthesis of glycopolymer brushes.…”

“…Sorbitol is a sugar-derived alcohol commonly used as an excipient in drug formulations and as a sugar substitute to sweeten candies, gums, and baked goods [ 114 ]. Potential antiviral sorbitol-containing polymer brushes grafted from surfaces have been prepared by the same research group that reported the synthesis of mannose-based brushes for antiviral purposes ( Figure 8 ) [ 18 ], following a similar strategy (i.e., comparing the performance of the sugar-based brush in the presence and absence of AM groups, which can act as binding sites for virus) [ 111 ]. The authors started this study by testing the sorbitol-free surface and found that increased concentration of AM groups led to faster adsorption of virus-like NPs.…”

“…Glycopolymer-coated surfaces are especially relevant considering the development of materials with anti-adhesive properties for applications on the biomedical field (e.g., implants) [17]. Studies showed that regardless the methodology used for the synthesis of glycopolymer brushes, it is known that a high brush density is required to enhance lectin-binding, thus preventing non-specific protein, cellular and bacterial adhesion to coated surfaces [18]. This review presents and discusses the literature describing the preparation and application of well-defined brush-like glycopolymers using mono or disaccharides monomer structures, by RDRP techniques.…”