Host-guest self-assembly toward reversible visible-light-responsive switching for bacterial adhesion

Here we report a facile method to construct reversible visible-light-responsive switching from antibacterial to bioadhesion by host-guest self-assembly of β-cyclodextrin (β-CD) and azobenzene functionalized polycation/polyanion. The visible-light-responsible azobenzene functionalized polycation, poly{6-[(2,6-dimethoxyphenyl)azo-4-(2',6'-dimethoxy)phenoxy]propyl dimethylaminoethyl methacrylate-random-poly(2-(N,N-dimethylaminoethyl) methacrylate) (Azo-PDMAEMA), was synthesized via quaternization reaction between 2,6,2',6'-tetramethoxy-4-(3-bromopropoxy)azobenzene (AzoOMeBr) and poly(2-(N,N-dimethylaminoethyl) methacrylate) (PDMAEMA), and the polyanion, poly{6-[(2,6-dimethoxyphenyl)azo-4-(2',6'-dimethoxy) phenoxy]hexyl acrylate-random-acrylic acid} (Azo-PAA), was synthesized via esterification reaction between 2,6,2',6'-tetramethoxy-4-(6-hydroxyhexyloxy) azobenzene (AzoOMeOH) and poly(acryloyl chloride) (PAC) and subsequent hydrolysis reactions. The switch surface could be achieved via the alternate host-guest assembly of Azo-PDMAEMA and Azo-PAA onto a β-CD-terminated substratum (Sub-CD) through visible light irradiation. The positively charged Azo-PDMAEMA with quaternary ammonium groups exhibited antimicrobial properties and few bacteria were adhered on the surface, while the negatively charged Azo-PAA with carboxyl acid groups exhibited excellent bioadhesive properties and a large number of bacteria were adhered. Interestingly, the switch between antibacterial and bioadhesive could be realized upon visible light irradiation via alternate assembly of Azo-PDMAEMA and Azo-PAA. The proposed approach to manufacturing visible-light-responsive surface with reversible and alterable biofunctionality switching between antibacterial and bioadhesive is simple and efficient, which is promising for preparation of multifunctional polymeric surfaces to encounter multifarious demands for the biomedical and biotechnological applications.

Light has attracted great attention in building biointerfaces for its precise spatiotemporal control and convenient operation. However, UV light may damage to biological samples and living tissues, which will limit its applications. This study demonstrates a novel visible-light-responsive surface fabricated through reversible assembly of azobenzene functionalized polycations/polyanions on cyclodextrin (CD)-terminated substrate by host-guest interactions between the visible-light-responsive azobenzene mAzo and CD, which has not been examined previously. It is noted that the azobenzene functionalized polycations show strong antibacterial activities, while the polyanions show excellent bioadhesive properties, as can be switched through the alternate assembly upon visible-light irradiation. This facile and versatile approach to visible-light-responsive surfaces holds great potential for switching of bioadhesion.