Controllable Wrinkling Patterns on Chitosan Microspheres Generated from Self-Assembling Metal Nanoparticles

Materials with surface wrinkles at a micro/nanoscale possess extraordinary fascinating properties, and various techniques have been employed to create controllable wrinkles. Herein, natural polysaccharide was used to construct the surface wrinkled microsphere with controllable wrinkling patterns. A robust microsphere with an average size of about 55 μm fabricated from chitosan in alkali/urea aqueous solution was swelled and then coated orderly by introducing rigid silver nanoparticles (Ag NPs) with an average size of about 5 nm as the shell onto the surface through electrostatic layer-by-layer (LBL) self-assembly followed by deswelling, resulting in a surface wrinkled microsphere. The significant difference in the swelling behaviors between the stiff Ag shell and swelled chitosan microsphere could generate enough driving forces to form 3D micro- and nanoscale wrinkling surface topography. The surface wrinkled microspheres exhibited the hierarchically porous structure and hydrophobicity, and the topographical patterns could be adjusted by controlling the thickness of the Ag NP layer to achieve the sizes of wrinkling ranging from 60 to 300 nm. It was demonstrated that the wrinkled microspheres were superior as 3D surface-enhanced Raman spectroscopy (SERS) substrates, in which the wrinkled structure with spatial periodicity was proved to be effective for enhancing the SERS signal. The microsphere with controllable wrinkled surface topography could be applied to be a miniature 3D device, which promises potential technological applications in various areas.