Fabrication of topologically anisotropic microparticles and their surface modification with pH responsive polymer brush

This paper describes the fabrication of topologically anisotropic cup shaped polylactide (PLA)/poly[methyl methacrylate-co-2-(2-bromopropionyloxy) ethyl methacrylate] (poly(MMA-co-BEMA)) (75/25) composite particles of similar to 6 mu m size using electrojetting technique. An attempt was made to understand the mechanism of cup shape formation from the miscible blend by electrojetting. Both the solution parameters and the processing conditions affected the particles' shape which can be varied from cup shaped to discoid type. Surface initiated atom transfer radical polymerization (ATRP) of stimuli responsive DMAEMA (2-dimethylamino ethyl methacrylate) was subsequently carried out for 1 h onto the surface of cup shaped particles to observe pH responsiveness of the modified anisotropic particles. Interestingly, morphology of the cup shaped particles was changed to elongated cup which did show significant swelling under acidic pH (swelling ratio:similar to 1.6) and enhanced dye adsorption at specific pH as observed by optical microscope and confocal laser scanning microscope implying that DMAEMA polymerization happened onto the surface of the composite microparticles. The Raman microscopy and FTIR spectra obtained from the particles after polymerization further confirmed the immobilization of pH responsive poly(DMAEMA) brushes onto the cup shaped particles which may potentially function as triggered/targeted drug delivery vehicles. Moreover, the brush modified cup shaped particles were found to be two times more efficient in adsorbing dye compared to disc shaped one indicating a clear advantage of using cup shaped particles over other shapes for immobilizing/adsorbing charged species e.g. sensitive biomolecules.