Photoreactive, core–shell cross-linked/hollow microspheres prepared by delayed addition of cross-linker in dispersion polymerization for antifouling and immobilization of protein

When dispersion polymerization of styrene (St) had run for 3 h, after particle rapidly growing stage, 4,4′-dimethacryloyloxybenzophenone (DMABP) cross-linker was added to reaction system and photoreactive, core(PSt)–shell(Poly(St-co-DMABP)) particles with rich benzophenone (BP) groups on surface were prepared. Polymerization of DMABP could occurred mainly on the preformed core of PSt because its diffusion could be impeded by (1) compactness of particles formed at the moment of cross-linker addition (more than 80% of monomer had been consumed, particles were no longer fully swollen by monomer), (2) reduced polarity of continuous phase, and (3) immediate occurrence of cross-linking. Subsequently, photoreactive, cross-linked hollow particles were yielded by removal of uncross-linked core in THF. SEM and TEM observation demonstrated the formation of core–shell structure and improvement of shell thickness when DMABP content increased. UV–vis spectra analysis on polymer dissolved in THF indicated that there is no polymer of DMABP in core. FTIR spectra analysis and XPS measurement further revealed that BP component on particle surface was enriched when amount of DMABP increased. Finally, an anti-fouling polymer (poly (ethylene glycol), PEG) and protein of mouse IgG was immobilized on particle surface under UV irradiation, as confirmed by FTIR spectra analysis, SEM observation and TMB color reaction.

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► Photoreactive core–shell/hollow particles were prepared by delaying addition of DMABP to dispersion polymerization.
► Mechanism for formation of cross-linked shell in one-pot was discussed.
► Volumes of photoreactive BP moieties were incorporated on particle surface.
► PEG (4 0 0) and protein of mouse IgG were photoimmobilized on particles.