Anomalously Shaped Functional Particles Prepared by Thiol-Isocyanate Off-Stoichiometric Click Dispersion Polymerization.

Abstract

Anomalously shaped microparticles have attractive advantages in applications. They are usually prepared by chain-growth polymerizations in heterogeneous systems. Recently, thiol-X step-growth polymerizations have been used to produce functional particles with a regular shape but rarely anomalous shapes. Herein, we report the preparation of anomalously shaped particles by thiol-isocyanate dispersion polymerization (Dis.P) in ethanol using polyvinylpyrrolidone (PVP) as a stabilizer and catalyst. Papillae-shaped, raspberry-like, and multibulged particles are prepared by tuning monomer combinations, contents, and feed ratios. Particle morphology evolutions during polymerization are observed by scanning electron microscopy (SEM). Distinct from previous works, particles with residual -SH groups are obtained even with equal moles of monomers added initially. The residue of -SH groups is revealed by Fourier transform infrared spectroscopy (FT-IR) analyses and confirmed by detection with a fluorescent probe containing disulfide linkage. Moreover, fluorescent particle probes are formed by the reaction of excess -NCO groups on particles with fluorescein isothiocyanate isomer I (FITC) and dithioacetal-functionalized perylenediimide (DTPDI). The probes are sensitive in detection of glutathione (GSH) and Hg2+ in water. Hg2+ as low as 1-0.1 ppb is detected using a raspberry-like particle probe with DTPDI.