A series of nanoparticles with phase-separated structures by 1,1-diphenylethene controlled one-step soap-free emulsion copolymerization and their application in drug release
A facile one-step approach to synthesize various phase-separated porous, raspberry-like, flower-like, core–shell and anomalous nanoparticles and nanocapsules via 1,1-diphenylethene (DPE) controlled soap-free emulsion copolymerization of styrene (S) with glycidyl methacrylate (GMA), or acrylic acid (AA) is reported. By regulating the mass ratio of S/GMA, transparent polymer solution, porous and anomalous P(S-GMA) particles could be produced. The P(S-GMA) particles turn from flower-like to raspberry-like and then to anomalous structures with smooth surface as the increase of divinylbenzene (DVB) crosslinker. Transparent polymer solution, nanocapsules and core–shell P(S-AA) particles could be obtained by altering the mole ratio of S/AA; anomalous and raspberry-like P(S-AA) particles are produced by adding DVB. The unpolymerized S resulted from the low monomer conversion in the presence of DPE aggregates to form nano-sized droplets, and migrates towards the external surfaces of the GMA-enriched P(S-GMA) particles and the internal bulk of the AA-enriched P(S-AA) particles. The nano-sized droplets function as in situ porogen, porous P(S-GMA) particles and P(S-AA) nanocapsules are produced when the porogen is removed. This novel, facile, one-step method with excellent controllability and reproducibility will inspire new strategies for creating hierarchical phase-separated polymeric particles with various structures by simply altering the species and ratio of comonomers. The drug loading and release experiments on the porous particles and nanocapsules demonstrate that the release of doxorubicin hydrochloride is very slow in weakly basic environment and quick in weakly acidic environment, which enables the porous particles and nanocapsules with promising potential in drug delivery applications.
Keywordsphase separation 1,1-diphenylethene controlled polymerization porous nanocapsules controlled release
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- Hu, R.; Yang, C. B.; Wang, Y. C.; Lin, G. M.; Qin, W.; Ouyan, Q. L.; Law, W. C.; Nguyen, Q. T.; Yoon, H. S.; Wang, X. M. et al. Aggregation-induced emission (AIE) dye loaded polymer nanoparticles for gene silencing in pancreatic cancer and their in vitro and in vivo biocompatibility evaluation. Nano Res. 2015, 8, 1563–1576.CrossRefGoogle Scholar
- Zůrková, E.; Bouchal, K.; Zdeňková, D.; Pelzbauer, Z.; Svec, F.; Kálal, J.; Batz, H. G. Preparation of monodisperse reactive styrene-glycidyl methacrylate latexes by the emulsifier- free dispersion copolymerization technique. J. Polym. Sci.: Polym. Chem. Ed. 1983, 21, 2949–2960.Google Scholar
- Gerweck, L. E.; Seetharaman, K. Cellular pH gradient in tumor versus normal tissue: Potential exploitation for the treatment of cancer. Cancer Res. 1996, 56, 1194–1198.Google Scholar