PEGylated functional nanoparticles from a reactive homopolymer scaffold modified by thiol addition chemistry

Wong, L; Sevimli, S; Zareie, HM; Davis, TP; Bulmus, V

PEGylated functional nanoparticles from a reactive homopolymer scaffold modified by thiol addition chemistry

Wong, L Sevimli, S Zareie, HM Davis, TP Bulmus, V

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Publication Type:: Journal Article
Citation:: Macromolecules, 2010, 43 (12), pp. 5365 - 5375
Issue Date:: 2010-06-22

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Field	Value	Language
dc.contributor.author	Wong, L	en_US
dc.contributor.author	Sevimli, S	en_US
dc.contributor.author	Zareie, HM	en_US
dc.contributor.author	Davis, TP	en_US
dc.contributor.author	Bulmus, V	en_US
dc.date.issued	2010-06-22	en_US
dc.identifier.citation	Macromolecules, 2010, 43 (12), pp. 5365 - 5375	en_US
dc.identifier.issn	0024-9297	en_US
dc.identifier.uri	http://hdl.handle.net/10453/13359
dc.description.abstract	Well-defined reactive polymer scaffolds are useful building blocks for a variety of biomedicine and nanotechnology applications. In this study, we have converted a RAFT-synthesized thiol-functional homopolymer scaffold (poly(pyridyl disulfide ethyl methacrylate), PPDSM) to poly(ethylene glycol) conjugated (PEGylated) nanoparticles via a straightforward approach. Poly(ethylene glycol) (PEG) was grafted to the reduced PPDSM via radical-mediated thiol - ene or Michael additions. The yield of PEG grafting via radical-mediated thiol - ene reaction and Michael addition was 68 ± 2 and 73 ± 1 mol %, respectively, of the total functional groups on the scaffold, as determined by 1H NMR spectroscopy. The grafting yield via Michael addition reactions was non-linearly proportional to the reducing agent concentration used (thus the number of free thiols created on the polymer chain). It was observed by UV - vis spectroscopy that PEG grafting via Michael addition to the PPDSM takes place simultaneously with inter- and intrachain thiol - disulfide exchange reactions. Dynamic light scattering (DLS) measurements of PEG-acrylate (M n = 2000 g/mol) grafted PPDSM (74 mol % grafting yield) in water showed the presence of particles with an average hydrodynamic diameter of 99 ± 8 nm and polydispersity index (PDI) of 0.22 ± 0.02. Atomic force microscopy (AFM) analysis of the same sample revealed the presence of spherical shape particles. 1H NMR analysis of the same PEG grafted PPDSM nanoparticles in different solvents revealed that the PPDSM backbone in water was surrounded by PEG chains. Overall, the results indicate that simply grafting PEG to PPDSM homopolymer scaffold can be a straightforward route to the generation of nanoparticles with a biocompatible, stealth shell, and the present synthetic approach can be exploited further for the generation of PEGylated functional nanoparticles for potential drug delivery applications. © 2010 American Chemical Society.	en_US
dc.relation.ispartof	Macromolecules	en_US
dc.relation.isbasedon	10.1021/ma100221y	en_US
dc.subject.classification	Polymers	en_US
dc.title	PEGylated functional nanoparticles from a reactive homopolymer scaffold modified by thiol addition chemistry	en_US
dc.type	Journal Article
utslib.citation.volume	12	en_US
utslib.citation.volume	43	en_US
utslib.for	0903 Biomedical Engineering	en_US
utslib.for	03 Chemical Sciences	en_US
utslib.for	09 Engineering	en_US
dc.location.activity	ISI:000278631900026	en_US
pubs.embargo.period	Not known	en_US
pubs.organisational-group	/University of Technology Sydney
pubs.organisational-group	/University of Technology Sydney/Faculty of Science
pubs.organisational-group	/University of Technology Sydney/Faculty of Science/School of Mathematical and Physical Sciences
utslib.copyright.status	closed_access
pubs.issue	12	en_US
pubs.publication-status	Published	en_US
pubs.volume	43	en_US

Abstract:

Well-defined reactive polymer scaffolds are useful building blocks for a variety of biomedicine and nanotechnology applications. In this study, we have converted a RAFT-synthesized thiol-functional homopolymer scaffold (poly(pyridyl disulfide ethyl methacrylate), PPDSM) to poly(ethylene glycol) conjugated (PEGylated) nanoparticles via a straightforward approach. Poly(ethylene glycol) (PEG) was grafted to the reduced PPDSM via radical-mediated thiol - ene or Michael additions. The yield of PEG grafting via radical-mediated thiol - ene reaction and Michael addition was 68 ± 2 and 73 ± 1 mol %, respectively, of the total functional groups on the scaffold, as determined by 1H NMR spectroscopy. The grafting yield via Michael addition reactions was non-linearly proportional to the reducing agent concentration used (thus the number of free thiols created on the polymer chain). It was observed by UV - vis spectroscopy that PEG grafting via Michael addition to the PPDSM takes place simultaneously with inter- and intrachain thiol - disulfide exchange reactions. Dynamic light scattering (DLS) measurements of PEG-acrylate (M n = 2000 g/mol) grafted PPDSM (74 mol % grafting yield) in water showed the presence of particles with an average hydrodynamic diameter of 99 ± 8 nm and polydispersity index (PDI) of 0.22 ± 0.02. Atomic force microscopy (AFM) analysis of the same sample revealed the presence of spherical shape particles. 1H NMR analysis of the same PEG grafted PPDSM nanoparticles in different solvents revealed that the PPDSM backbone in water was surrounded by PEG chains. Overall, the results indicate that simply grafting PEG to PPDSM homopolymer scaffold can be a straightforward route to the generation of nanoparticles with a biocompatible, stealth shell, and the present synthetic approach can be exploited further for the generation of PEGylated functional nanoparticles for potential drug delivery applications. © 2010 American Chemical Society.

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