title: Design of core--shell-type nanoparticles carrying stable radicals in the core.
abstract: Utilizing the self-assembled core-shell-type polymeric micelle technique, high-performance nanoparticles possessing stable radicals in the core and reactive groups on the periphery were prepared. The anionic ring-opening polymerization of ethylene oxide (EO) was carried out using potassium 3,3-diethoxypropanolate as an initiator, followed by mesylation with methanesulfonyl chloride to obtain acetal-poly(ethylene glycol)-methanesulfonate (acetal-PEG-Ms; 1). Compound 1 was reacted with potassium O-ethyldithiocarbonate, followed by treatment with n-propylamine to obtain heterobifunctional PEG derivatives containing both sulfanyl and acetal terminal groups (acetal-PEG-SH) (2) in a highly selective and quantitative manner. Poly(ethylene glycol)-block-poly(chloromethylstyrene) (acetal-PEG-b-PCMS) (3) was synthesized by the free-radical telomerization of chloromethylstyrene (CMS) using 2 as a telogen. The chloromethyl groups in the PCMS segment of the block copolymer (3) were quantitatively converted to 2,2,6,6-tetramethylpiperidinyloxys (TEMPOs) via the amination of 3 with 4-amino-TEMPO to obtain acetal-PEG-b-PCMS containing TEMPO moieties (4). The obtained 4 formed core-shell-type nanoparticles in aqueous media when subjected to the dialysis method: the cumulant average diameter of the nanoparticles was about 40 nm, and the nanoparticles emitted intense electron paramagnetic resonance (EPR) signals. The TEMPO radicals in the core of the nanoparticles showed reduction resistance even in the presence of 3.5 mM ascorbic acid. This means that these nanoparticles are anticipated as high-performance bionanoparticles that can be used in vivo.
authors.affiliation: Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki, Japan.
authors.forename: Toru
authors.initials: T
authors.lastname: Yoshitomi
authors.forename: Daisuke
authors.initials: D
authors.lastname: Miyamoto
authors.forename: Yukio
authors.initials: Y
authors.lastname: Nagasaki
mesh_terms: D003497:Cyclic N-Oxides / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D046911:Macromolecular Substances / Q000138:chemical synthesis* / Q000737:chemistry; D008823:Micelles; D053758:Nanoparticles / Q000737:chemistry*; D010316:Particle Size; D011092:Polyethylene Glycols / Q000138:chemical synthesis / Q000737:chemistry*; D013499:Surface Properties
chemical_list: D003497:Cyclic N-Oxides; D005609:Free Radicals; D046911:Macromolecular Substances; D008823:Micelles; D011092:Polyethylene Glycols; C003959:TEMPO