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Spontaneous Formation of Nanoparticles from Peptide-Vinyl Polymer Diblock Hybrids Prepared by RAFT Polymerization and Their Interactions with Cells.

ABSTRACT: Novel polymeric nanoparticles (NPs) with uniform sizes were prepared from peptide-vinyl polymer diblock hybrids by the self-organized precipitation method. Hybrid polymers of polystyrene (PSt) and tetrapeptide (cell-binding epitope RGDS, reverse SDGR, cationic KKKK, and anionic DDDD) were successfully synthesized by combining solid-phase peptide synthesis and reversible addition fragmentation chain transfer polymerization methods. Narrowly dispersed hybrid polymers (polydispersity index < 1.25, M n 14?000-17?000) were obtained. Altering the preparation conditions easily tuned the size and size distribution of the NPs. When the ?-potentials for the NP suspensions were measured at pH 6.0, the obtained values corresponded to the net charge of each peptide segment. More importantly, the NPs could encapsulate fluorescent Nile red (NR) and magnetic iron oxide NP (MNP), which might be suitable for fluorescent imaging and magnet-induced patterning of cells, respectively. The interactions of NPs with cells (NIH/3T3 fibroblast) and the magnetic effects were examined for NR/MNP-loaded PSt-RGDS and -SDGR NPs. Both NPs were readily incorporated into cells, but only NR/MNP-loaded PSt-RGDS NP showed magnetic responsiveness in cell adhesion and cultures.

SUBMITTER: Higashi N

PROVIDER: S-EPMC6648836 | biostudies-literature | 2019 May

REPOSITORIES: biostudies-literature

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Spontaneous Formation of Nanoparticles from Peptide-Vinyl Polymer Diblock Hybrids Prepared by RAFT Polymerization and Their Interactions with Cells.

Higashi Nobuyuki N Narimatsu Kiyoshiro K Okumura Minori M Nishimura Shin-Nosuke SN Koga Tomoyuki T

ACS omega 20190502 5

Novel polymeric nanoparticles (NPs) with uniform sizes were prepared from peptide-vinyl polymer diblock hybrids by the self-organized precipitation method. Hybrid polymers of polystyrene (PSt) and tetrapeptide (cell-binding epitope RGDS, reverse SDGR, cationic KKKK, and anionic DDDD) were successfully synthesized by combining solid-phase peptide synthesis and reversible addition fragmentation chain transfer polymerization methods. Narrowly dispersed hybrid polymers (polydispersity index < 1.25, ...[more]

PMID: 31459901

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Project description:A poly(2-(dimethylamino)ethyl methacrylate) (PDMA) chain transfer agent (CTA) is used for the reversible addition-fragmentation chain transfer (RAFT) alcoholic dispersion polymerization of benzyl methacrylate (BzMA) in ethanol at 70 °C. THF GPC analysis indicated a well-controlled polymerization with molecular weight increasing linearly with conversion. GPC traces also showed high blocking efficiency with no homopolymer contamination apparent and Mw/Mn values below 1.35 in all cases. 1H NMR studies confirmed greater than 98% BzMA conversion for a target PBzMA degree of polymerization (DP) of up to 600. The PBzMA block becomes insoluble as it grows, leading to the in situ formation of sterically stabilized diblock copolymer nanoparticles via polymerization-induced self-assembly (PISA). Fixing the mean DP of the PDMA stabilizer block at 94 units and systematically varying the DP of the PBzMA block enabled a series of spherical nanoparticles of tunable diameter to be obtained. These nanoparticles were characterized by TEM, DLS, MALLS, and SAXS, with mean diameters ranging from 35 to 100 nm. The latter technique was particularly informative: data fits to a spherical micelle model enabled calculation of the core diameter, surface area occupied per copolymer chain, and the mean aggregation number (Nagg). The scaling exponent derived from a double-logarithmic plot of core diameter vs PBzMA DP suggests that the conformation of the PBzMA chains is intermediate between the collapsed and fully extended state. This is in good agreement with 1H NMR studies, which suggest that only 5-13% of the BzMA residues of the core-forming chains are solvated. The Nagg values calculated from SAXS and MALLS are in good agreement and scale approximately linearly with PBzMA DP. This suggests that spherical micelles grow in size not only as a result of the increase in copolymer molecular weight during the PISA synthesis but also by exchange of individual copolymer chains between micelles and/or by sphere-sphere fusion events.

Dataset Information

Spontaneous Formation of Nanoparticles from Peptide-Vinyl Polymer Diblock Hybrids Prepared by RAFT Polymerization and Their Interactions with Cells.

Publications

Spontaneous Formation of Nanoparticles from Peptide-Vinyl Polymer Diblock Hybrids Prepared by RAFT Polymerization and Their Interactions with Cells.

Similar Datasets

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