Functionalization of Magnetic Nanoparticles with Dendritic–Linear–Brush-Like Triblock Copolymers and Their Drug Release Properties

Novel water-soluble dendritic–linear–brush-like triblock copolymer polyamidoamine-b-poly(2-(dimethylamino)ethyl methacrylate)-b-poly(poly(ethylene glycol) methyl ether methacrylate) (PAMAM-b-PDMAEMA-b-PPEGMA)-grafted superparamagnetic iron oxide nanoparticles (SPIONs) were successfully prepared via...

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Bibliographic Details
Published in:Langmuir 2012-08, Vol.28 (32), p.11929-11938
Main Authors: He, Xiaohua, Wu, Xiaomeng, Cai, Xin, Lin, Shaoliang, Xie, Meiran, Zhu, Xinyuan, Yan, Deyue
Format: Article
Language:English
Subjects:
Animals
Antineoplastic Agents - chemistry
Antineoplastic Agents - metabolism
Antineoplastic Agents - pharmacology
Chemistry
Colloidal state and disperse state
Dendrimers - chemistry
Dendrimers - toxicity
Dendrites - chemistry
Doxorubicin - chemistry
Doxorubicin - metabolism
Doxorubicin - pharmacology
Drug Carriers - chemistry
Drug Carriers - toxicity
Exact sciences and technology
Feasibility Studies
General and physical chemistry
HeLa Cells
Hemolysis - drug effects
Humans
Hydrogen-Ion Concentration
Magnetite Nanoparticles - chemistry
Male
Mice
NIH 3T3 Cells
Physical and chemical studies. Granulometry. Electrokinetic phenomena
Polymers - chemistry
Polymers - toxicity
Polymethacrylic Acids - chemistry
Polymethacrylic Acids - toxicity
Rabbits
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Summary:Novel water-soluble dendritic–linear–brush-like triblock copolymer polyamidoamine-b-poly(2-(dimethylamino)ethyl methacrylate)-b-poly(poly(ethylene glycol) methyl ether methacrylate) (PAMAM-b-PDMAEMA-b-PPEGMA)-grafted superparamagnetic iron oxide nanoparticles (SPIONs) were successfully prepared via a two-step copper-mediated atom transfer radical polymerization (ATRP) method. The macroinitiators were immobilized on the surface of Fe3O4 nanoparticles via effective ligand exchange of oleic acid with the propargyl focal point PAMAM-typed dendron (generation 2.0, denoted as propargyl-D2.0) containing four carboxyl acid end groups, following a click reaction with 2′-azidoethyl-2-bromoisobutylate (AEBIB). PDMAEMA and PPEGMA were grown gradually from nanoparticle surfaces using the “grafting from” approach, which rendered the SPIONs soluble in water and reversed aggregation. To the best of our knowledge, this is the first report that describes the functionalization of magnetic nanoparticles with dendritic–linear–brush-like triblock copolymers. The modified nanoparticles were systematically studied via TEM, FT-IR, DLS, XRD, NMR, TGA, and magnetization measurements. DLS measurement confirmed that the obtained dendritic–linear–brush-like triblock copolymer-grafted SPIONs had a uniform hydrodynamic particle size of average diameter less than 30 nm. The dendritic–linear–brush-like triblock copolymer-grafted SPIONs possessed excellent biocompatibility by methyl tetrazolium (MTT) assays against NIH3T3 cells and hemolysis assays with rabbit erythrocytes. Furthermore, an anticancer drug, doxorubicin (Dox), was used as a model drug and loaded into the dendritic–linear–brush-like triblock copolymer-grafted SPIONs, and subsequently, the drug releases were performed in phosphoric acid buffer solution pH = 4.7, 7.4, or 11.0 at 37 °C. The results verify that the dendritic–linear–brush-like triblock copolymer-grafted SPIONs possess pH-responsive drug release behavior. The Dox dose of the loaded and free drug required for 50% cellular growth inhibition was 2.72 and 0.72 μm/mL, respectively, according to MTT assay against a Hella cell line in vitro. Therefore, on the basis of its biocompatibility and drug release effect, the modified SPION could provide a charming opportunity to design some excellent drug delivery systems for therapeutic applications.
ISSN:0743-7463
1520-5827
DOI:10.1021/la302546m