Bilateral Project Romania-France 315/14.05.2009 (Dossier 19064SA)
"Syntesis and Characterization of Magnetite-Polyethylene Glycol Nanoparticles"
Project goals :
To prepare, characterize, and analyse the properties of novel coated magnetic particles for biomedical applications.
In particular, magnetic nano-particles of controlled size coated with polyethyleneglycole were prepared. Romania will synthesize and determine the dimensions of particle size and their magnetic properties. France will study rheological and electro-rheological properties of suspensions.
Results of the first year (2009)
According to the discussions between the partners, the several syntheses were performed and the polymers and nano-particles obtained were characterized:
- Stable magnetic colloids, prepared by using siloxane polymer as stabilizer were prepared in silicon fluids (Fig. 1.). The stabilization process was induced by reacting –OH groups of magnetite surfaces with PDMS-TES by two different preparation methods. The magnetite particles covered and uncovered have spherical shapes and nanosizes depending on the synthesis method. The magnetic colloids are stable in time; only up to 5 wt % losses were recorded after 90 days aging. The laser diffractometry measurements of aging dispersions showed that the particles were monodisperse with an average diameter varying from 28 nm to 277 nm (prepared in situ) and 800 nm when the magnetite obtained separately. Rheological studies on aging dispersions illustrated that the viscosity value depends on the molecular weight of carrier, the shear rate, magnetic field value, and applied field intensity and on temperature. Increasing the shear rate the viscosity value is decreasing to a value characteristic of applied magnetic field.
- An amphiphilic graft copolymer having an average of 4-5 carboxyester-terminated PEG grafted sequences on each polydimethylsiloxane main chain was obtained by a multistep procedure (Scheme 1, Fig.2.). Through fluorescence, surface tension and laser diffractometry methods the graft copolymer was proved to undergo micellization in aqueous media. In water, the critical micellization concentrations (CMC) are depending on pH. Two CMC values were established for pH = 4, i.e. CMC1 = 1.01 g/L and CMC2 = 1.73 g/L corresponding to the transition from single chain to multiple chain micelles and to intermicellar agregation, respectively. Between CMC1 and CMC2, the dimensions of micelles are increasing from 18 nm to 46 nm. The graft copolymer was proved to efficiently act as surfactant in the preparation of core-shell microparticles with a hydrophobic siloxane shell.
- Surface-functionalized core-shell magnetic particles were obtained by reacting the hydroxyl groups on the surface of pre-prepared magnetite particles with 3-glycidoxypropyltrimethoxysilane (Fig. 1). Fourier transform infrared spectra indicated that epoxy silane molecules were chemically bound onto the surface of magnetite particles through Fe–O–Si linkages. As proved by atomic force microscopy and environmental scanning microscopy combined with energy dispersive X-ray spectroscopy, particles with average core diameter and shell width of about 700 and 70 nm, respectively, were obtained. The covered magnetite particles showed a lower saturation magnetization (46 emu g-1) as compared to the uncoated magnetite (64 emu g-1) (Fig. 1.)
Results in the second year (2010):
In 2010 stable magnetic colloids were prepared by following steps:
- Coating of Fe3O4 nanoparticles with trimethoxysilanpropylamine (Romania) (Fig. 1.)
- Synthesis of magnetite-double shell particles by two steps (Scheme 2): (a) synthesis of magnetite –polydimethylsiloxane one shell particles; (b) synthesis of hydrophilic magnetite – double shell particles by hydrophobic interaction of single shell particles with polydimethylsiloxane-g-PEG copolymer (Romania). Characterization of core-shell particles is presented in Fig.3-6.
- Synthesis of magnetite-double shell particles with oleic acid (Romania)
- Studies of rheological and electro-rheological properties of suspensions of core-shell particles in presence of DNA and polyamidephosphite. (France).
Publications:
- A. Durdureanu-Angheluta, L.Pricop, I.Stoica, C.-A. Peptu, A.I.Dascalu, N. Marangoci, M.Spulber, M.Pinteala, B.C. Simionescu, « Silicon magnetic fluids based on magnetite particles covered with α-trietoxysilil- polydimethylsiloxane », Journal of Magnetism and Magnetic Materials 322, 2956–2968 (2010)
- L.Pricop, A.Durdureanu-Angheluta, M.Pinteala, M.Spulber, A.Fifere, N.L.Marangoci, A.I.Dascalu, R.Tigoianu, V.Harabagiu, B.C.Simionescu « Synthesis and micellization of polydimethylsiloxane – carboxy-terminated poly(ethylene oxide) graft copolymer in aqueous and organic media », e-Polymers no. 093 (2010).
- A.Durdureanu-Angheluta, I.Stoica, M.Pinteala, L.Pricop, F.Doroftei, V.Harabagiu, B.C.Simionescu, H.Chiriac « Glycidoxypropylsilane-functionalized Magnetite as Precursor for Polymer-covered Core-shell Magnetic Particles », High Performance Polymer, 21, 548-561 (2009).
- T. Budtova, A. Durdureanu-Angheluta, L. Pricop, F. Doroftei, I. Dascalu, A. Fifere, N. Marangoci, B.C. Simionescu, Bioconjugates of PEGulated magnetite particles with DNA, Journal of Biomaterials and Nanobiotechnology – in preparation.
Congress participations
- A. Durdureanu-Angheluta, L. Pricop, M. Pinteala, V. Harabagiu, B. C. Simionescu, PARTICULE MAGNETIQUES “CORE-SHELL“ OBTENU PAR POLYSILOXANES GREFFE AVEC CARBOXYLIQUES GROUPS, IXème Colloque Franco - Roumain sur les Polymères SYNTHESE ET PROPRIETES DES POLYMERES; LES POLYMERES ET L’ENVIRONNEMENT, Alba Iulia, Roumanie 27 – 29 Août 2009.
- Anamaria Durdureanu-Angheluta, Lucia Pricop, Mariana Pinteala, Radu Tigoianu, Iuliana Stoica, Andrei Dascalu, Valeria Harabagiu, Bogdan C. Simionescu, Micellization in amphiphilic siloxane/α-carboxyester-poly(ethylene oxide) graft copolymers solutions. Applications, Frontiers in Macromolecular and Supramolecular Science Second Cristofor I. Simionescu Symposium, Iasi, Romania, 02-03.06.2009
Budget
Budget for the first year of the project:
Financement |
Chercheurs français |
Chercheurs roumains |
Par la France |
2 voyages pour 14 jours |
Les voyages en roumanie |
Par la Roumanie |
3 voyages pour 23 jours. |
Les voyages en France |
Budget for the second year of the project:
Financement |
Chercheurs français |
Chercheurs roumains |
Par la France |
2 voyages pour 14 yours |
Les voyages en Roumanie |
Par la Roumanie |
1 voyage por 25 jours. |
Les voyages en France |
|
Core-shell magnetic particles |
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SEM image of magnetite particles |
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Fig.1. Synthesis and characterization of magnetic particles |
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Fig. 2. 1H-RMN spectrum of PDMSg-PEG-COOH copolymer
Schema 2. Coating of hydrophobic and hydrophilic magnetic particles.
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Fig. 4. High (a) and faze (b) AFM images of Ma/PDMSgPEG-COOH particles (5 x 5 μm2, 22 particles)
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Fig. 6. Magnetisation curbe Ma/PDMSgPEG-COOH particles. |
Bibliografie
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