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Synthesis and functionalization of rod-like iron oxide nanoparticles
Jéssica Alves Marins, Tom Montagnon, Hinda Ezzaier, Agnès Bée, Delphine Talbot, O. Sandre, Dalis Baltrunas, K Mazeika, Alexander Petrov, N
Kalanda, et al.
To cite this version:
Jéssica Alves Marins, Tom Montagnon, Hinda Ezzaier, Agnès Bée, Delphine Talbot, et al.. Synthesis and functionalization of rod-like iron oxide nanoparticles. GDR SLaMM, Nov 2019, Roscoff, France. �hal-02426129�
Synthesis and functionalization of rod-like iron oxide nanoparticles
J.Alves Marins
1
, T.Montagnon
1
, H.Ezzaier
1,2
, A.Bee
3
, D.Talbot
3
, O.Sandre
4
, D.Baltrunas
5
, K.Mazeika
5
, A.Petrov
6
, N.Kalanda
6
, P.Kuzhir
1*
1
University Côte d’Azur, CNRS UMR 7010 Institute of Physics of Nice, Parc Valrose 06108 Nice, France
2
Laboratory of Physics of Lamellar Materials and Hybrid Nano-Materials, Faculty of Sciences of Bizerte, University of Carthage, 7021 Zarzouna, Tunisia
3
University Pierre and Marie Curie, CNRS UMR 8234 PHENIX - CC51 - 4 Place Jussieu, 75252 Paris, France
4
University of Bordeaux, CNRS UMR 5629, Laboratoire de Chimie des Polymères Organiques, ENSCBP 16 avenue Pey Berland 33607 Pessac, France
5
Nuclear Gamma Resonance Laboratory, State research institute Center for Physical Sciences and Technology, Savanorių ave. 231, LT-02300 Vilnius, Lithuania
6
Cryogenic Research Division, Scientific-Practical Materials Research Centre of the National Academy of Sciences of Belarus, P. Brovka Str., 19, 220072 Minsk, Belarus
kuzhir@unice.fr
Two step synthesis
Akaganéite
b
-FeOOH
)
Conclusions:
1. Two-step nanorod synthesis + grafting of 3 different polymers/polyelectrolytes;
2. Optimum polymer amount for minimal aggregation (X=0.5) interplay: steric repulsion vs depletion;
3. Nanorods/PAA or Polymethacryl-PEG: stable at 8<pH<11; Nanorods/bi-phosphonate-PEG: stable at 1.5<pH<11.
4. Best stability with bi-phosphonate-PEG grafted at acidic pH
5. Theoretical estimations suggest stronger nanorod aggregation for smaller grafting density (PCP vs OPT)
Introduction
Objectives / State of the art
Adsorbed molecules
Antibodies Magnetic micro- or nanobeads: • MR imaging;
• Cell separation; • Hyperthermia;
• Detection of biomolecules by ELISA
Magnetic nanorods:
Same applications with enhanced magnetization
field
H
0
H=0
Light nanorod biomolecule absorbance time Detection of biomolecules by magneto-optic effects • Follow light absorption by
nanorod suspension in response to H
• Relate Cads to change of relaxation time
Start-up CMD (Exeter, UK)
We seek for iron oxide nanorods
: High specific surface small enough If using B1 mT
d5 nm L 25 nm Milosevic et al. J. Phys. Chem. (2011) No stabilization Mohaparta et al. Nanoscale (2015) Stabilization by PEI Orza et al.
ASC Appl. Mater. Int. (2017)
Stabilization by PEG-NH2 High interaction with H large enough
Strong MO response L/d>5
Well dispersed in water graft polymers/polyelectrolytes
Key question
van der Waals interaction is much stronger for rods than for beads (larger contact area)
L~30nm, d~6nm;
h ~0.5 nm – two water layers separating particle surfaces
To get 𝑼𝒗𝒅𝒘~𝟏𝒌𝑩𝑻 separate nanorods at h7-8 nm using a polymer 𝑈𝑣𝑑𝑤 = − 𝐴𝐻 24 2 𝐿 𝑑 𝑑 ℎ 3 2 ~ − 60𝑘𝐵𝑇
Our work: go further in realization and
understanding of nanorod dispersion
Detailed study of nanorod stability is missingPEI
+
Fe+3 Solution
= 80°C - 4h - 625rpm
Hydrolysis of FeCl3 .6H2O at 80°C The protocol with PEI
Mohaparta et al. Nanoscale (2015)
The protocol without PEI
Blesa et al. Reactivity of Solids (1986)
NH2 groups affinity with specific crystal phases anisotropic crystal growth
-polyethyleneimine
Reduction of
b
-FeOOH to iron oxide
b-FeOOH
pH7
Dissolution re-crystallisation (Schwertmann et al. Iron oxydes, 2000)
Effect of number of cycles, duration and microwave power
Low hyperfine field: no hematite
Akaganéite Iron oxyde
Saturation magnetization : MS = 67 kA/m Remnant magnetization : MR= 15 kA/m 3 X 45 sec 200 W 67 kA/m Mossbauer spectra:
11 % ordered magnetic phase (ferrimagnetic g-Fe2O3/Fe3O4 giving remnance)
89 % disordered magn. phase
(superparamagn. g-Fe2O3/Fe3O4 + non-transformed weakely paramagnetic akaganeite contributing to low Ms) Why so small? Why remnance?
Iron oxide room temperature magnetization
Dispersion of IO nanorods in water
Before: pH=1.2 or 6 pH=1.2 pH=1.2
Adjustment of pH to 8-9
precipitation-redispersion
[Sehgal, …, Berret, Langmuir (2005)] After: pH=1,2 or 3
chemisorption
phosphonate on iron oxyde
H H bi-phosphonate-PEG 2,2k Polyacrylic acid 15k Polymethacrylate-PEG 22.5 k
Characterization of polymer coated IO nanorods
DLS intensity distribution of diameters
Z Poorest dispersibility of PMethaCryl-PEG Best dispersibility of Bi-phosp-PEG grafted at pH1.2: Best condition for IO-phosphonate reaction
[Torrisi et al. Biomacromol. (2014)]
Bi-phosp-PEG
Bi-phosp-PEG PAA PMethaCryl-PEG
DLS z-average versus polymer amount X and pH
X=0,5 mg/mg
Bi-phosp-PEG
X= ratio added polymer mass/ nanorod mass [mg/mg]
X=0,5 mg/mg
TEM Chryo-TEM
Best stabilization: PEG-bi-Phosphonate
grafted at acidic pH at X=0.5 mg/mg
•
Smaller aggregates in chryo-TEM pictures
•
Lateral aggregation of rods
What leads to this aggregation?
Interaction energy between nanorods
1. Magnetic attraction due to remnant magnetization (~15 kA/m):
Umag << kBT (rods are too Brownian)
2. Electrostatic repulsion due to electric double layer overlap: 𝑼𝒆𝒍 ≪ 𝒌𝑩𝑻 (short Debye length k-1<1 nm)
van der Schoot & Odjik J. Chem. Phys. [1992]
3. van der Waals attraction:
Patel & Russel, Coll. Surf. (1988) + Derjaguin approximation
h d 3/ 2
1
24 2
vdW HL d
U
A
d
h
4. Steric repulsion due to polymer layers overlap :
5 /12 2 1/ 2 1 5 / 4 7 / 4 1/ 2 2 2 11/ 6 1 1/ 2 2 1/ 2 1 /(2 ) 7 ( ) ( ) 5 / 7 12 / 7 ( / 2) 2 ( ) ( ) 5 [ /(2 )] st B c c c h h k u x L d y y U L d dh k T k N a n dy x h a k y h d d d d
5. Depletion attraction due to osmotic pressure asymmetry (Russel “Colloidal dispersions” 1989):
dep ex