Magnetic nanoparticles: synthesis, properties and biomedical applications

(1)

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Magnetic nanoparticles: synthesis, properties and

biomedical applications

Olivier Sandre

To cite this version:

Olivier Sandre. Magnetic nanoparticles: synthesis, properties and biomedical applications: Part 1:

Synthesis and physical properties. Master. Física Aplicada, Universidad de Granada, Spain. 2017,

pp.62. �cel-02105959�

(2)

MAGNETIC NANOPARTICLES: SYNTHESIS, PROPERTIES AND

BIOMEDICAL APPLICATIONS

Olivier Sandre, senior CNRS researcher at Univ. Bordeaux, France

[email protected]

@olive_free

(3)

(4)

(5)

Magnetic nanoparticles (MNPs) Part 1:

Synthesis and physical properties

• Part 1A: Chemistry of iron oxides and oxo-hydroxides:

Diversity of methods to prepare colloidal nanoparticles,

either in non aqueous

solvents: hydrothermal synthesis, polyol synthesis, thermal decomposition…

or in water: alkaline co-precipitation of iron salts (also in EG, DEG…)

• Part 1B: Magnetic behavior

(ferro- /ferri- /antiferro- /superpara– magnetism…) and

optical properties of MNPs

(UV-vis absorption, magnetic birefringence)

• Part 1C: MNPs as contrast agents in

Magnetic Resonance Imaging

Universal law for relaxometry (T

₁

/T

₂

of water H spins near MNPs)

• Part 2A Magnetic Hyperthermia (‘Tumor catabolism’)

• Part 2B Nanomedicines

– Magnetic carrier – Magnetic Guiding (‘Tumor homing’)

• Part 2C Drug Delivery Systems (DDS)

based on

Magnetic Core

@

Polymer Shells

,

Magnetic Polymer Shells, Magnetic Micelles, or Vesicles (‘Polymersomes’)

(6)

Diversity of iron oxides and oxo-hydroxides

(7)

From solution of Fe

2+

_{et Fe}

3+

_{salts towards solid phase}

D.K. Kim et al.,

Chem. Mater. 2003, 15, 1617-1627

in De la solution à

l’oxyde

, J.-P. Jolivet

Spinelle structure

(8)

Very narrow pH stability of Fe

3+

_(H

2 O)

6 soluble ion

(9)

Antiferromagnetic clays made of iron

+III

_{oxo-hydroxides}

200 nm

Accicular Haematite α–Fe

₂

O

₃

(spindle-like)

Goethite nanolaths γ−

FeOOH

(rod-like)

Orthorombic structure of γ−FeOOH

(Fe

3+

_{in octahedral sites)}

Goethite is

antiferromagnetic

= 0

Resulting

magnetization

(10)

Synthesis of antiferromagnetic goethite nanorods

NaOH

1M

Fe 

NO

₃



₃

N

_i



NO

₃



₂

ou Co 

NO

₃



₂

1/ ferrihydrite alkaline precipitation

2/ Slow dissolution X days at pH>11

→ goethite formation (ochre)

goethite

3/ Washings H

₂

O

(5000 rpm)

Dispersion in HNO

₃

at pH=3

Fe NO

_{3 3}

Ni NO

_{3 2}

ou

Co NO

_{3 2}

FeOOH

o

PhD thesis J. Hernandez (UPMC 1998):

10 days ageing at T=25C & pH13

o

S. Krehula et al. (Mat. Lett. 2002):

hydrophobic base (TMAOH)

Ageing during 1 – 21 days + “f

orced hydrolysis” (T=60 – 160C)

o

D. Thies-Weesie et al. (Chem. Mater. 2007)

Size-sorting by centrifugation steps

0.1M

o

Thermal

decomposition Fe

III

-oleate

Taekyung Yu et al. (JACS 2007)

(11)

Doping of goethite nanorods with M

n+

_cations

RX goethite témoin et dopée nickel 2,4%

0 0,2

0,4

0,6

0,8

1 1,2

15

25

35

45

55

65

75

85

95 2 théta

T1 goethite témoin non dopée

5 Ni1 goethite dopée Ni à 2,4%

Goethite orthorhombique (tables logiciel)

Sample pH

_ageing

Ni/Fe

Φ v/v

D

_hyd

nm

T

11.1

0 0.21%

205 1Ni

11 0.6%

0.19%

198 5Ni

11.9 2.4%

0.17%

142 10Ni

12 2.8%

0.10%

168 XRPD: no trace of Ni(OH)

₂

→

nickel on surface

Ageing conditions: 24h in oven at 70°C - pH=11-12



U. Schwertmann & R.M. Cornell, Iron Oxides in the Laboratory (1991)



B. Sing et al., Clay Minerals 2002 → Cr

3+

, Mn

3+

, Ni

2+



M. Mohapatra et al., Hydromelallurgy 2002 → Cu

2+

, Ni

2+

, Co

2+

, Mat. Chem. Phys. 2005 → Ce

4+

α−FeOOH: orthorombic mesh a=9.95Å b=3.01Å c=4.62Å

Sample pH

_ageing

Co/Fe

Φ v/v

D

_hyd

nm

T

11.1

0 0.21%

205 1Co

12 1.0%

0.25%

284 5Co

12.2 2.6%

0.15%

169

(12)

Goethite nanorods doped with Co

2+

0

5

10

15

20

25

0

32

5

40

0

47

5

55

0

62

5

70

0

77

5

85

0

92

5 ₁₀

00 ₁₀

75 ₁₁

50 ₁₂

25 Goethite

doped at 1%Co

Hydrodynamic diameter = 284 nm

Mean length by TEM = 715 nm

Goethite doped at 10%Co

Non monotonous effect of Co doping on rods’ size:

150

170

190

210

230

250

270

290

310

0

2

4

6

8

10 taux de dopage en Co (%)

di

a

m

è

tr

e

hy

dr

o (

nm

)

0

100

200

300

400

500

600

700

800 longue

ur

TE

M

(

nm

)

Large size associated with interesting

magnetic properties (1Co1

sample)

0

5

10

15

20

25 125 225 325 425 525 625 725 825 925 102

5

112

5

122

5

132

5

142

5

152

5

(13)

Antiferromagnetic nanorods of even smaller sizes

50 nm

Akaganeite Fe

₈

O

₈

OH

₈

Cl

_1.35

SANS on PAXY LLB-Saclay (oct. 2008)

V

_p

=L×w×t=2280 nm

3 w

≈t≈3.4 nm

0

10

20

30

40

50

60

70

80

4

8 ₁₂

₁₆

₂₀

₂₄

₂₈

₃₂

₃₆

₄₀

₄₄

₄₈

₅₂

₅₆

₆₀

Diameters (nm)

L

_TEM

=20.6±8.6 nm

∝q

-2

∝q

-4

Vol. fraction≈2% (SANS)

Density=3.726 (XRD table)

(14)

Magneto-orientational behavior of a suspension of

anti-ferromagnetic nanoparticles (NAF)

V

µ

H

_c

=

χ

_A

c

H

=

T

k

H

µ

_c

_B

=

β

Yu L Raikher, V. I. Stepanov (Perm, Russia) :

2 A

2

1 )

.

(

)

.

(

e

H

V

e

H

µ

U

=

−



+

χ



χ

_A

=

χ

_||

-

χ

_⊥

(15)

Magnetic behavior of antiferromagnetic nanorods

*measurement at

INSP lab. (UPMC)

0

500 1000

1500

2000

0,0

0,1

0,2

0,3

0,4

0,5

M

agnet

iz

at

ion /

Φ

[

em

u/

cm

3 ]

Magnetic field [Oe]

2'(T1)

5'

aka

µ

_Fe+III

=5 µ

_B

SQUID magnetometry at ambient temperature*

B. Lemaire, P. Davidson (LPS Orsay)

(16)

Magnetite: Crystalline Structure

Magnetite is

ferrimagnetic

=

Resulting

magnetization

Fe

3+

_(d

5 _{)=5 µ}

B

Fe

2+

_(d

6 _{)=4 µ}

B

Fe

+III

M

+II

M

O. Fe

₂

O

₃

Spinelle structure:

direct or inverse

Exercise: 1/calculate specific volume (cm

3 _⋅mol

-1

_{) and mesh size a}

Data: one unit cell is cubic and contains 8 Fe

₃

O

₄

molecules

Mass density ρ=5.18×10

3 _kg⋅m

-3

_{, Molar mass M=231.535 g⋅mol}

-1

1 Bohr magneton µ

_B

=9.274×10

-24

_A⋅m

2 Answers:

2/calculate the specific magnetization M

_S

of bulk Fe

₃

O

₄

in A⋅m

-1

=O

_h

=T

_d

a=8.396 Å

v=45 cm

3 _⋅

_mol

-1

(17)

Magnetic domains and Bloch boundaries (walls)

Size of mono-domain: ~ 30-50 nm for iron oxides

µ

_{= m}

_s

_V

One ~10 nm nanoparticle is a magnetic single domain

Exercise:

1:calculate magnetic moment (in nb of µ

_B

/MNP) for

diameters: d=4 / 8 / 16 nm

2: calculate total nb of Fe ions per MNP for all d’s

3: calculate nb of Fe ions on surface per MNP for all d’s

Data:

1 Bohr magneton µ

_B

=9.274×10

-24

_A⋅m

2 For nano-crystalline Fe

₃

O

₄

, M

_S

= 4×10

5 _A⋅m

-1

Macroscopic magnets (bulk materials) are multi-domains

Answer:

1: 1500 / 11000 / 90000 2: 1400 / 10700 / 87000

3: 290 (20%) / 1100 (10%) / 4500 (5%)

Rosensweig 1965, Néel 1955, Kittel 1946, Elmore 1938

Curie-Weiss

domains

(18)

08/12/2017

17 Shape anisotropy contribution to birefringence

"Rock-like" particles: S1C fraction, coated with PAA

_2k

(19)

Birefringence measurement under H field

0,0001

0,001

0,01

0,1

1

100 1000

10000

100000

1000000

H (A/m)

∆n/

∆ns

data montée

data descente

fit

d

₀

bir

_{(nm) = 6.0}

σ

bir

₌

_0.2

slope H

2 ∆n

spe

=4.10

-2

E. Hasmonay et al. EPJB 1998

P

Y//A

X

(L)

H

p

H

_P

Laser

S

P

2 P

1 P

A

Photo Cell

Gaussmeter

Photo Elastic Modulator (X, Y,

ω)

_{Lock-In Amplifier}

I

₁

(ω)∝sin(ϕ)

I

₂

(2 ω)∝(t

_║

- t

_┴

)

∆n=(n

_║

- n

_┴

)

ϕ = 2π ∆n e / λ

dichroism

birefringence

∆n

_sat

= ∆n

_spe

Φ

Plateau:

(20)

Starting materials : “True” ferrofluid

Ferrofluid = colloidal suspension of magnetic nanoparticles

which remains stable whatever the intensity of applied magnetic field

• no attraction of nanoparticles under B field gradient nor chaining by dipolar interaction

• but progressive orientation of dipoles according to Langevin’s laws:

Magnetization

0.0001

0.001

0.01

0.1

1

10

100 1000

10000

Champ (Gauss)

∆n/∆n

s

0.01

0.1

1

10

100 1000

10000

Champ magnétique (Gauss)

M/

Ms

d

o

(nm)= 6.0

σ = 0.2

φ = 0.09%

∆n

s

/

φ = 4.2E-02

d

o

(nm) = 6.6

σ = 0.2

Φ (%) = 3.0

0

0.1

0.2

0.3

0.4

0

10

20

30 P(d)

lognorm

Phi(d)

Birefringence

M

_s

=

Φ

m

_s

m

s

= 3,1.10

5 A/m (SI) m

s

/ 4π = 300 G (CGS)

(21)

08/12/2017

20 Mons, Belgium

Relaxivities:

Yves Gossuin,

Hypethermia:

Robert Müller,

Jena, Germany

Improved properties of the larger magnetic NPs

(22)

High Frequency Magnetic Susceptometry / Hyperthermia

High frequency AC susceptometer built at

the IMEGO company (Sweden)

AC signal source (A), current amplifier (B),

coil system and mechanics (C), lock-in

amplifier (D) and user interface software (E)

S

RF

H

V

f

SHP

=

πµ

₀

χ

″

₀

2 HF

Astalan, A.; Ahrentorp, F.; Jonasson, C.; Blomgren, J.; Yan, M.; Courtois, J.; Berret, J.-F.;

Fresnais, J.; Sandre, O.; Müller, R.; Dutz, S.; Johansson, C., AIP Conf. Proc. Series 2010

Hyperthermia set-up built by

R. Müller, Jena (Germany)

(23)

Role of the sizes’ (mono)dispersity on the SHP effect

G. Glöckl, R. Hergt, J. Phys.: Condens. Matter 18 (2006) S2935–S2949:

resonance effect

100 nm

5,3nm / 0,19

6,8nm / 0,20

8,0nm / 0,21

10,2nm / 0,28

≈ 20nm / 0,3

J-P. Fortin, C. Wihelm, J. Servais, C. Ménager, J-C. Bacri, F. Gazeau, J. Am. Chem. Soc. 129 2628 (2007)

M. Lévy, C. Wilhelm, J-M. Siaugue, O. Horner, J-C. Bacri, F. Gazeau, J. Phys. Cond. Mat. 20 204133 (2008)

SHP (at f =700 kHz, H

₀

=24.8 kAm

-1

_{) =}

(24)

Calibration sample: monodisperse Fe

₃

O

₄

nano-spheres

d

_TEM

=18.9±2.8 nm

Fe-oleate decomposition in n-hexane (4h 70°C)

Q. Bin, O. T. Mefford (Clemson Univ, USA)

according to Park et al, Angew. Ch. 2005)

Astalan, A.; Ahrentorp, F.; Jonasson, C.; Blomgren, J.; Yan, M.; Courtois, J.; Berret, J.-F.;

Fresnais, J.; Sandre, O.; Müller, R.; Dutz, S.; Johansson, C., AIP Conf. Proc. Series 2010

(25)

Role of MNP shape on the magnetic anisotropy K

_a

Astalan, A.; Ahrentorp, F.; Jonasson, C.; Blomgren, J.; Yan, M.; Courtois, J.; Berret, J.-F.;

Fresnais, J.; Sandre, O.; Müller, R.; Dutz, S.; Johansson, C., AIP Conf. Proc. Series 2010

spheres Ø19nm: weak χ’’, Néel’s band ~ 5MHz

rock-like particles Ø16nm :

large χ’’, Néel’s band ~ 2MHz

( )

₍

_{( )}

₎

( )

H

high

H

eff

C

dr

r

f

r

j

r

C

χ

ωτ

ω

χ

+

=

∫

1

6 B

N

τ

1

1 eff

+

=

kT

V

B

η

τ

=

3 )

exp(

a

0 kT

V

K

N

τ

=

SHP=215 W/g at:

f=410kHz

H

₀

=24kAm

-1

(26)

08/12/2017

25 Mons, Belgium

Relaxivities:

Yves Gossuin,

Hypethermia:

Robert Müller,

Jena, Germany

Improved properties of the larger magnetic NPs

(27)

Ionic Ferrofluids: the coprecipitation synthesis

R. Massart IEEE Trans. Magn.

17 1247 (1981)



Massart’s process:

Alkaline coprecipitation of FeCl

₂

& FeCl

₃

→ magnetite

Fe

₃

O

₄

nanoparticles

Oxidation by Fe(NO

₃

)

₃

→ maghemite

γ-Fe

₂

O

₃

nanoparticles

in acidic medium (HNO3): stabilized by

electrostatic surface charges (PZC≈7)

Fe

2+

(aq)

+ 2Fe

3+

(aq)

+

8OH

-

(aq)

→ Fe

3 O

4(s)

+ 4H

2 O

(l)

T. Ahm at al. J. Phys. Chem. (2012) pre-print

A. Abou-Hassan, O. Sandre, and V. Cabuil, Chapter 9:

Microfluidics for the synthesis of iron oxide nanoparticles, in

Microfluidic Devices in Nanotechnology: Applications, C.S.S.R.

Kumar, Editor.

2010, John Wiley & Sons, Inc: Hoboken, NJ, USA.

(28)

Microfluidics as a tool to get an insight of the

kinetics of the coprecipitation reaction

PhD thesis Ali Abou Hassan (2 oct 2009)

A. Abou Hassan, O. Sandre, V. Cabuil, P. Tabeling, Chem. Commun. 2008, 1783

H

+

_/

_FH

2 +

OH

-OH

-Fe

2+

(aq)

+ 2Fe

3+

(aq)

+

8OH

-

(aq)

→ Fe

3 O

4(s)

+ 4H

2 O

Answer to clogging issue: 3D geometry and non

flocculating counterion of base

TMA

+

OH

-OH

-Fe+II/Fe+III

Fe3O4 - -- --- - -Fe3O4 - -- --- - - - -- --- - - -- --- - -- Fe3O4 - -- --- - -Fe3O4 - -- --- - - - -- --- - - -- --- - -Fe3O4 -- -- -- -- -Fe3O4 -- -- -- -- - -- -- -- -- -- -- -- -- -Fe3O4- - - -- --- - -Fe3O4- - - -- --- - - - -- --- - - -- --- - -Fe3O4 - -- --- - -Fe3O4 - -- --- - - - -- --- - - -- --- - -Fe3O4 - -- --- - -Fe3O4 - -- --- - - - -- --- - - -- --- - -Fe3O4 - -- --- - -Fe3O4 - -- --- - - - -- --- - - -- --- - -Fe3O4 - - -- --- - -Fe3O4 - - -- --- - - - - -- --- - - - -- --- -

-Fe+II/+III

Fe3O4 - -- --- - -Fe3O4 - -- --- - - - -- --- - - -- --- - -- Fe3O4 - -- --- - -Fe3O4 - -- --- - - - -- --- - - -- --- - -Fe3O4 -- -- -- -- -Fe3O4 -- -- -- -- - -- -- -- -- -- -- -- -- -Fe3O4- - - -- --- - -Fe3O4- - - -- --- - - - -- --- - - -- --- - -Fe3O4 - -- --- - -Fe3O4 - -- --- - - - -- --- - - -- --- - -Fe3O4 - -- --- - -Fe3O4 - -- --- - - - -- --- - - -- --- - -Fe3O4 - -- --- - -Fe3O4 - -- --- - - - -- --- - - -- --- - -Fe3O4 - - -- --- - -Fe3O4 - - -- --- - - - - -- --- - - - -- --- -

-Fe+II/+III

Fe3O4 - -- --- - -Fe3O4 - -- --- - - - -- --- - - -- --- - -- Fe3O4 - -- --- - -Fe3O4 - -- --- - - - -- --- - - -- --- - -Fe3O4 -- -- -- -- -Fe3O4 -- -- -- -- - -- -- -- -- -- -- -- -- -Fe3O4- - - -- --- - -Fe3O4- - - -- --- - - - -- --- - - -- --- - -Fe3O4 - -- --- - -Fe3O4 - -- --- - - - -- --- - - -- --- - -Fe3O4 - -- --- - -Fe3O4 - -- --- - - - -- --- - - -- --- - -Fe3O4 - -- --- - -Fe3O4 - -- --- - - - -- --- - - -- --- - -Fe3O4 - - -- --- - -Fe3O4 - - -- --- - - - - -- --- - - - -- --- - -Fe3O4 - -- --- - -Fe3O4 - -- --- - - - -- --- - - -- --- - -- Fe3O4 - -- --- - -Fe3O4 - -- --- - - - -- --- - - -- --- - -Fe3O4 -- -- -- -- -Fe3O4 -- -- -- -- - -- -- -- -- -- -- -- -- -Fe3O4- - - -- --- - -Fe3O4- - - -- --- - - - -- --- - - -- --- - -Fe3O4 - -- --- - -Fe3O4 - -- --- - - - -- --- - - -- --- - -Fe3O4 - -- --- - -Fe3O4 - -- --- - - - -- --- - - -- --- - -Fe3O4 - -- --- - -Fe3O4 - -- --- - - - -- --- - - -- --- - -Fe3O4 - - -- --- - -Fe3O4 - - -- --- - - - - -- --- - - - -- --- -

-Fe+II/+III

OH

-Nanoparticles

at the interface

(29)

Microfluidics as a tool to get an insight of the

mechanism of goethite formation

Fe

III

TMAOH

water

µR1: nucleation

(seeds)

µR2: growth

T=60°C

“2-lines ferrihydrite” nanodots ∅ = 4±1 nm

A. Abou-Hassan, O. Sandre, S. Neveu, V. Cabuil, Angew. Ch.

48 1-5 (2009)

200 nm

15 min / 60°C: Goethite nanorods

L=30±17 nm and w=7±4 nm

J. F. Banfield et al. Science 2000, 289, 751

→ check “oriented aggregation” mechanism

Two micro-reactors in-line

(30)



FEM lab simulations

OH

-OH

-x

(a)

(b)

(a)

(b)

H

+

_/

_FH

2 +

OH

-OH

-z

x

y

(Nernst-Planck)

Hydrodynamics (Navier-Stokes) and mass transport



Confocal Laser Scanning Microscopy:

Fluorescein as pH reporter dye

A. Abou-Hassan, J-F. Dufrêche, O. Sandre, G. Mériguet, O. Bernard, V. Cabuil, J. Chem. Phys. C 2009

pH = f(α) with α = Q

_OH-

/ Q

_H+

Microfluidics as a tool to get an insight of the

mechanism of goethite formation

(31)

y

x

α = 400

α = Q

_OH-

/ Q

_H+

Numerical simulations vs. confocal

microscopy

Microfluidics as a tool to get an insight of the

mechanism of goethite formation

(32)

Detector nose

Lindemann

glass capillary

∅

_{= 1,6 mm}

(wall thickness

= 10 µm)

Internal capillary

∅

_int

_{= 100 μm}

∅

_ext

_{= 350 µm}

beam 300 x 100 µm

cross-section at fixed

position

X-ray beam

travel

z

x

SAXS measurements on SWING line at

SOLEIL synchrotron (July 2009)

Detection of first seeds using SAXS in microfluidics

Abou Hassan, O. Sandre,

V. Dupuis, Olivier Spalla

(33)

SAXS capillary

∅

=1,6 mm

R=780 µm

Internal capillary

∅

_int

=100 μm

∅

_ext

=350 µm

X-rays (∆x=150µm, ∆z=50µm)

Scan x=-250 to +250 µm every 50µm

Travel of internal

capillary by steps 500

±

10 µm

x

y

z

x

0 x=250µm

x+∆x

x-∆x

R

_jet

µm

Q

_in

/

Q

_out

10/400

10/200

1/400

88

123

28 (

x

)

R

(

x

)

x

z

R

z

R

V

_jet

diffusant

jet

∆

π

×













₋

₊

₋

₊

×

=

2

Scattering volume in SAXS

geometry

(34)

z

x

0 α

_{= 400/10=40 R}

_jet

_{= 88 µm}

1,E-05

1,E-04

1,E-03

1,E-02

1,E-01

1,E+00

0,001

0,01

0,1

1 q (Å

-1

)

I (c

m

-1

)

z = 2 mm

z = 3 mm

z = 3,5 mm

z = 4 mm

z = 5,5 mm

z = 6,5 mm

z = 7 mm

z = 8 mm

2H

R

X-rays

space (z) ≈ time equivalency?

(35)

0 1000

2000

3000

4000

5000

6000

0.67

1.00

1.33

1.67

2.00

2.33

2.67

3.00 Tem ps de réaction (s)

V

o

lu

m

e

(

n

m

3 )

0

5

10

15

20

25

30

35

40

45

0.5

0.6

0.7

0.8

0.9

1

1.1

1.2

1.3

1.4

1.5

1.6

1.7

1.8

1.9

2 pH d'après sim ulations

R

e

n

d

e

m

e

n

t (

%

) o

u

R

a

p

o

rt

d

'asp

ect

Vol. (nm3)

Rend. %

Aspect R/H

Anisotropy R/H

2H

R

Preliminary SAXS results: fits as disk form factor

(36)

Epitaxial growth rate ≈ 9Å/s

Fe(OH)

₃

as fractal gel or

cristallyne structure Bernalite

Preliminary SAXS results: fits as disk form factor

y = 4.5816x

0

2

4

6

8

10

12

14

0.67

1.00

1.33

1.67

2.00

2.33

2.66

3.00 Ha

u

te

u

r (

Å)

0

50

100

150

200

250

300

0.5

0.6

0.7

0.8

0.9

1

1.1

1.2

1.3

1.4

1.5

1.6

1.7

1.8

1.9

2 pH d'après simulations

R

a

y

o

n

(

Å

)

½-haut H (Å)

rayon R (Å)

Linéaire (½-haut H (Å))

(37)

Coatings of iron oxide and oxo-hydroxide NPs for their

dispersion in various media

Different coatings to insure colloidal

stability :



surfactants (oleic acid, phosporic

di-ester ,…) for organic solvents (alkanes,

chlorinated,…)



sodium citrate in aqueous neutral

medium (pH=7.2) or sodium

polyacrylate (2000 or 5000 g/moL)

F e

O

F e

O

C

O

C H 2

O

-

F e

O

F e

C

C H 2

H O

C

O

O -

0

7

14

0

7

14 J. A. Galicia, O. Sandre, F. Cousin, D. Guemghar, C. Ménager, V.

Cabuil, J. Phys.-Cond. Mat.

2003. 15 S1379.

(38)

50 nm

0

5

10

15

20 50 nm

0

5

10

15

20  Size Polydispersity: P(d, nm)

 Fractionated separations

R. Massart, E. Dubois, V. Cabuil, E. Hasmonay,

J. Magn. Magn. Mater. 149 1 (1995)

835mL ferrofluide acide DE1,

Φ=2.5% d

₀

=7nm σ=0.39

HNO3 en excès

C1

250mL Φ=6.4%

d

0 =8.6nm σ=0.35

S1

C1S

200mL Φ=3.5%

d

0 =7.6nm σ=0.30

C1C

HNO

₃

HNO

₃

S1S-HNO3

85mL Φ=1.8%

d

₀

=6.6nm σ=0.21

S1S-Na3Cit

20mL Φ=3.2%

d

0 =6.6nm σ=0.21

[Na

₃

Cit]

=1.4x10

-2

_M

1) Na

₃

Cit 2) dialyse

S2-HNO3

160mL Φ=1.2%

d

0 =7.1nm σ=0.26

S2-CH

₂

Cl

₂

25mL Φ=1.2%

d

0 =6.8nm σ=0.24

HNO

₃

C2

140mL Φ=2.8%

d

₀

=8.5nm σ=0.29

S1C

65mL Φ=4.2%

d

₀

=7.4nm σ=0.25

Φ (%)

1.E+06

1.E+07

1.E+08

1.E+09

1.E+10

1.E+11

0.01

0.1

1

10

100 Π

V

(Pa.Å

3 )

F

G

L

S

C

G+L

(39)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 2000

4000

6000

8000

10000

M/Ms

at

Applied magnetic field (Oe)

0

5

10

15

20

25

30

0

0.05

0.1

0.15

0.2

0.25

0.3 TEM diameter (nm)

USPIO

fraction

Given name

in this

work

D

H

of bare

MNPs in

HNO

3 nm / PDI

Average

diameters

by TEM

Average

diameters

by VSM

Saturation

magnetization

emu/g

A/m

r

₂

(4.7T)

s

-1

_mM

-1

Fe

SLP at

f=800 kHz,

H

₀

=11 kA/m

W/g

S1S2S3

6-7 nm

11 / 0.12

d

n

_w

=4.9 nm,

=6.9 nm

(N=600)

d

_n

=6.5 nm,

d

w

=7.5 nm

55±1

2.8×10

5

70 2±1

(40)

USPIO

fraction

Given name

in this

work

D

H

of bare

MNPs in

HNO

3 nm / PDI

Average

diameters

by TEM

Average

diameters

by VSM

Saturation

magnetization

emu/g

A/m

R

₂

(4.7T)

s

-1

_mM

-1

Fe

SHP at

f=800 kHz,

H

₀

=11 kA/m

W/g

S1S2S3

6-7 nm

11 / 0.12

d

n

_w

=4.9 nm,

=6.9 nm

(N=600)

d

_n

=6.5 nm,

d

w

=7.5 nm

55±1

2.8×10

5

70 2±1

Size-sorted “ionic ferrofluid” as elementary bricks

0

5

10

15

20

25

30

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

0.18 TEM diameter (nm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 2000

4000

6000

8000

10000

M/Ms

at

Applied magnetic field (Oe)

USPIO

fraction

Given name

in this

work

D

H

of bare

MNPs in

HNO

3 nm / PDI

Average

diameters

by TEM

Average

diameters

by VSM

Saturation

magnetization

emu/g

A/m

r

₂

(4.7T)

s

-1

_mM

-1

Fe

SLP at

f=800 kHz,

H

₀

=11 kA/m

W/g

S1S2S3

6-7 nm

11 / 0.12

d

n

_w

=4.9 nm,

=6.9 nm

(N=600)

d

_n

=6.5 nm,

d

w

=7.5 nm

55±1

2.8×10

5

70 2±1

S1C2

8-10 nm

23 / 0.16

d

w

n

=8.5 nm,

=11.6 nm

(N=3800)

d

n

=8.2 nm,

d

_w

=10.0 nm

3.0×10

60

5

104 9±1

(41)

USPIO

fraction

Given name

in this

work

D

H

of bare

MNPs in

HNO

3 nm / PDI

Average

diameters

by TEM

Average

diameters

by VSM

Saturation

magnetization

emu/g

A/m

R

₂

(4.7T)

s

-1

_mM

-1

Fe

SHP at

f=800 kHz,

H

₀

=11 kA/m

W/g

S1S2S3

6-7 nm

11 / 0.12

d

n

_w

=4.9 nm,

=6.9 nm

(N=600)

d

_n

=6.5 nm,

d

w

=7.5 nm

55±1

2.8×10

5

70 2±1

Size-sorted “ionic ferrofluid” as elementary bricks

USPIO

fraction

Given name

in this

work

D

H

of bare

MNPs in

HNO

3 nm / PDI

Average

diameters

by TEM

Average

diameters

by VSM

Saturation

magnetization

emu/g

A/m

R

₂

(4.7T)

s

-1

_mM

-1

Fe

SHP at

f=800 kHz,

H

₀

=11 kA/m

W/g

S1S2S3

6-7 nm

11 / 0.12

d

n

_w

=4.9 nm,

=6.9 nm

(N=600)

d

_n

=6.5 nm,

d

w

=7.5 nm

55±1

2.8×10

5

70 2±1

S1C2

8-10 nm

23 / 0.16

d

w

n

=8.5 nm,

=11.6 nm

(N=3800)

d

n

=8.2 nm,

d

_w

=10.0 nm

3.0×10

60

5

104 9±1

0

5

10

15

20

25

30

0

0.02

0.04

0.06

0.08

0.1

0.12 TEM diameter (nm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 2000

4000

6000

8000

10000

M/Ms

at

Applied magnetic field (Oe)

USPIO

fraction

Given name

in this

work

D

H

of bare

MNPs in

HNO

3 nm / PDI

Average

diameters

by TEM

Average

diameters

by VSM

Saturation

magnetization

emu/g

A/m

r

₂

(4.7T)

s

-1

_mM

-1

Fe

SLP at

f=800 kHz,

H

₀

=11 kA/m

W/g

S1S2S3

6-7 nm

11 / 0.12

d

n

_w

=4.9 nm,

=6.9 nm

(N=600)

d

_n

=6.5 nm,

d

w

=7.5 nm

55±1

2.8×10

5

70 2±1

S1C2

8-10 nm

23 / 0.16

d

w

n

=8.5 nm,

=11.6 nm

(N=3800)

d

n

=8.2 nm,

d

_w

=10.0 nm

3.0×10

60

5

104 9±1

C1C2S3S4

10-15 nm

38 / 0.26

d

n

=13.8 nm,

_w

=20 nm

(N=1140)

d

_n

=10.4 nm,

d

w

=14.8 nm

70±1

3.5×10

5

293 80±5

(42)

0.01

0.1

1 A

im

an

tat

io

n

o

rm

al

is

ée

p

ar

p

lat

eau

(M

/M

sa

t

)

Champ magnétique B appliqué (mTesla)

15-19 nm raising field

15-19 nm lowering field

15-19 nm Langevin fit

10-15 nm raising field

10-15 nm lowering field

10-15 nm Langevin fit

8-10 nm raising field

8-10 lowering field

8-10 nm Langevin fit

6-7 nm raising field

6-7 nm lowering fit

6-7 nm Langvin fit

∼6nm

∼8nm

∼10nm

1

10

100 1000

∼20nm

(43)

Group Meeting

42

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 2000

4000

6000

8000

10000

Champ magnétique appliqué (gauss)

M/

Ms

0

0.05

0.1

0.15

0

10

20

30

40 P(d)

lognorm

Phi(d)

Larger nanoparticles for larger physical effects?

d

_w

= <d

4 _>/<d

3 _>

VSM or TEM

≈ 16 nm

Obtained by multiple phase separation

(C1C2C3C4)

<d>

_TEM

= 13.9 nm

100 nm

<d

n

_>=d

0 n

exp(nσ

2 /2) → d

w

=<d

4 >/<d

3 >)=d

0 exp(3.5σ

2 )

<d>

_VSM

= 11.8 nm

0

5

10

15

20

25

30

1

4

7 ₁₀

₁₃

₁₆

₁₉

₂₂

₂₅

₂₈

Diameter (nm)

Numbe

r of particles

0 0,2

0,4

0,6

0,8

1

0

10

20

30 Diameter (nm)

Fraction

o

f pa

rticle

s

TEM

Log-normal

(44)

Group Meeting

₄₃

Size-sorted fraction: C1C2S3S4

d

_w

= <d

4 _>/<d

3 _>

VSM

= 14.8 nm

<d>

_TEM

= 13.3 nm

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 2000

4000

6000

8000

10000

Champ magnétique appliqué (gauss)

M/

Ms

0

0.05

0.1

0.15

0

10

20

30

40

0

0.02

0.04

0.06

0.08

0.1 P(d) lognorm

Phi(d)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 2000

4000

6000

8000

10000

Champ magnétique appliqué (gauss)

M/

Ms

0

0.02

0.04

0.06

0.08

0.1

0.12

0

10

20

30

40

0

0.02

0.04

0.06

0.08

0.1 P(d) gamma

Phi(d)

Distributions des diamètres de l'échantillon

RP1-C1C2S3S4@BNE-A d'après TEM et fits VSM

0

0.01

0.02

0.03

0.04

0.05

0.06

0

10

20

30

40 diamètre (nm)

0

20

40

60

80

100

120

140

160 P(d) TEM

d3P(d) Log-normale

d3P(d) Gamma

(45)

Group Meeting

44 0,0001

0,001

0,01

0,1

1

100 1000

10000

100000

1000000

H (A/m)

∆n/

∆ns

data montée

data descente

fit

0,001

0,01

0,1

1

100 1000

10000

100000

1000000

H (A/m)

∆n/

∆n

s

data montée

data descente

fit

Static Magneto-birefringence

d

₀

bir

_{(nm) = 6.0}

σ

bir

₌

_0.2

d

₀

bir

_{(nm) = 13.2}

σ

bir

_{= 0.35}

c.

d.

slope H

2 ∆n

_s

=4.10

-2

∆n

_s

=10

-1

more monodisperse and superparamagnetic

larger, ferrimagnetic and more anisotropic

Vibrating sample magnetometry

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 2000

4000

6000

8000

10000

Champ magnétique appliqué (gauss)

M/

Ms

Smaller NPs

(S1S fraction d=6nm)

d

₀

aim

_{(nm) = 6.6}

σ = 0.21

Φ (%) = 1.1

a.

χ

H

m

_s

=2,6x10

5 _A/M

0 0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1

0 2000

4000

6000

8000

10000

Champ magnétique appliqué (gauss)

M/Ms

Larger NPs

(C1C fraction d=9nm)

d

₀

aim

_{(nm) = 9.1}

σ = 0.35

Φ (%) = 2.7

b.

χ

_H

m

_s

=3,5x10

5 _A/M

1 st

_order

Langevin’s curve

M

_sat

= m

_s

Φ

∆n

_sat

= ∆n

_s

Φ

2 nd

_order

Langevin’s curve

Magnetic/magneto-optical properties of size-sorted MNPs

∫

=

f

D

dD

kT

H

D

M

L

D

M

V

M

S

_LN

S

)

(

)

6 (

6

1 π

3 µ

₀

π

3

(46)

Particle form factors by small angle neutron scattering

0.01

0.1

1

10

100 1000

0.001

0.01

0.1

1 SANS Intensity normalized by volume fraction

Φ

(cm

-1

₎

S0

S1S2

S1C2

C1S2

C1C2A

Guinier

Porod

𝐼 ≅ ΦΔ𝜌

2 𝑉

_{𝑉 𝑒}

2 −𝑞

2 𝑅

𝐺

2 ⁄

3 Scattering vector q (Å

-1

₎

𝐼 ≅ 2𝜋Φ 1 − Φ Δ𝜌

2 _𝑉

𝑆

S

₀

:

9.2

7.3

0.72

209 R

_G

(nm) 𝑅

_𝑉

2 _⁄

_𝑉

(nm) R

_G

/R

_H

C

₁

C

₂

A: 16.7

21.2

0.4

145 S

_spe

(m

2 _/g)

(47)

Synthesis & properties of multi-core “nanoflowers”

L. Lartigue, P. Hugounenq, D. Alloyeau, S. P. Clarke, M. Lévy, J-C. Bacri, R. Bazzi, D. F. Brougham, C.

Wilhelm, F. Gazeau, ACS Nano 6, 10935–10949 (2012)

→

_{superior heating properties}

(here values at H

_max

=29 kA/m)

→

also high transverse relaxivity:

r

₂

=365 s

-1

_mM

Fe

-1

at 9.25MHz

(48)

Nanoflower synthesis: the New Orleans method

D. Caruntu, G. Caruntu, Y. Chen, C. J. O’Connor, G. Goloverda,

V. L. Kolesnichenko, Chem. Mater.

2004, 16, 5527-5534

Polyol mixture: N-methyl diethanolamine / DEG (1:1)

Ferrite slab for magnetic

sedimentation

Aspiration flask for

washing steps

Stirring shaft

Reflux

Internal T-probe

Dry heating mantle

(up to 250°C)

2 nd

_{heat/stirrer for}

precursor dissolution

•

• Precursor

Polyol composition

• Temp/Duration

• Water content

• 2 mmol FeCl

₂

• 4 mmol FeCl

₃

• 16 mmol NaOH

• 40 g DEG

• 40 g NMEDA

• 220°C 5h

(49)

Forced hydrolysis mechanistic pathway (Caruntu)

1) D. Caruntu, G. Caruntu, Y. Chen, C. J. O’Connor, G. Goloverda, V. L. Kolesnichenko,

Chem. Mater.

2004, 16, 5527-5534;

2) S. Sun and H. Zeng et al, J. A. C. S.,

2002, 124, 8204-8205 and 2004, 126, 273-279

3) F.A. Tourinho, R. Franck, R. Massart, J. Materials Science

1990, 25, 3249-3254

(50)

Large library of sample batches

Batch name Nomenclature

15ff

DN1000

_HU

-5h

17ff

D5000

HI

-20m

25ff

DN500

_HU

-4h

30ff

DN1000

_HU

-5h

31ff

DN500

_HU

-1h

32ff

DN500

_HU

-5h

34ff

DN100

_HU

-5h*

35ff

DN100

_HU

-5h

36ff

DN100

_HU

-5h

Batch name

Nomenclature

28AA

DN100

_HU

-220-5h-Cl

29AA

DN200

HU

-220-5h-Cl

02MA

DN300

_HU

-220-5h-Cl

09MA

DN400

_HU

-220-5h-Cl

10MA

DN500

_HU

-220-5h-Cl

11MA

DN50

_HU

-220-5h-Cl

27MA

DN0-220-5h-Acac

12MA

DN100-220-5h-Acac

17MA

DN200-220-5h-Acac

18MA

DN300-220-5h-Acac

19MA

DN400-220-5h-Acac

20MA

DN500-220-5h-Acac

15JA

DD100-250-5h-Cl

10JA

TD100-250-5h-Cl

D=pure DEG

DN=DEG/NMDEA (1:1)

DD=DEG/DEA (1:1)

TD=TEG/DEA (1:1)

HU=heating up

HI=hot injection

* no stirring

Cl=2 mmol FeCl

Acac=6 mmol Fe(acac)

2 , 4 mmolFeCl

₃

,16 mmol NaOH

3 ,16 mmol NaOH

Vary µL water in 120 g polyol mixture:

EG: Ethylene Glycol

DEG: Diethylene Glycol

TEG: Triethylene Glycol

DEA: Diethanolamine

NMDEA: N-methyldiethanolamine

TEA: Triethanolamine

(51)

(52)

(53)

Study of polyol route: fate of solvent molecules

Right after synthesis

→

_{PZC = pKa of NMDEA}

After washings

(precipitation-redispersion cycles at alkaline pH)

• Can be oxidized in boiling Fe(NO

₃

)

₃

: Fe

₃

O

₄

→

γ–Fe

₂

O

₃

(54)

a)

b)

c)

d)

h)

f)

g)

i)

j)

k)

l)

m)

n)

_o)

_p)

_q)

_r)

Hydrodynamic size by DLS

Figure

Batch

D

_h

(nm)

PDI

a

5ff

36

0.22 b

7ff

32

0.14 c

12ff

44

0.18 d

15ff

46

0.23 e

17ff

24

0.32 f

19ff

22

0.18 g

20ff

16

0.21 h

21ff

27

0.14 i

22ff

43

0.14 j

25ff

55

0.26 k

26ff

36

0.10 l

27ff

50

0.11 m

29ff

37

0.16 n

31ff

33

0.08 o

32ff

21

0.13 p

33ff

45

0.12 q

34ff

30

0.19 r

35ff

36

0.13

(55)

Variety of Fe

₃

O

₄

NP batches synthesized in DEG:NMDEA

𝑑 = 𝑑

₀

𝑒

𝜎

2 ⁄

2 𝑣𝑣𝑣 𝑑 = 𝑑

₀

2 𝑒

𝜎

2 ⁄

2 − 1

4FF: d=6.2±1.0 nm

23FF: d=10.5±1.9 nm

15FF: d

_out

=36.3±4.8 nm

25FF: d=14.2±3.2 nm

29FF: d

_out

=26.6±4.2 nm

30FF: d

_out

=41.1±8.6 nm

G. Hemery, A. C. Keyes Jr., E. Garaio, I. Rodrigo, J. A. Garcia, F. Pazaola, E. Garanger,

O. Sandre, arXiv preprint: 1701.05858

(56)

Example of ultra-small nanosphere sample: 17FF

d=4.3±1.1nm

0

5

10

15

20

0

0.1

0.2

0.3

0.4

0.5 TEM diameter (nm)

Fr

eque

nc

y

(57)

Example of medium size nanosphere sample: 25FF

0 5 10 15 20 25 30 35 40 45 50

0

0.05

0.1

0.15

0.2 TEM diameter (nm)

Fr

eque

nc

y

d=14.2±3.2nm

(58)

Example of very large size nanosphere sample: 34FF

0

20

40

60

80

0

0.02

0.04

0.06

0.08

0.1 TEM diameter (nm)

Fr

eque

nc

y

d=32±5nm

(59)

Example of nanoflower sample: 15FF

0

5

10

15

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4 Core diameter (nm)

10

30

50

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16 Outer diameter (nm)

d

_out

=36.3±4.8 nm

d

core

=7.4±1.4 nm

(60)

0.001

0.01

0.1

1

10

100 1000

0.01

0.1 ff30 Iexp

ff30 Ifit

ff15 Iexp

ff15 Ifit

ff25 Iexp

ff25 Ifit

A

b

s

o

lu

te

i

n

te

n

s

ity

I (

c

m

-1

)

Scattering vector q (Å

-1

)

Particle form factors by small angle neutron scattering

Guinier

Porod

𝐼 ≅ ΦΔ𝜌

2 𝑉

_{𝑉 𝑒}

2 −𝑞

2 𝑅

𝐺

2 ⁄

3 𝐼 ≅ 2𝜋Φ 1 − Φ Δ𝜌

2 _𝑉

𝑆

30ff:

18.9 18.1±3.9 23.5 ± 4.2

31.7

33.1 R

_G

(nm) 𝑅

_𝑉

2 _⁄

_𝑉

(nm) 𝑅

_TEM

(nm)

15ff:

19 10.6±3.9 17.5 ± 2.4

89.9

56.6 𝑆spe

(m

2 /g)

𝑆spethe

PACE spectrometer

with Annie Brûlet

𝑆

𝑉

the

= 3 𝑅

�

_𝑉

2 _⁄

_𝑉

Scattering vector q (Å

-1

₎

25ff:

10.5 10.4±2.3 7.1 ± 1.6

52.6

57.7

(61)

Necessity to measure precisely iron oxide concentration

Experimental measurement

of all properties (m

_S

, ∆n

_S

,

SHP, P(q), r

₁

, r

₂

…) require

the total iron concentration.

Available methods are:

• Atomic Absorption

Spectroscopy (or ICP):

sensitive (10

-5

_{M) but ±5%}

• Redox titration (Charlot) by

K

₂

Cr

₂

O

₇

/SnCl

₂

: precise (±1%)

but not sensitive (10

-1

_M)

• Whole UV-Vis curve: precise

(±1%) and sensitive (10

-4

_M)

1.E+00

1.E+01

1.E+02

1.E+03

1.E+04

200

300

400

500

600

700

800 λ

(nm)

ε=

A

b

s

/c

/l

(mo

l/

L

/cm)

unknown concn.

calibration curve

• “Ferrozine assay”: highly sensitive (10

-7

_{M) from OD}

(62)

61 ν

ν

ε

h

E

h

c

(

-

_g

bulk

)

1 /

2 =

UV-Vis molar extinction

coefficient

3,6 eV for Fe

₂

O

₃

Shannon, J. Phys. Chem.

Ref. Data 2002

Constant

UV-Vis extinction is independent on MNP size distribution

0 1E+12

2E+12

3E+12

4E+12

5E+12

6E+12

7E+12

2

2.5

3

3.5

4

4.5

5

5.5 hν en eV

(ε

*h

ν)

2 S1=5.8nm

S=7.7nm

CS1=8.6 nm

CC1=9.3nm

E

_gap

=3.6 eV

A. Abou-Hassan

UPMC thesis 2009

2010 Best thesis

prize

in physical

chemistry

(SFP/SCF)

→ no size-dependent

gap in the case of

γ-Fe

₂

O

₃

(the exciton

diffusion length is

presumably much

smaller than th

e size

of the USPIOs, thus no

confinment)

Direct band-gap semi-conductor (CdS, AsGa…)

Brus, J Chem Phys 1984, Science 273, 87 1996