AUTOENSAMBLAJE

Por auto-ensamblaje molecular se entiende un proceso por

el cul un conjunto de molculas se organiza dando lugar a
una nueva estructura supramolecular en la cual las
molculas individuales se mantienen unidas mediante
enlaces no covalentes (fuerzas de Van der Waals, basadas
en el carcter hidrfobo/hidrfilo, puentes de hidrgeno,
etc.).
 En el caso de los slidos silceos nanoestructurados,
las molculas orgnicas responsables de la
estructuracin del slido, son molculas anfiflicas,
es decir, estn formadas por al menos dos dominios
con propiedades muy diferenciadas, en general una
zona hidrfila y otra hidrfoba (Anyonietti, A. 2001).
 Esta caracterstica propia de los surfactantes
provoca que, en disolucin, se produzca la
organizacin supramolecular o autoensamblaje
de estas molculas en micelas con distintas
geometras dependiendo de la naturaleza del
surfactante, la concentracin y la temperatura:
 REVERSE MICELLES
Reverse micelles are small Collision by Brownian motion

aqueous droplets separated Au+3 SO3=

from the bulk organic phase

by a surfactant layer, and are
prepared according to a Intermicellar
water to surfactant molar exchange process

ratio (w).
gold (nm)

They act as nanoreactors

gold (nm)

which collide continuously Separation

exchanging their water
content. Fig.1. Representation of the micellar
exchange process.
 Structure of AOT

v
Packing parameter: 1.0
al

Fig.2. Illustration of AOT molecular structure.

 Determination of the water pool radius Rw
Film of N AOT molecules A spherical shape is
assumed for the reverse micelle
structure:
Water pool
V vw wN (1)
RW
where vw is the volume of a free
water molecule (30 3), and N is
the surrounding film of AOT.

The total interfacial area (S), is given by: S aN , (2)

Where a is the area per head group of AOT molecule (60 2), then:
V 1
w( ) (3) from geometrical considerations: V 1 Rw (4)
S 2 ; S 3
Taking equations (3) and (4): Rw 1.5w ( ) (5) (*)
(*) M. Pileni. J of Phys Ch, vol 97 p.p 6961-6973, 1993
 OBJECTIVES

Synthesize gold nanoparticles from a metal salt and sulfite in

water-AOT-Isooctane reverse micelles with w = 10
Describe the optical properties of gold nanoparticles from
extinction measurements
Determine their average sizes, using Dynamic Light
Scattering (DLS), and Transmission Electron Microscopy (TEM)
Study the stability of gold nanoparticles in microemulsions
Use time correlated UV-Vis extinction measurements to
follow the formation of gold nanoparticles in reverse micelles
 MATERIALS

Auric potassium tetrachloride (KAuCl4)

Potassium sulfite (K2SO3)
Gold colloids (size range: 5-100 nm)
Deionized and degasified water
Organic solvent: 2,2,4-trimethylpentane (isooctane)
Surfactant: Sodium bis-(2-ethylhexyl) sulfosuccinate (AOT)
 METHODS
1. Determination of reverse micelle size.
16
Dh 6.6 0.3w (11)
14
Free water molecules
1.2 nm 12

Dh (nm)
10

Dh 8

4
Water molecules hydrating
4 6 8 10 12 14 16
AOT film
w =[H2O]/[AOT]
Water molecules at the
micellar periphery Fig. 7. Determination of
reverse micelle size.
Fig. 6. Hydrodynamic diameter of a reverse micelle.
 2. Preparation of reverse micelles.
Sample [KAuCl4] mM [K2SO3] mM

Fig.8. Phase diagram for reverse micelles Au1 38 129.498

with w = 10: Aqueous/AOT/Isooctane. Au2 57.55 194.24

Au3 76.74 258.99

100%

Table 1. Aqueous salt precursor

XAOT =0.252% concentration
Metallic salt microemulsion Reduction agent microemulsion
w= 10
Xisoo =0.644%
*
Mixing

Reactants Exchange

100%
100%
Xw =0.1032% Formation of gold nanoparticles

Fig. 9. Schematic representation of reverse micelle synthesis.

 3. Gold nanoparticle synthesis.

2 Au 3 3SO32 3H 2O 2 Au 0 3SO42 6 H (12)

Fig. 10. Gold nanoparticles synthesized in reverse micelles with w = 10.

 CHARACTERIZATION
1. Extinction measurements.
1.2 2.5

60 nm w10-10 nm
100 nm w10-30 nm
1.0 5 nm w10-50 nm
2.0 w10-80 nm
w10-100 nm
10 nm 80 nm
0.8

15 nm 50 nm 1.5
0.6
20 nm

30 nm 1.0
0.4 40 nm

Normalized absorption
Normalized absorption

0.2
0.5

0.0
400 450 500 550 600 650 700 300 400 500 600 700

(nm) (nm)

Fig.11. Gold colloid in aqueous Fig.12. Gold colloid in reverse

medium (v < 1%) micelles (v < 0.1%)
 4. Transmission Electron Microscopy (TEM)

8-10 nm
individual particle

Aggregation of
particles

Fig. 18. TEM of gold nanoparticles synthesized with Au3 concentration in

w =10 reverse micelles.
 Arcoleo and co-workers (*) have synthesized gold
nanoparticles in reverse micelle formed by water/AOT/n-
heptane. They observed from AFM measurements:

aggregation of gold nanoparticles was attributed to an

attractive interaction between particles (confirmed latter
by AFM measurements)

presence of individual particles suggest the existence of a

surfactant layer adsorbed at the nanoparticles surface.

Our TEM measurements agree with these observations.

(*) V. Arcoleo et al. Chemical Physics Letters. Vol 258 p.p 223-227, 1996
 DISCUSSION
Gold nanoparticles were synthesized in reverse micelles
with w=10. A possible core shell geometry with AOT
molecules is expected after the synthesis, which is in
agreement with the observations of Arcoleo and co-
workers.

Peak wavelength red shifts were observed from SFR

measurements. This could be interpreted as particle
agglomeration according to the interaction analysis and
DLS measurements. For this reason, Mie theory cannot
be used to correlate the maximum extinction wavelength
to a time evolution of effective particle size.
 CONCLUSIONS
A core-shell Mie model provided the best fit to
extinction measurements as a function of particle size of
gold nanoparticles in water-AOT-isooctane

DLS measurements showed a considerable degree of

particle agglomeration of gold nanoparticles in reverse
micelles

Micelle-micelle interaction energy analysis indicated

that flocculation may occur for gold nanoparticles larger
than 8 nm