1
Franck ARTZNERInstitut de Physique de Rennes
UMR CNRS 6251Université Rennes 1
Auto-assemblages bio-inspirés : peut-on fabriquer sans effort des structures complexes avec une
précision sub-nanométriques ?
Journée "Nanosciences pour l’énergie" Auto-assemblages bio-inspirés : peut-on fabriquer des structures complexes
avec une précision sub-nanométriques ?
- Introduction+ Exemple d’enjeux de la précision sub-nanométrique+ Intérêts des auto-assemblages biologiques
- Deux mécanismes d’auto-assemblages :+ Contrôle du diamètre de nanotubes de silice+ Cristallisation de nanoparticules
Quantum Dots : QDs
λémission
d = 2 nm
r
Fluorescent semi-conductor nanocrystal
d = 6 nm
d
Shell (ZnS) Core (CdSe)
HydrophobicLigands
VB
CB
Noginov, Nature 2009
Some nanostructures…with well defined lengths
Spasereffect
quenching no couplingResonance :doptimum
d d d
LPNFedotov, PRL 2010
Some nanostructures…with well defined lengths
Purcell effect
Coherence
High Accuracy (<1nm) is required
Tobacco Mosaic Virus (TMV) Self-assembly
Self-assemblyof 2130 proteins
- Monodisperse (length, diameter)- Spontaneous self-assembly- Reproducibility - Parallel Processes- Triggering
2
Virus-Enabled Silicon Anode for Lithium-Ion BatteriesChen, ACS NANO, 2010
Dujardin, NanoLetters, 2003
Belcher, Science, 2002
Gold nanoparticles
SiliconZnS nanoparticles
18nm
Applications… Silica Marine Sponge : Euplectella sp.
Aizenberg, PNAS, 2004
Aizenberg, Science 2005, …
A perfectoptical fiber
inout
Silica Marine Sponge : Euplectella sp.
1μm
10μm
100nm
100μm
1mm
1cm
10cm
5mm
20μm
5μm
1cm
500nm
HierarchicalOrganization :
From centimeter to nanometer
1μm
10μm
100nm
100μm
1mm
1cm
10cm
10µm
1cm
Bio-inspired self-assembliesSome advantages …
1cm500nm
+ Monodispersity+ Reproducibility+ High Accuracy- Length tuning
+ Hierarchical self-organisation
+ Simple and low cost :No external work,…
+ Simultaneous processesHigh throughput,…
Objective :Design of bottom-up processes
generating well-defined nanostructures ??
Bio-inspired Scaffolds to manufacture nanomaterials :
nanotubes & Quantum Dots arrays
Objectives :+ Shape+ Crystallization+ Monodispersity+ Length Modulation
Objectives :+ Shape+ Crystallization+ Monodispersity+ Length Modulation
Which Scaffolds or template ????
Bio-inspired Scaffoldsto manufacture nanomaterials :
nanotubes & Quantum Dots arrays
3
Bio-inspired Scaffolds to manufacture hybrids materials :
Silica nanotubes & QDs metacrystals
Biological Self-Assemblies…
Virus φ=25nmProteins :
Size : 3-6 nm
Part 1 Part 2
Outline : 2 examples with- Scaffold- Nanomaterials- Properties
A Peptidic Template to Manufacture Silica Nanotubes
Self-assembly process ?
1,8nm
2+
Self-assembly process ?
I] PeptidicNanotubes
II] Mineralization
A Peptidic Template to Manufacture Silica Nanotubes
A
300 nm300nm
A Peptidic Nanotube Template
Freeze Etching EM
Lanreotide: synthetic octapeptideColl. Maité Paternostre (Saclay)
Diameter :24.4 nm
Wall thicknesse = 2 nm
water
5%(w/w)
Structure by Fiber Diffraction =>Valery & al, PNAS (2003)
Phase diagram in water :Valery & al, Biophys. J. (2004)
Self-assembly mechanism :Pouget & al, J.A.C.S (2010)
Ipsen-Pharma
Céline Valery PhD thesis 2003
4
3) Hydrophilic :+ H20
+
+
+
2) Aliphatic/Aliphatic :
4) Hydrogen Bonds :
1) Aromatic/Aromatic :
1,8nm
2+
Biological Interactions in Water :A nanometer scale Lego
Orientation !!!
aliphatic
aromatic
Self-assembly Rules
A Hierarchical Organisation
Step 1 Step 2
Step 3
26 protofilaments
18 Å
+ water
+
+
+
An dynamical equilibrium in water
+
++
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++++
+
+++
++
++
+
+ ++
++
++
+
++
++
+ + +
- Electrostatic repulsion- Translation entropy
- Aromatic- Aliphatic
2+
Nanotube mineralization1 the organic template:
Lanreotide
1,8nm
24 nm
2 nm
octapeptide
2+
H2O
2 the inorganic compounds:silica
TEOS: Si(OEt)4
?Emilie Pouget PhD thesis 2006Christope Tarabout PhD thesis 2009
Morphological control: limited diffusion by a gel containing the peptide in a solution of silica precursors (TEOS)
Synthesis: spontaneous organic/inorganic assembly
"chimie douce" : in water, room T°, neutral pH
time≈48h
peptide
TEOS/waterFibers
~1cm
Capillarydiameter=1,5mm
Pouget & al, Nature Materials (2007)
1μm
10μm
100nm
100μm
1mm
1cm
10nm
1nm
Macroscopique FibersPolarising Ligth Optical Microscopy
=> Orientationnal order parallel to fiber axis
200μm
Dry Fiber
1mm
As synthesised
1mm
=> Centimeter Length
5
1μm
10μm
100nm
100μm
1mm
1cm
10nm
1nm
Transmission Electron Microscopy
Nanotubes Bundles
1 μm
Mineralisation possible !!
Coll. Erik Dujardin, Annie Cavalier
200nm
Long nanotubes with a monodisperse diameter
1μm
10μm
100nm
100μm
1mm
1cm
10nm
1nm
1μm
10μm
100nm
100μm
1mm
1cm
10nm
1nm
B
C
A
25nm 25nm
50nm
Silica Double walled Nanotubes
2 spatial frequencies :- 3.4nm with cos-like phase = FT (double dirac ) => double wall- 25.4nm with Jo-like phase = FT (thin cylinder)
1μm
10μm
100nm
100μm
1mm
1cm
10nm
1nm
SAXS (Small Angle X-ray Scattering)SAXS Beam Line ID O2, ESRF, T. Narayanan, T. Weiss
0,2Å-1
TemplateStructure
isconserved
0
0,01
0,02
0,03
0,04
0,05
0,06
0,07
0,08
0,09
0,1
0,05 0,15 0,25 0,35 0,45
q(A-1)
log
(I
0,096Å-1
Δq=0,025Å-1
q(Å-1)
Log
(I)
Lanreotide
Silica
<d> = 24.6nm
Simple model
r (nm)
SiLan
Siρ
1.4 2.0 1.4
1μm
10μm
100nm
100μm
1mm
1cm
10nm
1nm
Hierarchical Characterisation
Formation mechanism ?
Silica : 1,4nm
Lanreotide: 2nm
<d> = 24,6nm
Initial template Mineralisation ?
Lanreotide.Initial Nanotubes
TEOS/water
Dynamical template
Time ≈48h
6
++
++
2+2+
--
++
++
--
Pouget & al, Nature Materials (2007)
- dynamical template- kinetic coupling of reactions
A step by step construction :- dynamical template- kinetic coupling of reactions
A step by step construction :
Infinite growing ?????
Optical fibers ?
Duval et al, Electronic Letters, 2008
Diameter (µm) Loss (dB/cm)
4 -1.2
10 -2.3
20 -5.7
50 -6.6
35nm
9nm
Diameter Control ? Coll. J.C Cintrat (CEA Saclay)N. Fay, M. Paternostre (Saclay)
… a Peptides Library.
Close contact model :Diameter prediction : > 95%
NH
NN
N
O
O
O
H
H
H O
NH2
NN
O
OH
H
O
N
H
N
O
H
NH2
OH
HN
+H3N
OH
SS
A Diameter library from ..
24nm
Tarabout et al, PNAS 2011
From a Bio-inspired Scaffoldto Silica Nanotubes
StructureInteractions
- Aromatic- Aliphatic- Hydrophylic- H-bonding- Coulomb
Mutations+ Diameter
From 9 to 35 nm
- Shape (ribbons,…)Library of 20 mutants
Nano-optics within Bundles
Mineralisation
Part 2 :
Bio-inspired Scaffolds to manufacture nanomaterials :
nanotubes & Quantum Dots arrays
7
Toward 3D template : lipids multilayers
4 nm
Phospholipids
Lipid membrane in water :
O
O
O
O
N
O
O
O
O
OP
N
O OO
DMTAP
DMPC
++
+
++ +
+
+
++++
+SUV50nm
lipids multilayers
Bending Energy :
E = ½.kbend.u2.q4
E ∝ ½. kbend.u2/d4u
d = 2π/q
Colloid adhesion effects ?
+ Strong adhesion+ Large size
Flat 1D 2D
Can we generate in plane orderwith planar membranes ? Quantum Dots : QDs
λémission
d = 2 nm
r
Fluorescent semi-conductor nanocrystal
d = 6 nm
d
Shell (ZnS) Core (CdSe)
HydrophobicLigands
Coll. Valérie Marchi-Artzner (Chemistry@Rennes)
Functionnalization
1. Hydrosoluble QDs2. Anionic QDs
-
---
-
-
- -
3. QDs size (= λemission)
3.0 nm
dQD~6-8 nm
-Hydrophilic linksSulfur
Coll. Valérie Marchi-Artzner (Chimie@Rennes)
Crystallization by adhesion ?
++
++++
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+
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--
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- -
++
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+ ++
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+ ++
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+ ++
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+
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++++
++
+ ++
++++
++
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++++
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+ ++
++++
++
+
--
- --
-
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- -
Coll. Marc Schmutz (ICS)
A. Dif, E. Henry et al, J.A.C.S. 2008
Coll. Valérie Marchi-Artzner (Chimie@Rennes)
8
G-actin
Actin filament
6nm
Anionic Polyelectrolyte
8nm
- 43 kDa- 375 AA- charge 4 à 6 –
Self Assembly
How to improve in-plane order ?
-
---
-
-
- -3.0 nm
dQD~6-8 nm
In-plane (2D) orderVery weak
35nm
300 µm
300 µm
++
++++
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- -
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+ ++
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+
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+ ++
++++
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+
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++++
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+ ++
++++
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+
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+ ++
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+
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+ ++
++++
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+
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380<λex<420 nm
Toward the 3D crystallization ?
2 phases …
Phase 1: 1D crystallization….Small Angle X-ray ScatteringSWING@SOLEILFlorian Meneau
6nm
6nm
10nm
10nm
Chains of Quantum Dots
8
9
10
2
3
0.250.200.150.100.050.00q[Å-1]
Phase 2 : 3D Crystallization
26.5nm
18.9nm
35.5nm
Small Angle X-ray ScatteringSWING@SOLEILFlorian Meneau
expe
3D model
Nanoparticules crystallisation by template strategyHenry et al, Nano Letters 2011
300 µm
380<λex<420 nm
Dynamical Templating
Post doc A. Dif
10
8
6
4
2
0
Inte
nsity
/ a.
u.
600580560540520500wavelength / nm
10
8
6
4
2
0
Inte
nsity
/ a.
u.
600580560540520500wavelength / nm
I (u.
a.)
Longueur d’onde d’émission (nm)
Excitation à 405 nm
Nanostructuration and optical properties
9
b c
2
1
)(0
01)( ∑
=
⋅−=−ΓN
l
rkki leN
kkrrrrr
Superradiance :
Conclusion : The scaffold is the key
Nanosciences pour l’énergie Auto-assemblages bio-inspirés
Transport optique Cohérence optique
AcknowledgementsBiomimetic@Rennes+ Emilie Pouget (Silica nanotubes)+ Christophe Tarabout (Diameter Modulation)+ Etienne Henry (Actin/QDs)+ Cristelle Mériadec (X-ray)+ Marie Postic (QDs crystallization)+ Open Postdoc Position (X-ray, biomimetic)
Synchrotron :T. Narayanan (ESRF)F. Meneau (SOLEIL)
Electron MicroscopyErik Dujardin (Toulouse)Marc Schmutz (Strasbourg)A. Cavalier (Rennes)
CEA@SaclayMaité PaternostreNicolas FayJ.C. CintratB. Rousseau
IPSEN PharmaCéline Valéry
Institut Curie François Amblard (actin)
Chemistry Dpt (Rennes) Valérie Marchi-Artzner (QDs)Aurélien Dif
€ ACI nano (2002-04)Région Bretagne, Rennes Métropoles