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Supramolecular NanoMaterials and Interfaces Laboratory
Institute of materials - Institut de Matériaux
20 µm
“Striped” Nanoparticles and
Lipid BilayersFrancesco Stellacci
Institute of Materials, EPFL, Lausanne, [email protected]
@frstella
S u N M I L -‐ Ins&tute of Materials
Scanning Tunneling Microscopy (STM) Images of ‘Striped’ Nanoparticles
b
5 nm
2 nm2 nm
ab c
c d
Jackson, Myerson, Stellacci, Nat. Mat., 2004; Jackson, Silva, Hu, Stellacci, JACS., 2006
S u N M I L -‐ Ins&tute of Materials
Stripe Formation in Mixed Monolayers
Entropy gainin stripe formation
with Sharon Glotzer, U. Mich; PRL 2007
Size
DeVries, Stellacci, Science 315, 358, 2007Carney, JACS 2008Unpublished data
TEM,NMR, Noesy
Gel Electrophor.AUC
Singh, PRL 2007
S u N M I L -‐ Ins&tute of Materials
Mixed SAMs on Flat surfaces
Stranick,, Weiss. Nanotechno. 1996 Smith; Weiss, J. Phys. Chem. B, 2001
!
Entropy
Enthalpy
with Sharon Glotzer, manuscript in prep.
Two problems: composition, annealing
S u N M I L -‐ Ins&tute of Materials
Kinetics of SAM formation
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!
!
45º Rotation
Scale bar: 100 nm
20 nm
with Sharon Glotzer, manuscript in prep.
S u N M I L -‐ Ins&tute of Materials
Janus Particles
STM in air (Veeco multimode)! STM in UHV (Omicron)!
d=10.37±1.01nm! r=0.39±0.06!
Nanoparticles diameter! Ligands ratio!(based on the measured area)!
JavierReguera
S u N M I L -‐ Ins&tute of Materials
Imaging Self Assembled Monolayers
3 nm
OT
MPA
OT
Scanning Tunneling Microscopy
S u N M I L -‐ Ins&tute of Materials
STM Image Analysis
STM in air(Veeco Multimode)
2007<s>= 0.95 nm
10 nm
New Data: Dr. Miao Yu10 nm
STM in vacuum(Omicron)
2010<s>=1.05 nm
Qualitativeand
Quantitative
Tip Speed Dependenceof Average Spacing
Regression Analysis (α=0.05)
Hu et al. J. Scan. Probe Micr. 2010
S u N M I L -‐ Ins&tute of Materials
0 20 40 60 80 100% Blue
Perfect Mixing vs Phase Separation
PERFECT MIXING model
PHASE SEPARATION model 0 50 100% Blue
Koda%, V. R. et al. J. Phys. Chem. 1994; Malicki, M. et al. Phys. Chem. Chem. Phys. 2010
Qualitative plots
The intermolecular coupling between similar molecules decreases with dilution
a.u.
a.u.
Centrone et al., Small, 2006
S u N M I L -‐ Ins&tute of Materials
NMR Analysis of Mixed Ligand Nanoparticles
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! !!
2,7-dimethyl octanethiol (br-OT)
!
4.5 nm 2.5 nm 4.5 nm
S u N M I L -‐ Ins&tute of Materials
Polar Molecules
!
1:3 (2.9)
1.2 (2.4)
1:2 (2.4)
2:3 (1.5)
2:3 (1.7)
6
6.4
4.8
5.7
5.6
DPT:DDT (measured)
Polar Mol.
Assuming 371 ligands per par%cle on 4.4 nm nanopar%cles, the number of pole molecules per par%cle is on average 5.7±0.5
S u N M I L -‐ Ins&tute of Materials
WSLAB = xAWSL
A + xBWSLB
Structure Effects on Surface Energy
Kuna, Voitchovsky,, Stellacci, Nature Mat. 2009
Wsl = xAWslA + xBWsl
B + f(structure)Wsl = xAWslA + xBWsl
B + f(structure)
S u N M I L -‐ Ins&tute of Materials
Effect of Structure on Properties
1 x 1
SolubilityExperiments
Theory
with Nicola Marzari; PNAS 2008
MolecularRecognition Catalysis
Xiang Liu Small on line
Anirban GoshAngewandte Chemie on line
S u N M I L -‐ Ins&tute of Materials
Cellular Trafficking of Carriers
Diffusion
Biological Materials Synthetic Materials
Challenge/Fundamental Problem: Cell membrane penetration
Poration
S u N M I L -‐ Ins&tute of Materials
Effect of Nanoparticle Coating
Protein Interactions
Verma, Uzun, Irvine, Stellacci, Nature Mat. 2008
S u N M I L -‐ Ins&tute of Materials
Cell Uptake of Rippled Nanoparticles
All MUS MUS brOT 2:1 MUS OT 2:1
Verma, Uzun, Irvine, Stellacci, Nature Mat. 2008
Incubation in serum free conditionsIncubation in serum containing conditions
S u N M I L -‐ Ins&tute of Materials
Effect of Ripples on Cell Uptake
E
Comparable results have been obtained in studies made with or without serum media during
incubation and with particles with or without fluorescent ligand
Verma, Uzun, Irvine, Stellacci, Nature Mat. 2008
S u N M I L -‐ Ins&tute of Materials
A B C D
Cell Membrane Penetration
The absence of endocytosis has been independently confirmed via TEM studies
4 0C Experiment
Verma, Uzun, Irvine, Stellacci, Nature Mat. 2008
S u N M I L -‐ Ins&tute of Materials
Endocytosis Inhibitors
CalceinOnly
Z-Stack Images
No
sodi
um a
zide
and
2-d
eoxy
gluc
ose
sodi
um a
zide
and
2-d
eoxy
gluc
ose
Calceinand
‘Striped’NPs
Calceinand
TriMethyl Ammonium
NPs
PI Staining
CyQuant
Verma, Uzun, Irvine, Stellacci, Nature Mat. 2008
S u N M I L -‐ Ins&tute of Materials
The Tale of Two Supramolecular Systems
Striped Nanoparticles Lipid Bilayers
• Gel Phase• Ligand Mobility mostly vertical• Conformational Entropy• Unique Wetting properties
see Centrone, PNAS, 2008 Kuna, Nat. Materials, 2009
• Fluid Phase• Ligand Mobility mostly in plane• Positional Entropy• Wetting Properties?
S u N M I L -‐ Ins&tute of Materials
At the more fundamental level….
AFM images of supported bilayers and striped particles
70 nm
Dr. Kislon Voitchovsky, unpublished data
S u N M I L -‐ Ins&tute of Materials
Towards an Understanding
V, I
• 1,2 diphytanoyl-sn-glycero phosphocholine lipid
bilayer• pH 8.1 Tris-HCl 0.1 M, KCl 2 M• Reference Ag/AgCl electrodes
V
t
I
t
In collab. with Prof. Yann Astier, University of Lisbon, Portugal
S u N M I L -‐ Ins&tute of Materials
Nanoparticle/Bilayer Interactions
All TMA/MUS Blank
Blank T=30min
0.8 mg/ml T=1h
1.6 mg/ml T=1h30
2.0 mg/ml T=2h20
MUS OT 2:1
MUS/brOT
S u N M I L -‐ Ins&tute of Materials
The Role of Nanoparticle Size
unpublished data, Randy Carney
4 5 6 7 8 9
nm
Carney, Stellacci, BakrNature Communications on line
S u N M I L -‐ Ins&tute of Materials
Acknowledgements
Graduate StudentsJin Young KimHyewon KimRandy CarneyEun Seoun ChoMaria RicciPaulo Jacob SilvaPost-DocsJavier RegueraXiang LiuYun TanMarta MameliMiao YuQuy Ong Senior ScientistKislon Voitchovsky
NSF: CAREER NIH TPEN ProgramDeshpande Center CMSE-MRSEC DMR 02-13282MARCO 3M Non Tenured Faculty Award3M Innovation Award DuPont Young Professor AwardPackard Foundation Singapore MIT Alliance 2MITEI, ENI Tata Chemicals
2003 2006
2008 2010
Alumni:
Graduate StudentsRobert J. Barsotti, Jr. (Arkema. Senior Sci.)Gretchen A. DeVries (Patent Lawyer)Alicia M. Jackson (DARPA manager)A. Amy Yu (Samsung, senior scientist)Suelin Chen (Post Doc )Sarah Thevenet (Mol. Stamping, Production Eng.)Tan Mau Wu (Patent Lawyer )Benjamin Wunsch (Post Doc )Osman Bakr (Ass. Prof. KAUST )Jeffrey Kuna Ozge Akbulut (Post Doc)Hijuan Zhang (Samsung, scientist)
Post-DocsMarkus Brunnbauer (Infineon, Senior Scientist)Xiaogang “Bruno” Liu (NUS, Ass. Professor)Brenda Long (U. Birgh., post doc)Andrea Centrone (MIT, post doc)Kazuya Nakata (NIAST, Japan, Ass. Professor)Oktay Uzun (Dow Chemicals)Cedric Dubois (Nestle’)Ayush Verma (Novartis’)Ying Hu (Infinity, scientist)Jin-Mi Jung (Samsung, scientist)Anirban Gosh (Tata Chemicals, scientist)