Institute of materials - Institut de Matériaux “Striped” Stellacci.pdf · A. Amy Yu (Samsung, senior scientist) ... (Samsung, scientist) Post-Docs Markus Brunnbauer ... Jin-Mi

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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


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


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


Kinetics of SAM formation

!"#$%&" '!"#$%&" ()"#$%&" *'"#$%&"

!

!

45º Rotation

Scale bar: 100 nm

20 nm

with Sharon Glotzer, manuscript in prep.


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


Imaging Self Assembled Monolayers

3 nm

OT

MPA

OT

Scanning Tunneling Microscopy


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


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


NMR Analysis of Mixed Ligand Nanoparticles

!

! !!

2,7-dimethyl octanethiol (br-OT)

!

4.5 nm 2.5 nm 4.5 nm


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



Striped Particles

~5 nm


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)


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


Cellular Trafficking of Carriers

Diffusion

Biological Materials Synthetic Materials

Challenge/Fundamental Problem: Cell membrane penetration

Poration


Effect of Nanoparticle Coating

Protein Interactions

Verma, Uzun, Irvine, Stellacci, Nature Mat. 2008


Cell Uptake of Rippled Nanoparticles

All MUS MUS brOT 2:1 MUS OT 2:1


Incubation in serum free conditionsIncubation in serum containing conditions


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



A B C D

Cell Membrane Penetration

The absence of endocytosis has been independently confirmed via TEM studies

4 0C Experiment



Photothermal Imaging

with Brahim Lounis


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



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?


At the more fundamental level….

AFM images of supported bilayers and striped particles

70 nm

Dr. Kislon Voitchovsky, unpublished data


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


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


The Role of Nanoparticle Size

unpublished data, Randy Carney

4 5 6 7 8 9

nm

Carney, Stellacci, BakrNature Communications on line


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)

Documents

Institute of materials - Institut de Matériaux “Striped” Stellacci.pdf · A. Amy Yu (Samsung, senior scientist) ... (Samsung, scientist) Post-Docs Markus Brunnbauer ... Jin-Mi