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Interaction of Fluids with Nano/Bio Materials

Nick Quirke

Use of Simulation, Theory and Experiment to Explore Nanofluidics

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acknowledgements

• Nano-imbibition – Steven Supple (PhD 2005), Matthew Longhurst( PhD 2007)

• Nanotubes in solution– Matthew Longhurst( PhD 2007)

• Nanoparticles at bio-interfaces– Mario Franco-Melgar( PDRA )

• Experimental nanofluidicsMax Whitby (PhD 2009), Nimisha Wajli (PhD 2010), John Lin (MRes 2008), Maya

Thanou (Royal Society University Research Fellow)

• Two and Three Phase flowsT Myoshi (PhD 2008), Matt Schneemilch (PDRA), Matthew Groombridge (MRes 2007,

PhD 2010)

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• Microfluidics to

• Nanofluidics

motivation

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Gene Therapy Main Challenge: Delivery

Viral vs non-viral (synthetic)

Adeno-associated virus Polymer/DNA Liposome/DNA

25nm 70-100nm70 -100nm

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LUNG AIRWAYS:

Nanotoxicology

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S. Supple, N Quirke, Phys Rev Letts 90, 214501 (2003), J Chem Phys,121, 8571 (2004)

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Dynamic response of systems over very short time scales

dchem =1.4 nm

Transient responses – average over NE ensembles

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0

100

200

300

400

500

600

700

800

900

0.5 1 1.5 2 2.5 3 3.5 4 4.5

d (nm)

v (

m/s

)For ‘nanofluidic scales’ , L~ms, t< s, we expect ultrafast imbibition

122dL

V rdt

theory

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1 1

2 1

at

at

ex at

at e

L tx

ns

CNT

Exponents for general materials:

1 nanosecond

Falls to 1/2

Non carbon tube

S. Supple and N. Quirke, Nanocapillarity: II: Density profile and molecular Structure for decane in carbon nanotubes, J Chem Phys, 122, 104706, (2005)

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Raman Scattering from Nanotubes

hlaser

laser + vib

laser - vib

RBM R-1

Pick out RBM

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Simulation of the RBM• We can measure the RBM directly from

simulation by performing an FFT on the average radial velocity component of the C atoms

• Presence of water causes upshift in agreement with experiment (4-10 wavenumbers)

RBM 300 K in vacuum / cm-1

120 140 160 180 200 220 240

f

/ cm

-1

0

2

4

6

8

10

12

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M. Longhurst and N. Quirke, Environmental effects on the radial breathing modes of carbon nanotubes in water, J Chem Phys 124, 234708 (2006)

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Determination of CNT-water interaction

•Upshift as a function of nanotube diameter

•Solid line – theory

•Circles – εC-water (42)

•Triangles – εC-water (86)

•Short dotted line – C-C bond hardening due to Laplace curvature effects

RBM 300 K in vacuum / cm-1100 120 140 160 180 200 220 240

f

/ c

m-1

0

2

4

6

8

10

water-C / kJ mol-10.0 0.2 0.4 0.6 0.8

f

/ cm

-1

0

2

4

6

8

10

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(a)

(b)Upshift as a function of nanotube-water

interaction strength

Solid line – theory

triangles – simulation data

long dotted line corresponds to the experimental shift of Izard et al..

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Low frequency vibration of hydration water

• Low wave number radial vibration of water

• Shifts upwards with pressure

• At higher pressures there is more mode mixing and the nanotube RBM frequency is also visible

• Should be possible to detect using low wave number notch filters for Raman

Wavenumber / cm-10 100 200 300 400 500

Co

rre

latio

n /

arb

itra

ry u

nits

0 MPa1000 MPa

M. Longhurst and N. Quirke , ‘Pressure dependence of the radial breathing mode of carbon nanotubes: The effect of fluid adsorption’ , Physical Review Letters 98, 145503 (2007)

137,7

22,0

Longhurst, Thesisd 2007

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LUNG AIRWAYS:

Nanotoxicology

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water

DPPC monolayer nanoparticle

Head (hydrophilic)

Tail (hydrophobic)

MODEL SYSTEM:

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2207 H2O32 DPPCT=315K

OxygenCarbonNitrogenPhosphorus(Hydrogen atoms are implicit)

1-2-a-dipalmitoyl-L-phosphatidylcholine (DPPC16)

Mario A Franco-Melgar , Quirke to be published

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OxygenCarbonNitrogenPhosphorus(Hydrogen atoms are implicit)

1-2--dipalmitoyl-L-phosphatidylcholine (DPPC16)

Mario A Franco-Melgar , Quirke to be published

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Contact Angle

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High resolution SEM image of nanopipe arrayHigh resolution SEM image of nanopipe array

M. Whitby and N Quirke, ‘Fluid flow in carbon nanotubes and nanopipes’ Nature Nanotechnology 2, 87, 2007

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Controlled release of dextrans from carbon nanopipesControlled release of dextrans from carbon nanopipes

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Nanomedicines across barriers: nanoparticles in mucus

100 frames movie superimposed to show thetrajectory of nanoparticles through CF mucus.

Confocal Microscope image of 100nm Nanoparticles in reconstituted cystic fibrosis mucus.

Polystyrene nanoparticles labelled with fluorescein used as models for gene delivery vectors (Nimisha Walji, Max Whitby, Maya Thanou)

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20 40 60 80 100 1200.0

0.2

Equation 4 Stokes-Einstein Nanoviscosity Stokes-Einstein

Dif

fus

ion

Co

eff

ice

nt

(m

2s-1

)

Nanoparticle Radius (nm)

r

kTD

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polystyrene nanoparticles through mucus

1.Nimisha Walji, N. Quirke, Maya Thanou, ‘The Diffusion of Nanoparticles less than 100nm in Mucus: Using Multiple Particle2. Tracking to Understand Nanoscale Phenomena.’, Biophysical Journal (submitted)

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It is significant that the size range of nanomaterials discussed in this talk is essentially the size range of many important biological entities (antibodies, viruses). Larger molecules such as DNA can be uncoiled to fit.

• Carbon nanopipes are potential conduits, collimators, sensors, encapsulators and probes for medical applications

• Nanoparticles are potential therapeutic vectors

Clearly there are still many challenges ahead before such devices become viable including:

• Toxicology• Controlling the mechanical strength of nano-elements in contact

with cells and tissue;• Methods for the assembly of huge numbers of very small

components;• Fouling of the nanopipes and surfaces; management of defects in

components;• Managing the information flow from large arrays of nanoscale

sensors to the outside world.

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