Interaction of Fluids with Nano/Bio Materials Nick Quirke

1. Interaction of Fluids with Nano/Bio Materials Nick Quirke Use of Simulation, Theory and Experiment to Explore Nanofluidics

2. 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 nanofluidics Max Whitby (PhD 2009), Nimisha Wajli (PhD 2010), John Lin (MRes 2008), Maya Thanou (Royal Society University Research Fellow) • Two and Three Phase flows T Myoshi (PhD 2008), Matt Schneemilch (PDRA), Matthew Groombridge (MRes 2007, PhD 2010)

3. motivation • Microfluidics to • Nanofluidics

4. Gene Therapy Main Challenge: Delivery Viral vs non-viral (synthetic) Polymer/DNA Liposome/DNA Adeno-associated virus 70 -100nm 25nm 70-100nm

5. Nanotoxicology LUNG AIRWAYS:

6. Dynamic response of systems over very short time scales 13,13 dchem =1.4 nm S. Supple, N Quirke, Phys Rev Letts 90, 214501 (2003), J Chem Phys,121, 8571 (2004) Transient responses – average over NE ensembles

7. For ‘nanofluidic scales’ , L~ms, t< s, we expect ultrafast imbibition theory

8. CNT Exponents for general materials: L tx Non carbon tube Falls to 1/2 ns 1 nanosecond S. Supple and N. Quirke, Nanocapillarity: II: Density profile and molecular Structure for decane in carbon nanotubes, J Chem Phys, 122, 104706, (2005)

9. Raman Scattering from Nanotubes hlaser laser + vib laser - vib Pick out RBM RBM  R-1

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

11. 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 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..

12. 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 M. Longhurst and N. Quirke , ‘Pressure dependence of the radial breathing mode of carbon nanotubes: The effect of fluid adsorption’ , Physical Review Letters98, 145503 (2007)

13. Longhurst, Thesisd 2007 7,7 22,0

14. Nanotoxicology LUNG AIRWAYS:

15. water MODEL SYSTEM: nanoparticle DPPC monolayer Head (hydrophilic) Tail (hydrophobic)

16. Mario A Franco-Melgar , Quirke to be published 2207 H2O 32 DPPC T=315K 1-2-a-dipalmitoyl-L-phosphatidylcholine (DPPC16)

17. 1-2-a-dipalmitoyl-L-phosphatidylcholine (DPPC16) Mario A Franco-Melgar , Quirke to be published Oxygen Carbon Nitrogen Phosphorus (Hydrogen atoms are implicit)

18. Contact Angle

19. High resolution SEM image of nanopipe array M. Whitby and N Quirke, ‘Fluid flow in carbon nanotubes and nanopipes’ Nature Nanotechnology 2, 87, 2007

20. Controlled release of dextrans from carbon nanopipes

21. Nanomedicines across barriers: nanoparticles in mucus Confocal Microscope image of 100nm Nanoparticles in reconstituted cystic fibrosis mucus. 100 frames movie superimposed to show the trajectory of nanoparticles through CF mucus. Polystyrene nanoparticles labelled with fluorescein used as models for gene delivery vectors (Nimisha Walji, Max Whitby, Maya Thanou)

22. polystyrene nanoparticles through mucus • Nimisha Walji, N. Quirke, Maya Thanou, ‘The Diffusion of Nanoparticles less than 100nm in Mucus: Using Multiple Particle • Tracking to Understand Nanoscale Phenomena.’, Biophysical Journal (submitted)

23. 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.