1. Tubing Through the Nano World: Nanotube Functionalization and Practical Applications Nicola J. Burrmann McMahon and Moore Groups September 27, 2007

2. 2 Outline –What are NTs? Structure Characterization Synthesis –Covalent functionalization –Noncovalent functionalization –Applications of functionalized NTs

3. 3 Nanotube (NT) Structure –(m,n) vector v = ma 1 + na 2 Zigzag (9,0) Armchair (5,5) Chiral (10,5) Odom, T. W. et al. Nature. 1998, 391, 62-64. Dai, H. Acc. Chem. Res. 2002, 35, 1035-1044. Iijima, S. et al. Nature. 1993, 363, 603-605.

4. 4 SWNTs vs. MWNTs –MWNT (Multi-Walled Nanotube) (1991) –SWNT (Single-Walled Nanotube) (1993) Iijima, S. Nature. 1991, 354, 56-58. Iijima, S. et al. Nature. 1993, 363, 603-605.

5. 5 Characterization –TEM (Transmission Electron Microscopy) –SEM (Scanning Electron Microscopy) –AFM (Atomic Force Microscopy) Iijima, S. Nature. 1991, 354, 56-58. Sun, Y.-P. et al. Acc. Chem. Res. 2002, 35, 1096-1104. Holzinger, M. et al. J. Am. Chem. Soc. 2003, 125, 8566-8580.

6. 6 Synthesis Dai, H. Acc. Chem. Res. 2002, 35, 1035-1044. Bahr, J. L. et al. J. Mater. Chem. 2002, 12, 1952-1958. High Pressure Carbon Monoxide (HiP CO ) Arc-DischargeLaser Ablation Chemical Vapor Deposition (CVD) Method Fe(CO) 5 and hot CO Electrical Arc, Graphite Electrodes Laser Pulses, Graphite and Metal Catalyst Flowing Hydrocarbon Gas, Metal Catalyst Type of NTSWNT MWNT LatticeHexagons Some Pentagons and Heptagons Purity Significant Byproducts Minimal Byproducts Pros Specific Range of Diameters Controlled Diameters, Arrays, < 500 °C Cons> 1000 °C

7. 7 Great Potential, But… –Unique composition and bonding configuration –Extraordinary electronic properties –Interesting optical properties –Incredible strength and stiffness Dai, H. Acc. Chem. Res. 2002, 35, 1035-1044. Guldi, D. M. Acc. Chem. Res. 2005, 38, 871-878. Liu, Y. et al. J. Phys. Chem. C. 2007, 111, 1223-1229. –The catch……The solution

8. 8 Outline –What are NTs? –Covalent functionalization Oxidation Amidation/Esterification Fluorination Aryl diazonium addition Azomethine ylide 1,3-dipolar cycloaddition –Noncovalent functionalization –Applications of functionalized NTs

9. 9 Acid Oxidation –H 2 SO 4, HNO 3, H 2 O 2 Bahr, J. L. et al. J. Mater. Chem. 2002, 12, 1952-1958. Sinnott, S. B. J. Nanosci. Nanotech. 2002, 2, 113-123. Guo, Z. et al. Adv. Mater. 1998, 10, 701-703.

10. 10 Amidation Chen, J. et al. Science. 1998, 282, 95-98. Lian, Y. et al. J. Phys. Chem. B. 2004, 108, 8848-8853. Sun, Y.-P. et al. Acc. Chem. Res. 2002, 35, 1096-1104. EDAC = DCC =

11. 11 Amidation and Esterification Ramanathan, T. et al. Chem. Mater. 2005, 17, 1290-1295. Lin, S.-T. J. Phys. Chem. 2007, 111, 13016-13021. Sun, Y.-P. et al. Acc. Chem. Res. 2002, 35, 1096-1104.

12. 12 Fluorination Bahr, J. L. et al. J. Mater. Chem. 2002, 12, 1952-1958. Boul, P. J. et al. Chem. Phys. Lett., 1999, 310, 367-372. Stevens, J. L. et al. Nano Lett. 2003, 3, 331-336.

13. 13 Aryl Diazonium Reactions Bahr, J. L. et al. J. Mater. Chem. 2002, 12, 1952-1958. Bahr, J. L. et al. J. Am. Chem. Soc. 2001, 123, 6536-6542.

14. 14 Azomethine Ylides Georgakilas, V. et al. J. Am. Chem. Soc. 2002, 124, 760-761. Cahill, L. S. et al. J. Phys. Chem. B. 2004, 108, 11412-11418.

15. 15 Hydrophobic Interactions Sun, Y.-P. et al. Acc. Chem. Res. 2002, 35, 1096-1104. Dai, H. Acc. Chem. Res. 2002, 35, 1035-1044.

16. 16 Outline –What are NTs? –Covalent functionalization –Noncovalent functionalization Polymer wrapping Non-specific protein adsorption π-Stacking interactions –Applications of functionalized NTs

17. 17 Polymer Wrapping Dalton, A. B. et al. J. Phys. Chem. B. 2000, 104, 10012-10016. O’Connell, M. J. et al. Chem. Phys. Lett. 2001, 342, 265-271.

18. 18 Non-Specific Protein Adsorption Balavoine, F. et al. Angew. Chem. Int. Ed. 1999, 38, 1912-1915. Lin, Y. et al. J. Phys. Chem. B. 2004, 108, 3760-3764.

19. 19 π-Stacking Kauffman, D. R. et al. J. Phys. Chem. C. 2007, 111, 3539-3543. Chen, R. J. et al. J. Am. Chem. Soc. 2001, 123, 3838-3839. Dai, H. Acc. Chem. Res. 2002, 35, 1035-1044.

20. 20 Covalent vs. Noncovalent Functionalization CovalentNoncovalent Solubility Organic and Aqueous Solubility Organic and Aqueous Solubility (Reversible) Binding Interaction Reversible under Harsh Conditions Reversible with Varying Solvent Conditions Hybridizationsp 3 sp 2 ConjugationDecreasedUnaffected Electronic Properties AlteredUnaffected Chen, R. J. et al. J. Am. Chem. Soc. 2001, 123, 3838-3839. Dai, H. Acc. Chem. Res. 2002, 35, 1035-1044.

21. 21 Outline –What are NTs? –Covalent functionalization –Noncovalent functionalization –Applications of functionalized NTs Photovoltaics Biosensing Cellular transport

22. 22 NT Electron Transfer Guldi, D. M. Acc. Chem. Res. 2005, 38, 871-878.

23. 23 Photovoltaics (PV) Guldi, D. M. Acc. Chem. Res. 2005, 38, 871-878.

24. 24 PV Applications Nanohybrid t CS (ns) t CR (  s) SWNT–PyreneNA SWNT/Pyrene + NA SWNT–Fc3.61.1 SWNT/Pyrene + /ZnP 8- 0.20.4 MWNT/Pyrene + /ZnP 8- 0.25.8 SWNT–PSS/H 2 P 8+ 0.314 Guldi, D. M. Acc. Chem. Res. 2005, 38, 871-878. t CS = Charge separation time t CR = Charge recombination time

25. 25 Specific Molecular Detection Shim, M. et al. Nano Lett. 2002, 2, 285-288.

26. 26 Specific Molecular Detection Shim, M. et al. Nano Lett. 2002, 2, 285-288.

27. 27 Biosensors Lee, C.-S. et al. Nano Lett. 2004, 4, 1713-1716.

28. 28 Biosensors Lee, C.-S. et al. Nano Lett. 2004, 4, 1713-1716.

29. 29 Biosensors Lee, C.-S. et al. Nano Lett. 2004, 4, 1713-1716.

30. 30 Cellular Transport Pantarotto, D. et al. Chem. Commun. 2004, 16-17.

31. 31 Targeted Cell Death Jin, N. et al. Nano Lett. 2007, ASAP.

32. 32 Targeted Cell Death Jin, N. et al. Nano Lett. 2007, ASAP.

33. 33 Summary –Interesting properties Mechanical Electrical –Functionalization Covalent Noncovalent –Applications Photovoltaics Biosensing Cellular Transport

34. 34 Thank You! Prof. Bob McMahon McMahon Group: Phillip Thomas Caroline Pharr Jessica Menke Chris Shaffer Katherine Traynor Prof. John Moore Moore Group: Diane Nutbrown Caroline Pharr Janice Tomasik Alex KhrizmanJulee Byram Kristy KounovskyBrian Esselman Nick HillLaura Kopff Rachel BainAndrew Greenberg Chanteau, S. H. et al. J. Org. Chem. 2003, 68, 8750-8766.