Transcript Slide 1

Tubing Through the Nano World:
Nanotube Functionalization and Practical Applications
Nicola J. Burrmann
McMahon and Moore Groups
September 27, 2007
Outline
– What are NTs?
Structure
Characterization
Synthesis
– Covalent functionalization
– Noncovalent functionalization
– Applications of functionalized NTs
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Nanotube (NT) Structure
– (m,n) vector
• v = ma1 + na2
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.
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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.
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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.
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Synthesis
High Pressure
Carbon Monoxide
(HiPCO)
Arc-Discharge
Laser 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 NT
SWNT
SWNT
SWNT
MWNT
Lattice
Hexagons
Hexagons
Hexagons
Some Pentagons and
Heptagons
Purity
Significant
Byproducts
Significant
Byproducts
Significant
Byproducts
Minimal Byproducts
Pros
Specific Range of
Diameters
Specific Range
of Diameters
Cons
> 1000 °C
Dai, H. Acc. Chem. Res. 2002, 35, 1035-1044.
Bahr, J. L. et al. J. Mater. Chem. 2002, 12, 1952-1958.
Controlled Diameters,
Arrays, < 500 °C
> 1000 °C
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Great Potential, But…
–
–
–
–
–
Unique composition and bonding configuration
Extraordinary electronic properties
Interesting optical properties
Incredible strength and stiffness
The catch…
…The solution
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.
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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
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Acid Oxidation
– H2SO4, HNO3, H2O2
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.
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Amidation
EDAC =
DCC =
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.
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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.
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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.
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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.
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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.
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Hydrophobic Interactions
Sun, Y.-P. et al. Acc. Chem. Res. 2002, 35, 1096-1104.
Dai, H. Acc. Chem. Res. 2002, 35, 1035-1044.
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Outline
– What are NTs?
– Covalent functionalization
– Noncovalent functionalization
Polymer wrapping
Non-specific protein adsorption
π-Stacking interactions
– Applications of functionalized NTs
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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.
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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.
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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.
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Covalent vs. Noncovalent Functionalization
Covalent
Noncovalent
Solubility
Organic and Aqueous
Solubility
Organic and Aqueous
Solubility (Reversible)
Binding
Interaction
Reversible under Harsh
Conditions
Reversible with Varying
Solvent Conditions
Hybridization
sp3
sp2
Conjugation
Decreased
Unaffected
Electronic
Properties
Altered
Unaffected
Chen, R. J. et al. J. Am. Chem. Soc. 2001, 123, 3838-3839.
Dai, H. Acc. Chem. Res. 2002, 35, 1035-1044.
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Outline
– What are NTs?
– Covalent functionalization
– Noncovalent functionalization
– Applications of functionalized NTs
Photovoltaics
Biosensing
Cellular transport
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NT Electron Transfer
Guldi, D. M. Acc. Chem. Res. 2005, 38, 871-878.
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Photovoltaics (PV)
Guldi, D. M. Acc. Chem. Res. 2005, 38, 871-878.
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PV Applications
tCS
(ns)
tCR
(ms)
SWNT–Pyrene
NA
NA
SWNT/Pyrene+
NA
NA
SWNT–Fc
3.6
1.1
SWNT/Pyrene+/ZnP8-
0.2
0.4
MWNT/Pyrene+/ZnP8-
0.2
5.8
SWNT–PSS/H2P8+
0.3
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Nanohybrid
tCS = Charge separation time
tCR = Charge recombination time
Guldi, D. M. Acc. Chem. Res. 2005, 38, 871-878.
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Specific Molecular Detection
Shim, M. et al. Nano Lett. 2002, 2, 285-288.
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Specific Molecular Detection
Shim, M. et al. Nano Lett. 2002, 2, 285-288.
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Biosensors
Lee, C.-S. et al. Nano Lett. 2004, 4, 1713-1716.
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Biosensors
Lee, C.-S. et al. Nano Lett. 2004, 4, 1713-1716.
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Biosensors
Lee, C.-S. et al. Nano Lett. 2004, 4, 1713-1716.
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Cellular Transport
Pantarotto, D. et al. Chem. Commun. 2004, 16-17.
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Targeted Cell Death
Jin, N. et al. Nano Lett. 2007, ASAP.
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Targeted Cell Death
Jin, N. et al. Nano Lett. 2007, ASAP.
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Summary
– Interesting properties
• Mechanical
• Electrical
– Functionalization
• Covalent
• Noncovalent
– Applications
• Photovoltaics
• Biosensing
• Cellular Transport
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Thank You!
Prof. Bob McMahon
Prof. John Moore
McMahon Group:
Phillip Thomas
Caroline Pharr
Jessica Menke
Chris Shaffer
Katherine Traynor
Moore Group:
Diane Nutbrown
Caroline Pharr
Janice Tomasik
Alex Khrizman
Kristy Kounovsky
Nick Hill
Rachel Bain
Chanteau, S. H. et al. J. Org. Chem. 2003, 68, 8750-8766.
Julee Byram
Brian Esselman
Laura Kopff
Andrew Greenberg
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