Chemistry and

Nanomaterials
Nanoscale = billionths -9
(10 )

6 billion people 10 billion components

8000 mile diameter 8 inch diameter
 Effects of Nanoscale

Structural differences:
Nanoscale Carbon
Bulk Carbon

C60 (Buckeyball)
Smalley, Curl, Kroto
1996 Nobel Prize

Graphite Diamond
Carbon Nanotubes
Sumio Iijima - 1991
Instrumentation / Imaging

• “Quantum
Corral”
• 48 Fe atoms
positioned by
the STM
used to
image them

http://www.nano.gov/html/facts/home_facts.html
 Dimensional Issues

length scale: nm µm mm m

ONAMI
Chemistry molecules polymers supramolecular
assemblies

Biology amino
proteins cells/tissues organisms
acids

Electronics semi- transistors integrated computers

conductors circuits
 Chemistry Issues

• Structure / Dynamics / Synthesis

• Structure-Function Correlations
• Self-Assembled Systems
• Applications:
– Materials
– Biological
– Environmental
 Organic LEDs

Structure-Function Correlations (emission wavelengths)

 Quantum Effects

• Band gap depends on particle size

(number of atoms in the particle)

4 nm 2 nm

Fluorescence of cadmium selenide nanoparticles

ENERGY LEVELS: Root of Interactions
 Chemical Bonding

• Forces used to assemble structure:

– Ionic
– Metallic
– Covalent
– H-bonding
– Metal-ligand
– Van der Waals
– π-π stacking
 Ionic Bonding

• Molecular beaker
epitaxy
• Layer-by-layer
growth of
polyelectrolytes

• Tom Mallouk
Penn State U

http://www.mapr.ucl.ac.be/~jonas/Home_page_AJ/Research/ESA/ESA.html
Ionic / Electrostatic Effects

• A molecular
elevator
• Responsive to
acid/base

• J. D. Badjic, et al.,
Accts. Chem. Res.,
in press.
• J.F. Stoddart, UCLA
 Ionic / Electrostatic Effects

• Conformational Molecular Rectifiers, A. Troisi and M. A. Ratner,

Nano Lett., 4(4), 591-595 (2004).
 Metallic Bonding
Nanoscale gold has different properties than bulk gold, including:
appearance, solubility, and melting point.
Gold Statue Gold nanoparticles

thiol stabilized gold nanoparticle

melting point: 1337 °K

Jim Hutchison, U. Oregon gold nanoparticles (2 nm) in solution

http://darkwing.uoregon.edu/~hutchlab
melting point: 650 °K
Covalent Bonding - Carbon

Single-walled
carbon nanotubes:
• armchair - metallic
• zigzag - semiconducting
• chiral - semiconducting

• multi-walled - metallic
 Covalent Bonding - Carbon

Carbon nanotubes coated with diamond nanocrystals

M. L. Terranova, et al., Chem. Mater., 17(12) pp 3214 - 3220
 Hydrogen Bonding

DNA
Double
Helix

http://www.haveland.com/ graphics/dna-3d.jpg
π-π Stacking - Liquid Crystals
Charge-Trapping Memory Device

Liu, C-Y.; Bard, A.J.; Acc. Chem. Res.

(1999), 32, 235-234.
Self-Assembled Monolayer

10 nm
• Monolayer of
DDB on
graphite
(didodecylbenzene)

http://www.nanoscience.com/education/gallery/DDB_ani.htm
 Van der Waals Interactions

• SAMMS
Self-Assembled
Monolayers on QuickTime™ and a
TIFF (LZW) decompressor
Mesoporous are needed to see this picture.
Supports

Glen Fryxell, PNNL

http://samms.pnl.gov/
Polyporphyrin Interfacial Film (thin)
Polyporphyrin Interfacial Film (thick)
Photosynthetic Reaction Center
( 1988 Nobel Prize )

http://www.mpibp-frankfurt.mpg.de/~michael.hutter/rcenter.html
 Resources
• Nanochemistry references and websites:
 Handbook of Nanotechnology, B. Bhushan, ed. (2004)
 Molecular Nanotechnology, D. E. Newton, ed. (2002)
 Integrated Chemical Systems, A. J. Bard (1994)
 Engines of Creation, K. Eric Drexler (1986)
( http://www.foresight.org/EOC/ )
 “There’s Plenty of Room at the Bottom”, Richard Feynman (1959)
( http://www.zyvex.com/nanotech/feynman.html )

 National Nanotechnology Initiative ( http://www.nano.gov/ )

 Nano Letters - ACS Journal ( http://pubs.acs.org/journals/nalefd/ )
 Materials Today - British journal ( http://www.materialstoday.com )