Chemistry and Nanomaterials Carl C. Wamser Portland State University Nanomaterials Course - June 27, 2006

Nanoscale = billionths (10-9) 6 billion people 8000 mile diameter 10 billion components 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

Chemistry Issues Structure / Dynamics / Synthesis Structure-Function Correlations Self-Assembled Systems Applications: Materials Biological Environmental

Organic LEDs Structure-Function Correlations (emission wavelengths)

Fluorescence of cadmium selenide nanoparticles Quantum Effects Band gap depends on particle size (number of atoms in the particle) 4 nm 2 nm Fluorescence of cadmium selenide nanoparticles

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 Gold Statue Gold nanoparticles 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 http://darkwing.uoregon.edu/~hutchlab gold nanoparticles (2 nm) in solution 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 Mesoporous 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 )