Chemistry and Nanomaterials Carl C Wamser Portland State University Nanomaterials Course - June 27, 2006 Nanoscale = billionths (10-9) billion people 8000 mile diameter 10 billion components 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 ONAMI mm m Chemistry molecules polymers supramolecular assemblies Biology amino acids Electronics proteins cells/tissues organisms semitransistors integrated conductors circuits computers 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) nm 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 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 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture 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 ) [...]... 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... 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 http://darkwing.uoregon.edu/~hutchlab gold nanoparticles (2 nm) in solution melting point:... 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/... 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 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture Glen Fryxell, PNNL http://samms.pnl.gov/ Polyporphyrin Interfacial... 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 )