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Nanotechnology The Big and Small of it

Buckyballs and Nanotechnology Harry C. Dorn VA Tech. Nanotechnology The Big and Small of it. Richard Feynman “There’s Plenty of Room at the Bottom” Cal Tech, Dec. 29, 1959. Why can’t we write the entire 24 Volumes of the Encyclopedia Brittanica on the head of a pin?

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Nanotechnology The Big and Small of it

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  1. Buckyballs and Nanotechnology Harry C. Dorn VA Tech NanotechnologyThe BigandSmall of it

  2. Richard Feynman “There’s Plenty of Room at the Bottom” Cal Tech, Dec. 29, 1959 Why can’t we write the entire 24 Volumes of the Encyclopedia Brittanica on the head of a pin? How do we write small? Miniaturizing the Computer? Problems of Lubrication A hundred Tiny Hands Atoms in a Small World Origins of Nanotechnology

  3. Nanotechnology: A Matter of Size and Control Think very small (“nano” = 1 billionth of a meter) = 10 Hatoms; or, 1 human hair = 100,000 nanometers! The precise, highly controlled assembly of atoms and molecules into new materials and devices with unique, possibly revolutionary properties • Carbon Nanotubes • 100 times stronger than steel • Conduct electricity better than copper • Conduct heat better than diamonds • Depending on current, can either: - Act as a metal (conductor) - Act as semiconductor (transistor) • Markets now exist for nanotubes as raw material Individual iron atoms positioned in an oval “corral” on a copper surface, using a scanning tunneling microscope --IBM Almaden Research Center Single wall carbon nanotube with attached protein receptors

  4. Nanotechnology Future Vision: 2015 Tissues and organs artificially grown on nanopatterned scaffolds Major applications anticipated in: Biomedicine Defense/ Homeland Security Electronics/ Information Technology Energy/ Environment Nanostructured capsules deliver drugs directly to diseased tissue Optoelectric retinal implants for the blind Nanocoatings produce body friendly, longer lasting implants Cochlear implants to restore hearing Nanostructured materials reduce total weight carried from 120 to 50 pounds “Chameleon” uniform changes colors with background Ultralightweight power pack driven by fuel cell with nanomembranes Weapon fires superpenetrating projectiles or non-lethal net of carbon nanofibers Sensors imbedded in clothing monitor vital signs, detect toxins Nanofibers in fabric can close to block chemicals, or stiffien to form a splint “Nanomuscles” add strength and endurance when needed MIT, Institute for Soldier Nanotechnologies

  5. Diamonds Cubic, Crystalline sp3 hybridized High Melting Point Hardness 10 Allotropes of Carbon (Pre-1985) Graphite Hexagonal, Black Sheets sp2 hybridized High Melting Point Hardness 1-2

  6. New Carbonaceous Materials Bethune, Dorn, Stevenson Nature 1994 Stevenson, Balch, Bible, Dorn, et al Nature 1999 Iijima, et al Nature 1993 Bethune, et al Nature 1993 Smalley, et al Nature 1985

  7. Smalley, Kroto, and Curl (1984-5) Laser Apparatus Large Fullerenes C60, Fullerenes,BuckyBalls! 0.2 m 0.7 nm

  8. Single Wall Carbon Nanotubes (Don Bethune, IBM) Jan ‘93: 2% Co burn –“rubbery soot” and “spider web structures”

  9. Carbon Nanotubes Single-wall Carbon Nanotubes:A Major Application Two-dimensional imaging of electronic wavefunctions in carbon nanotubes S.G. LEMAY, et al. Nature412, 617 - 620 (2001) TU Delft/Gripp Design Nature412 (2001)

  10. Single Wall Carbon Nanotubes 0 1 2 3 Diameter (nm) - Bethune, et al., Nature 363, 605 (1993) • Iijima & Ichihashi, Nature 363, 603 (1993) - Fe catalyst, with methane

  11. NASA Space Elevator

  12. Discovery of Trimetallic Nitride Template (TNT)Endohedral Metallofullerenes“1109”

  13. Unoptimized Production of Sc3N@C80 m/e=1109 Stevenson, Dorn Anal. Chem. 1994

  14. Kratschmer-Huffman Electric-Arc Synthesis Source of nitrogen? Air leak! nitrogen, oxygen H. C. Dorn 1109 Hahn Hall!

  15. Trimetallic Nitride TemplateMetallofullerenes A3N@C80 Sc3N@C80 is the third most abundant fullerene or endohedral metallofullerene ! Stevenson, Balch, Bible, and Dorn, Nature 1999

  16. TNT Metallofullerenes:Encapsulation of Other Metals Various combinations: A3, A2B, AB2

  17. Enabling nanotechnologies for revolutionary advancement in medical diagnostics and therapeutics

  18. NANOMANUFACTURING CHALLENGES

  19. Cage Variations (Symmetry) in TNT Metallofullerenes Sc3N@C78 (D3h) Sc3N@C68 (D3) Sc3N@C80 (Ih)

  20. Nano and Macro Hexagon and Pentagon Motifs Devil’s Postpile National Monument, CA

  21. MedicalNanotechnologyApplications

  22. Total Hip Replacement-Osteolysis

  23. Therapeutics

  24. Sensors

  25. Nanotechnology- One Grand Challenge-Cancer • Family of diseases • Cancer is a disease process • Proliferation • Defects in Apoptosis • Micro-Invasion • Immune Evasion • Cellular Recruitment • Dissemination

  26. The human and economic burden of cancer on our society continues to grow… • Cancer is now the #1 killer This year: 570,300 Americans will die of cancer 1,372,900 Americans will hear the words “you have cancer…” More Progress is Needed to Reduce Death Rates* 586.8 1950 2002 600 500 400 Death Rate Per 100,000 300 241.7 193.2 193.9 180.7 200 56.5 100 48.1 22.8 0 HeartDiseases CerebrovascularDiseases Pneumonia/Influenza Cancer * Age-adjusted to 2000 US standard population. Sources: 1950 Mortality Data - CDC/NCHS, NVSS, Mortality Revised. 2002 Mortality Data–NVSR-Death Final Data 2002–Volume 53, No. 5. Cost data from American Cancer Society Cancer Facts & Figures 2005.

  27. The human and economic burden of cancer on our society continues to grow… • 9.6 million cancer survivors in the United States today • Healthcare costs attributable to cancer at $189 billion/year Chronic Disease with Need for Effective and Accessible Monitoring and New Therapy Strategies The number of people living with a diagnosis of cancer has increased dramatically Data Source : November 2003 Submission: Populations from January 2001 were based on the average of the July 2000 and July 2001 population estimates from the US Bureau of Census. Complete prevalence is estimated using the completeness index method (Capocaccia et. al. 1997, Merrill et. al. 2000). US Estimated Prevalence counts were estimated by applying US populations to SEER 9 Limited Duration Prevalence proportions.

  28. Nanotechnology and Cancer Fluorescein (detecting agent) Folic acid (targeting agent) G5-polyamidoamine (dendrimer platform) Methotrexate (therapeutic agent) Dr. James Baker, University of Michigan

  29. Nanotechnology and Cancer MTX30 mg/kg total Nano construct3 mg/kg total MTX Dr. James Baker, University of Michigan

  30. NIH: Metallofullerene NanoPlatform for Imaging & Treating Infiltrative Glioma Medical College of Virginia Panos Fatouros PhD, William Broaddus MD Joe Kalen PhD, Jim Tatum MD* Virginia Tech Harry Dorn PhD Harry Gibson PhD .

  31. neutron activation dipole-dipole Large atomic cross-section fluorescence activation unpaired electrons H2O Radiotherapy X-ray contrast Targeted contrast MRI contrast Nanoscale Physics and Medicine

  32. IDEALIZED PROBE: S1, S2 = signaling units; V = vector unit for targeted delivery; T = therapeutic unit. In this case T is endo but it can be exo. CURRENT PROBE: Pegylated-Hydroxylated fMFs: M3N@C80,(M=Gd, Lu, Tb) 3 A NEW NANOSPHERE PLATFORM: MULTI-MODAL FUNCTIONALIZED METALLOFULLERENES (fMFs) MULTI-MODALITY DIAGNOSTICS • M=Gd, MRI CONTRAST • M=Lu, X-RAY CONTRAST • M= Tb FLUORESCENCE • M=166Ho,177Lu RADIOLABEL DUAL DIAGNOSTIC AND THERAPEUTIC AGENTS • M=166Ho,177Lu RADIOISOTOPES • PHOTODYNAMIC THERAPY TARGETED DELIVERY APPROACHES • BONE VECTOR • BLOOD BRAIN BARRIER • DIRECT TUMOR INFUSION

  33. ENDOHEDRAL METALLOFULLERENE MRI Contrast Agents Shinohara (Nagoya), Wilson (Rice), and Bolskar (TDA) groups have reported significant increases in the 1H MRI T1 spin-lattice relaxivity ratesfor Gd@C82(OH)n andGd@C82(CO2H)n derivatives in comparison with commerical agents

  34. Signal Intensity profiles with respect to baseline profile along line shown in image Baseline 90 min 30 min 120 min 60 min 150 min 75 min 175 min Figure 10. T1-Weighted Images of Direct Infusion into Rat Brain of 0.0131 mM fMF 3a (left) and 0.5 mM Omniscan (right) Rat Brain T1w Images of Direct Infusion (0.2 ml/min) of 0.0131 mM Gd3-fMF(left)and 0.50 mM Gd-DTPA(right) 90 min 30 min 120 min 60 min 150 min 75 min 175 min

  35. T1w-MRI Images (2.4 T): Rat Tumor Delineation by Infused Gd3N-fMF Baseline e Baseline 12 min 0.2 uL/min 22 min 1.0 uL/min 37 min 2.0 uL/min 14 Days Post Tumor Implantation, Infused 12 ml of 0.013 mM Gd3N-fMF 18 Days Post Tumor Implantation 4 days Post Infusion of Gd3N-fMF 51 min 5.0 uL/min 62 min 0.2 uL/min 85 min 0.5 uL/min 98 min 0.5 uL/min 123 min 0.5 uL/min 133 min 0.5 uL/min 19 Days Post Tumor Implantation 5 days Post Infusion of Gd3N-fMF 17 Days Post Tumor Implantation 3 days Post Infusion of Gd3N-fMF August 15, 2003

  36. Nanotechnology and Cancer “A grand challenge is the ability to detect cancer earlier – and the answer almost certainly will be nanotechnology” “In addition to detecting cancer, nano-based techniques will enable physicians to determine whether a particular treatment is working” Dr. Richard Smalley, Nobel Laureate, October 2003 Leukemia Victim, October 2005

  37. “There’s no use trying” she said: “one can’t believe impossible things.” “I dare say you haven’t had much practice. “ said the Queen. When I was your age, I always did it for half an hour a day. Why, sometimes, I’ve believed as many as six impossible things before breakfast.” Lewis Carroll Alice Through the Looking Glass“If you don’t make mistakes, you’re not working on hard enough problems, and that’s a big mistake” F. Wilczek

  38. College of Natural Resources College of Science College of Engineering College of Agriculture & Life Sciences

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