Nanotechnology The Big and Small of it

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NanotechnologyThe BigandSmall of it
Buckyballs and Nanotechnology Harry C. Dorn VA
Tech
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Richard Feynman Theres Plenty of Room at the
Bottom Cal Tech, Dec. 29, 1959
Why cant 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
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Nanotechnology A Matter of Size and Control
Think very small (nano 1 billionth of a
meter) 10 H atoms 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
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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
Nanomuscles add strength and endurance when
needed
Nanofibers in fabric can close to block
chemicals, or stiffien to form a splint
MIT, Institute for Soldier Nanotechnologies
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Allotropes of Carbon (Pre-1985)
Diamonds Cubic, Crystalline sp3 hybridized High
Melting Point Hardness 10
Graphite Hexagonal, Black Sheets sp2
hybridized High Melting Point Hardness 1-2

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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
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Smalley, Kroto, and Curl (1984-5)
Laser Apparatus
Large Fullerenes
C60, Fullerenes, BuckyBalls!
0.2 m
0.7 nm
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Single Wall Carbon Nanotubes (Don Bethune, IBM)
Jan 93 2 Co burn rubbery soot and spider
web structures
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Carbon Nanotubes
Single-wall Carbon NanotubesA Major Application
Two-dimensional imaging of electronic
wavefunctions in carbon nanotubes S.G. LEMAY, et
al. Nature 412, 617 - 620 (2001)
TU Delft/Gripp Design Nature 412 (2001)
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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

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NASA Space Elevator
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Discovery of Trimetallic Nitride Template
(TNT)Endohedral Metallofullerenes1109
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Unoptimized Production of Sc3N_at_C80
m/e1109
Stevenson, Dorn Anal. Chem. 1994
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Kratschmer-Huffman Electric-Arc Synthesis
Source of nitrogen?
Air leak! nitrogen, oxygen H. C. Dorn 1109 Hahn
Hall!
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Trimetallic Nitride TemplateMetallofullerenes
A3N_at_C80
Sc3N_at_C80 is the third most abundant fullerene or
endohedral metallofullerene !
Stevenson, Balch, Bible, and Dorn, Nature 1999
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TNT MetallofullerenesEncapsulation of Other
Metals
Various combinations A3, A2B, AB2
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Enabling nanotechnologies for revolutionary
advancement in medical diagnostics and
therapeutics
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NANOMANUFACTURING CHALLENGES

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Cage Variations (Symmetry) in TNT
Metallofullerenes
Sc3N_at_C78 (D3h)
Sc3N_at_C68 (D3)
Sc3N_at_C80 (Ih)
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Nano and Macro Hexagon and Pentagon Motifs
Devils Postpile National Monument, CA
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MedicalNanotechnologyApplications
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Total Hip Replacement-Osteolysis
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Therapeutics
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Sensors

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Nanotechnology- One Grand Challenge-Cancer

• Family of diseases
• Cancer is a disease process
• Proliferation
• Defects in Apoptosis
• Micro-Invasion
• Immune Evasion
• Cellular Recruitment
• Dissemination

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• 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
180.7
193.9
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 DataNVSR-Death
Final Data 2002Volume 53, No. 5. Cost data from
American Cancer Society Cancer Facts Figures
2005.
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• 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.
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Nanotechnology and Cancer
Methotrexate (therapeutic agent)
Dr. James Baker, University of Michigan
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Nanotechnology and Cancer
MTX30 mg/kg total
Nano construct3 mg/kg total MTX
Dr. James Baker, University of Michigan
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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
.
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Nanoscale Physics and Medicine
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A NEW NANOSPHERE PLATFORM MULTI-MODAL
FUNCTIONALIZED METALLOFULLERENES (fMFs)

• MULTI-MODALITY DIAGNOSTICS
• MGd, MRI CONTRAST
• MLu, X-RAY CONTRAST
• M Tb FLUORESCENCE
• M166Ho,177Lu RADIOLABEL
• DUAL DIAGNOSTIC AND THERAPEUTIC AGENTS
• M166Ho,177Lu RADIOISOTOPES
• PHOTODYNAMIC THERAPY
• TARGETED DELIVERY APPROACHES
• BONE VECTOR
• BLOOD BRAIN BARRIER
• DIRECT TUMOR INFUSION

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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 rates for Gd_at_C82(OH)n and
  Gd_at_C82(CO2H)n derivatives in comparison with
  commerical agents

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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
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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
17 Days Post Tumor Implantation 3 days Post
Infusion of Gd3N-fMF
19 Days Post Tumor Implantation 5 days Post
Infusion of Gd3N-fMF
August 15, 2003
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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
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Theres no use trying she said one cant
believe impossible things. I dare say you
havent had much practice. said the Queen. When
I was your age, I always did it for half an hour
a day. Why, sometimes, Ive believed as many as
six impossible things before breakfast.

Lewis Carroll
Alice Through the Looking
GlassIf you dont make mistakes, youre not
working on hard enough problems, and thats a big
mistake
F. Wilczek
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