Creating

1
Creating Good Nanotechnology ?An emerging
technology in the 21st century
Dr. Vicki Colvin Director, CBEN Professor of
Chemistry Rice University
2
Comments today
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Defining Nanotechnology
From E56 ASTM terminology standard free on
www.astm.org
nanotechnology, nA term referring to a wide
range of technologies that measure, manipulate,
or incorporate materials and/or features with at
least one dimension between approximately 1 and
100 nanometers (nm). Such applications exploit
those properties, distinct from bulk or molecular
systems, of nanoscale components.
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Nanomaterials Small, Weird and Important
Cadmium Selenide nanocrystal 6 nm
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Nanoscale Magnets BETTER Magnets
13.96 1.62 nm
Magnetotactic bacteria
Artificial Magnetite
Nanoparticles
10 sec
Magnet
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Highlight Low Cost Arsenic Removal
Mason Tomson, Vicki Colvin, Doug Natelson
A family of four could treat their water for
several dollars a month and use magnetic sorbents
to remove contaminants such as arsenic
Magnetized plate
Material Sorbent (kg)/ month 1 gram treats ____ L water Waste to dispose of kg (1 yr) Backwash Frequency (day) Efficiency
Alumina Metal Oxide 0.24 3.8 2.9 14 0.003
Activated Neutralized Red Mud As(III) 360.7 0.002 4328.1 Periodic (0.003) est.
Ion Exchange No Removal of Toxic As(III) No Removal of Toxic As(III) No Removal of Toxic As(III) 3 0.014
Nano- magnetite 0.09 10 1.1 0 (7.5 to 75 ) est.

1. Efficiency as defined by NAE in the "Granger
   Challenge, June, 2005" The object is to maximize
   the efficiency.

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Nanotechnology and Your Life 50 Years?
8
Todays Comments
The Bad
The UGLY
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Nanotechnologys Fear Factors

• Engineered nanomaterials - New pollutants?
• Grey goo and transhumanism Enhanced people?
• Control and social justice New economies?

10
Nanomaterials Why Worry?
www.geo.mtu.edu
www.cccski.com

• Naturally occuring nanomaterials are widespread
• Incidentally produced nanomaterials linked to
  disease
• Legacy nanomaterials used for decades in key
  products

Jablonska et al ENVIRONMENTAL GEOLOGY 40 (8)
941-948 JUN 2001
Bracco et al ANNALS OF EMERGENCY MEDICINE 32 (5)
616-619 NOV 1998
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Environmental impacts of nanocarbons
Polyaromatic hydrocarbons
?
Carbon soot
12
Developmental toxicity of C60 (Zebrafish)
Mitigation by GSH suggest that toxicity is
related to oxidative stress
100
80
nC60/THF
nC60/THFGSH
60
Pericardial Edema ()
40
20
0
Lyon, Alvarez, Tomson
48
60
72
84
96
108
120
Hours Post-Fertilization
Zebrafish larva with pericardial edema due to
C60 exposure
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Fullerene Toxicology Surface Matters
C60 Type Cell Type LC 50 Notes
1. Polymer wrapped Mouse cells 300 ppm Uncontrolled light exposure
Mouse fibroblasts 1 ppm (light) 100 ppm (dark)
BALB/3T3 15 ppm (light) No dark xpts.
2. Malonic acid derivative Human Cervix Cells 30 ppm (light) gt 100 ppm (dark)
3. Ammonium salt Cortical Cells 7 ppm Uncontrolled light exposure
Cytotoxic response of derivatives 10-100X less
than nano-C60
1 A) Tsuchiya, T. et al FEBS 393 (1996) p.
139-145. B) Nakajima, N. Full. Sci. and Tech.
4(1) (1996) p. 1-19. C) Sakai, A. Full. Sci. and
Tech. 4(1) (1996) p. 1-19. 2 Yang, XL Tox. In
Vitro 16 (2002) p.41-46. 3 Cusan, C. Eur. J.
Org. Chem. (2002) p. 2928-2934.
14
Systematic Variation of Surface Chemistry
In
Increasing derivatization lowers photoinduced
singlet oxygen generation
More polar functionality creates higher water
solubility in materials
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Dose Response Curve for Fullerenes
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Safety by Design A New Paradigm
Aqueous oxidation of C60 can occur, and should
result in decreased environmental impacts.
John Fortner, Joe Hughes
Treatment schemes included in product packaging
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Towards Sustainable Nanotechnology
Are engineered nanoparticles dangerous?
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Can conventional risk management work?
Risk Function (hazard, exposure)
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Complexity explosion what exposure route?

• Good agreement on size of the market
• NO agreement on what materials/products will
  matter

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New Research Risk Forecasting

• Outcome A graphical and realistic multi-scale
  simulation that integrates data from diverse
  experiments to describe NP impacts on the
  environment.

If we can forecast hurricanes, we can forecast
environmental impact
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Todays Talk
The Good
We need nanotechnology
Do safety by design Think risk landscape
The Bad
The UGLY
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Who Are the Deciders?
Nanotechnologys Future
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NOT Scientists and Engineers
The Valley of Death for Science Policy
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New partnerships for communication

• International partnership which includes many
  stakeholders
• Pooled resources for risk assessment of
  nanotechnology
• Shared risk communication strategies
• Major effort in database and knowledge base for
  NanoEHS

www.rice.edu/icon
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Putting research into perspective
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Backgrounders Provide Context
Backgrounder Scientific context for Hot Paper
or Hot Topic

• For Peers
• Commentary in PNAS
• For Journalists and Public
• Lay-language backgrounder on NPs and amyloid
  diseases
• Qs As on Hot Paper
• Media Alert targeted to science writers

Promoting public dialogue and enhanced
understanding of nano environment, health and
safety research
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Scientists and Engineers Not Deciders
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Consumers as Deciders?
Product
Nano Inside
Value Added
Active Ingredient Nanoscopic TiO2/ZnO
Transparency
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Public Perception Not Yet Formed
Currall, S. C., E. B. King, et al. (2006). "What
drives public acceptance of nanotechnology?"
Nature Nanotechnology 1(3) 153-155.
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(No Transcript)
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The Government as Decider
Nano materials Bulk material for EHS
properties
Material Safety Data Sheet acc. to OSHA and ANSI
. 8. Physical and chemical properties        
Solubility in / Miscibility with Water Insoluble
11 Toxicological information         Acute
toxicity         Primary irritant effect
        on the skin Irritant to skin and
mucous membranes.         on the eye
Irritating effect.         Sensitization No
sensitizing effects known.         Subacute to
chronic toxicity Elemental carbon/carbon black
is mainly a nuisance dust. It is irritating to
the eyes and may cause conjunctivitis, cornea
damage, and inflammation of the eyelids.
Additional toxicological information To the
best of our knowledge the acute and chronic
toxicity of this substance is not fully known.
14. Ecological hazards National regulations
This product is not listed in the U.S.
Environmental Protection Agency Toxic Substances
Control Act Chemical Substance Inventory. Use of
this product is restricted to research and
development only.
32
Government Push on Nanotechnology

• Remarkable amount of government push for NT
• International space race mentality in
  investments
• Transition from laboratory into industry is just
  starting

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Toxic Substances Control Act
Any organic or inorganic substance of a
particular molecular identity, including any
combination of such substance
EPA has not treated the mere aggregation of
molecules into particles or varying physical
forms to result in different chemical substances
with different molecular identities for the
purposes of TSCA. TSCA Inventory Status of
Nanoscale Substances General Approach http//epa
.gov/oppt/nano/nmspfr.htm
WILSON CENTER
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What is the chemical identity?
Polyaromatic hydrocarbons
?
Carbon soot
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A Size Based Criteria for Chemical Identity
Pure Volume 4/3p(r-t)3
10-20 nm range new chemical substance
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Todays Talk
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My conclusions

• Nanotechnology does present a huge array of
  unknown risks, and also offers solutions to our
  most pressing social problems.
• National governments are not, and maybe cannot,
  act as effective deciders
• Proactive consumerism or local regulatory
  processes offer 21st century approaches

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Acknowledgements

• Colvin Group
• Dr. William Yu
• Ali Al-Somali
• Adina Boyd
• Joshua Falkner
• Jennifer Jamison
• Erika Bryant
• Karl Krueger
• Dr. Yunping Liu
• Michelle Mejia
• Tushar Prasad
• Cafer Yavuz

• Collaborators
• Dr. Christie Sayes
• Dr. Jennifer West
• Andre Gobin
• Roy Mesleyni
• Dr. David Warheit (Dupont)

• Dr. Wenh Guo
• Dr. Jane Grande-Allen
• Emmanuel Chang
• Dr. Rebekkah Drezek

NSF-NSEC CBEN www.rice.edu/cben Colvin_at_rice.edu
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• THE END

40
Defining Nanotechnology
From E56 ASTM terminology standard free on
www.astm.org
nanotechnology, nA term referring to a wide
range of technologies that measure, manipulate,
or incorporate materials and/or features with at
least one dimension between approximately 1 and
100 nanometers (nm). Such applications exploit
those properties, distinct from bulk or molecular
systems, of nanoscale components.
41
Systematic Variation of Surface Chemistry
In
Increasing derivatization lowers photoinduced
singlet oxygen generation
More polar functionality creates higher water
solubility in materials
42
Dose Response Curve for Fullerenes
43
Waste Treatment Schemes for Fullerenes
Aqueous oxidation of C60 can occur, and should
result in decreased environmental impacts.
John Fortner, Joe Hughes
Treatment schemes included in product packaging
44
Framing the question in nanotoxicology
Are engineered nanoparticles dangerous?
45
Nanotechnology Avoiding the Yuck factor

• Address societal issues using nanotechnology
• Distribute manufacturing and know-how globally
• Do safety by design
• Talk about risks, possible and known, openly

46
Can sound science control policy?
What are the barriers to high quality technical
data emerging quickly??
47
A Water Soluble C60 Nano-C60
Deguchi, S. et al., Langmuir, 17, pp. 6013-6017,
2001 Hughes, Colvin EST (2005)
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In-Vitro Studies of Aggregated C60
Human Cell Line LC50 (ppm)
HepG2 0.05
HDF 0.02
NHA 0.002
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Microbiological Impacts of Agg-C60
Less toxic
Nano-TiO2
(MIC in ppm)
Nano-C60
More toxic
Lyon, Alvarez, Hughes
Lyon, D. Y., L..K. Adams, J.C. Falkner, P.J.J.
Alvarez. Environ. Sci. Technol. (Article) 2006
Adams, L.K., D.Y. Lyon, P.J.J. Alvarez.
Comparative EcoToxicity of Nano-Scale TiO2, SiO2
and ZnO Water Suspensions. aubmitted to Water
Research.
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n-C60 Relative Cytotoxicity
Toxin LC50, mg/kg
C60-(OH)x gt 100,000
Ethyl Alcohol 17,000
THF 11,000
Toluene 1,600
Paraquat 100
Benzoapyrene 10
n-C60 0.02
Dioxin 0.001
National Institute of Health, Registry of
Cytotoxicity Data (ZEBET)
Aggregated C-sixty is a very toxic substance in
cell culture
51
Origins of fullerenes bioactivity
C60 can directly oxidize lipids (needs physical
contact) C60 is also a highly lipophilic substance
52
Nanocarbons distinct environmental properties
Polyaromatic hydrocarbons
?
Carbon soot
YES (for C60) - The Biological Properties Are
Distinctive
53
Lesson What goes in, isnt what comes out
www.Soileco.com
54
Emerging Technology The Challenge for Risk
Assessment
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Many exposures, many materials
56
NanoX Not Toxicology As Usual
Are single-walled carbon nanotubes toxic?
Basic structure-function relationships for
nanomaterials and biological impacts are necessary
57
Structure-Function for Nanomaterial Biology
58
New partnerships for communication

• International partnership which includes many
  stakeholders
• Pooled resources for risk assessment of
  nanotechnology
• Shared risk communication strategies
• Major effort in database and knowledge base for
  NanoEHS

www.rice.edu/icon
59
Critical Need Balanced Information on Risk
Best Practices Manual
EHS Knowledge Database
Example Nanoscale TiO2 is toxic to brain
cells. What does that mean?
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What is ICON?
Database of EHS technical literature
Survey of current workplace practices
ICONsultations with diverse stakeholders
International nanoEHS research needs assessment
NSF funded
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EHS Database has Broad Impact

• gt1400 records
• 50 of hits from outside the US
• gt50 websites mention database

62
Nanomaterials Not new, not manufactured
RISK HAZARD EXPOSURE
www.cccski.com
www.geo.mtu.edu

• Naturally occuring nanomaterials are widespread
• Incidentally produced nanomaterials linked to
  disease
• HUGE exposures here, how can engineered
  nanoparticles pose any real risk?

Jablonska et al ENVIRONMENTAL GEOLOGY 40 (8)
941-948 JUN 2001
Bracco et al ANNALS OF EMERGENCY MEDICINE 32 (5)
616-619 NOV 1998
63
The Chemical Identity of Materials
Nano materials Bulk material for EHS
properties
Material Safety Data Sheet acc. to OSHA and ANSI
. 8. Physical and chemical properties        
Solubility in / Miscibility with Water Insoluble
11 Toxicological information         Acute
toxicity         Primary irritant effect
        on the skin Irritant to skin and
mucous membranes.         on the eye
Irritating effect.         Sensitization No
sensitizing effects known.         Subacute to
chronic toxicity Elemental carbon/carbon black
is mainly a nuisance dust. It is irritating to
the eyes and may cause conjunctivitis, cornea
damage, and inflammation of the eyelids.
Additional toxicological information To the
best of our knowledge the acute and chronic
toxicity of this substance is not fully known.
14. Ecological hazards National regulations
This product is not listed in the U.S.
Environmental Protection Agency Toxic Substances
Control Act Chemical Substance Inventory. Use of
this product is restricted to research and
development only.
64
(No Transcript)
65
What is the chemical identity?
Polyaromatic hydrocarbons
?
Carbon soot
66
Public Information on U.S. Policy
http//www.epa.gov/osa/nanotech.htm
1. EPA whitepaper on nanotechnology
2. House Hearing on Nanotechnology (09/28)
Testimony by William Farland http//www.epa.gov/oc
ir/hearings/testimony/109_2005_2006/2006_0921_whf.
pdf
3. Extramural research funding under ORD about
10 million right now
1. Nanomaterials are not different and covered
under existing requirements
2. 1999 Ruling on Sunscreens micronized
titania is not new
EPA Reviews 15 New Nanoscale Chemicals, But
Finds Only One With Unique Properties Daily
Environmental Report, No. 158, Page A-7
Wednesday, August 16, 2006 -

• Case-by-case style for regulatory decisions from
  both agencies
• Recent decisions by EPA consistent with a Nano
  is not different policy
• Most officials will state that their policies are
  still evolving

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• RESEARCH
• NEEDS

68
Challenge Risk New Technologies

• Current climate
• High technical uncertainty
• Very diverse materials and uses

Essential Set priorities for research,
monitoring and policy
January and April 2007 Research Needs in
Nano-EHS EMAIL kk_at_rice.edu for information
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Challenge Reference Materials
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Challenge Standard Methods !
QDots absorption 20 mM 40 QDots cryo-TEM
8 mM 20 QDots atomic absorption 14 mM
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w/ Paul Howard (NCTR), Nigel Walker (NIEHS),
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Nanotechnology Standards Activities
Standards Developer
Standards Coordinators

• Created Nanotech Standards Panel to coordinate US
  activity
• Colvin, Co-chair
• Kulinowski, Member
• www.ansi.org/nsp

• Chair, Vicki Colvin
• Subcommittees
• E56.01 Terminology Nomenclature
• Colvin sub-chair
• E56.02 Characterization
• E56.03 Environmental Occupational Health and
  Safety
• E56.06 Risk Management/Product Stewardship
• Kulinowski sub-chair

• New technical committee on nanotech (TC 229)

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NanoX Not Toxicology As Usual
Are single-walled carbon nanotubes toxic?
Basic structure-function relationships for
nanomaterials and biological impacts are necessary
73
Environmental Cycling of Nanomaterials
Impact (or Risk) Exposure Effect
Sources
Transport
Fate
Receptors
What are source management alternatives?
Is there harm?
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Nanomaterials THEY ARE WEIRD
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Nanomaterials THEY ARE IMPORTANT