Nanotechnology: Beneficial Effects on Protecting AnimalsFood

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Nanotechnology Beneficial Effects on Protecting
Animals/Food

• Kenneth J. Klabunde
• Kansas State University
• Dept. of Chemistry
• and
• Founder, NanoScale Corporation

Introduction to the Nano-World Detection of
Toxins Mitigation of Toxins Benefits On-Going
Projects Products Available
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• What is Nano?
• What is Nanotechnology?
• What are Nanomaterials?
• What Good are Nanomaterials?
• Who Makes Nanomaterials?
• Can Nanomaterials be Dangerous?

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What is Nano?
Nano is derived from an ancient Greek word
nanos meaning Dwarf Nano means one
billionth of a unit i.e., one nanometer is one
billionth of a meter Nanometer a magical point
on the length scale, for this is the point where
the smallest man-made devices meet the atoms and
molecules of the natural world
---Eugene Wang, 1999
St. Nano
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How Small Are Nanoscale Particles?
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Nanomaterials possess at least one dimension in
the nano range, i.e., particle diameter,
crystallite size, layer thickness

to a
is as
to
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What is Nanotechnology?
Nanoscience and technology will change the
nature of almost every human-made object in the
21st century --- M.C. Roco, R.S.
Williams, P. Alivisatos, 1999 Just waitthe
21st century is going to be incredible. We are
about to be able to build things that work on the
smallest possible length scales, atom by atom.
These nanothings will revolutionize industries
and our lives
--- Richard Smalley, 1999
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Nano-sizing Causes Changes In
Color Crystal shape Conductivity Magne
tism Melting Points Chemical Reactivity Light
Absorption
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TEM Images of Commercial, Technical Grade and
Premium Grade Magnesium Oxide
PG-MgO Surface Area 750 m2/g Crystallite Size
4 nm
TG-MgO Surface Area 250 m2/g Crystallite Size
5 nm
CM-MgO Surface Area 30 m2/g Crystallite Size
40 nm
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High Resolution TEM Image ofNanocrystalline
Magnesium Oxide
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7 grams of reactive nanoparticles have a surface
area equivalent to a football field
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What Good are Nanomaterials?
Uses and Potential Uses of Nanomaterials/Devices
Sun Screen--Burn Treatments Drug
Delivery--DNA Recognition Computers--Information
Storage Book Preservation Environmental
Remediation--Air Purification--Water
Purification Solar Cells-- Better
Batteries--Refrigeration Self-Cleaning
Windows-- Paints Homeland Security

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Who Makes Nanomaterials?
NanoScale Corporation is located in Manhattan, KS
at 1310 Research Park Drive
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• FAST-ACT (First Applied Sorbent Treatment
  Against Chemical Threats) is a Chemical Hazard
  Containment and Neutralization System, which is
  effective against a broad range of TICs and CWAs
• Capable of addressing liquid and vapor hazards
• Non-toxic, non-flammable and non-corrosive
• Safe for application to any spill
• Easy to use

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What is Nanotechnology?
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• Odor Control
• Acid Gas Scrubbing
• Air and Water Filtration
• Smoke Reduction
• Heavy Metal Removal

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Nanosensors toward a Highly Integrated Microchip
for Pathogen Detection

• Dr. Jun Li
• Associate Professor
• Chemistry Department
• Kansas State University
• Manhattan, KS 66502
• junli_at_ksu.edu

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Core Technology Inlaid Nanoelectrode Array
As-grown CNTs on circuits
After Encapsulation and polishing
Micro- pattern
2 mm
Nano- pattern
5 mm
Precise control of vertically aligned carbon
nanotubes on electronic circuits for biosensing
Non- pattern
J. Li et al, Appl. Phys. Lett., 81(5), 910
(2002). J. Li et al, Appl. Phys. Lett., 82(15),
2491 (2003). J. Li, et al, Nanoletters, 3(5),
597-602 (2003).
500 nm
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Ultrasensitive Label-free Electrochemical DNA
Sensing
Multiplex DNA Array

• Demonstrated in detecting
• Oligonucleotide targets
• PCR amplicon of BRCA1 genes
• Advantages
• Label free
• Ultrahigh sensitivity (lt1000 molecules)
• Using inherent guanine oxidation
• Electric field to enhanc speed and accuracy
• Applications
• Direct mRNA analysis
• Multiplexing disposable cartridge for handheld
  detection devices
• Applicable for immunosensor

positive
negative
Mediator amplified guanine oxidation at CNT
nanoelectrodes
J. Li, et al, Nano Letters, 3(5), 597-602 (2003).
J. Li, et al, Nanotechnology, 14 (12), 1239
(2003).
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Bossmann and Co-Workers
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Electron Micrograph of AP-Al2O3
Sample composed of friable aggregates of
nanoparticles of alumina hydroxide (boehmite)
with disordered structure. They have the
morphology of strongly curved planes length
about 300Å, thickness 10-20Å.
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AP-Al2O3-MgO
(AlMg21) Aggregate of AlOOH-MgO consisting of
molecular planes AlOOH (boehmite) and MgO
nanocrystals with d2002.1Å.
20Å
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TiO2
Doping
TiO2-x X
M/TiO2
Non-metals (X B, C, N, S, F)
Metals (M Ni, Cr, Pd, Ag, Pt, Au )
codoping
AgNO3
(NH4SCN and NH2SCNH2)
Ag/(C,S)-TiO2
Some nonmetal precursors are TiC, TiS2, CO, NH4F,
H3BO3, H3PO3, NH3, , Urea etc
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Table 2

• BET Surface area Quantachrome Nova 1000 series,
  N2 adsorption at 77K
• Crystallite size Debye-Scheerer Eq. ( t
  0.9?/ßcos?)
• Band Gap 1239.8/ ?

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Fig. 3 - UVVisible absorption profiles of (a) C
and/or S doped-TiO2, and (b) Ag/(C, S)-TiO2 -01
catalysts at various temperatures compared to
P25-TiO2.
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Fig. 4 - Degradation of gaseous acetaldehyde on
Ag/(C, S)-TiO2-01 catalyst (annealed at 500oC/2h
in air) under (a) visible and (b) UV light.
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Fig. 6 - Production of CO2 from CH3CHO on
various catalysts under (a) visible and (b) UV
light.
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New Photocatalysts for the Decomposition of 2CEES
under UV light
Slow but steady decomposition by Cr-Al-MCM-41
(mesoporous silica). (SA, 1200m2/g). End
products include disulphide
Decomposition of 2CEES by P25 TiO2. (SA 55m2/g).
End products include disulphide
Complete destruction by TiO2SiO2 aerogel (SA,
550m2/g) better photocatalyst than even P25 TiO2

Complete destruction by Vanadium impregnated
Mesoporous silica, SBA-15. (SA, 700m2/g)
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Biological Decontamination

• Dry Powders vs. Spores
• Dry Powders vs. Common Household bacteria
• Nanoparticles vs. MS2 virus

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Inactivation of Vegetative Cells, but Not Spores,
of Bacillus anthrasis, B. Cereus, and B. subtilis
on Stainless Steel Surfaces Coated with
Anti-microbial Silver- and Zinc-Containing
Zeolite Formulation
Belinda Galeano, Emily Korff, and Wayne L.
Nicholson Department of Veterinary Science and
Microbiology, University of Arizona, Tucson,
Arizona Received 21 January 2003/ Accepted 3
April 2003
Stainless steel surfaces coated with paints
containing silver- and zinc-containing zeolite
(AgION antimicrobial) were assayed in comparison
to uncoated stainless steel for antimicrobial
activity against vegetative cells and spores of
three Bacillus species, namely, B. anthracis
Sterne, B. cereus T, and B. subtilis 168. Under
the test conditions (25oC and 80 relative
humidity), the zeolite coating produced
approximately 3 log10 inactivation of vegetative
cells within a 5- to 24-h period, but viability
of spores of 3 species was not significantly
affected.
Applied and Environmental Microbiology 69
4329-4331 (2003)
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TEM images of E. coli cells before (left) and
after (right) treatment with C, S-Ag-TiO2 (10).
Nine log kill after 5 minutes. B. Subtilis
spores gave a five log kill in 30 minutes.
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TEM image of SMAD silver nanoparticle powder
after evaporation of solvent (100 nm
scale bar ----------------------------)
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Silver nanoparticles capped with
3-mercapto-1,2-propanediol. The scale bar
represents 100 nm. ----------------------
--
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Air-SMAD powder interaction with E-coli bacterial
cell. Silver ions enter the cell, are reduced to
atoms, and agglomerate. Cell is destroyed.
(Cell is about one micron across).
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Silver nanoparticles capped with water soluble
ligand (3-mercapto-1,2-propane diol) enter the
E-coli cell, but do not kill it.
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Table 1. Quantitative Results from Analysis of
NA-Metal Oxide Plus Adducts
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Photographs of Halogen/Interhalogen Adducts of
(a) NA-Al2O3 Plus (b) NA-TiO2 (c) NA-CeO2.
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Table 11. Log kills of B. anthracis spores.
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Figure 18. TEM micrograph of untreated B.
anthracis cells displaying single cell
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Figure 21. TEM micrograph of treated B. anthracis
cells displaying a damaged cell.
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Figure 23. TEM micrograph of untreated B.
anthracis spores high magnification.
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Figure 24. TEM micrograph of treated B. anthracis
spores displaying damaged spore.
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Table 2. Log Reduction of MS2 virus by NA-Al2O3
Plus Adducts (10 mg/mL).
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Table 4. Log Reduction of MS2 virus by NA-CeO2
Adducts (10 mg/mL).
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Table 6. Log Reduction of MS2 virus by NA-TiO2
Adducts (10 mg/mL).
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Table 8. Log Reduction of Phi-X174 virus by
NA-Al2O3 Plus Adducts (10 mg/mL).
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Table 10. Log Reduction of Phi-X174 virus by
NA-CeO2 Adducts (10 mg/mL).
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Table 12 Log Reduction of Phi-X174 virus by
NA-TiO2 Adducts (10 mg/mL).
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Figure 1. TEM image of untreated MS2 virus
displaying several viruses.
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Figure 3. TEM image of treated MS2 virus
displaying remains.
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MECHANISM OF ACTION
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MECHANISM OF ACTION
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ANTITOXIN PROPERTIES

• Microcystins are toxins produced by the
  blue-green algae Microcystis Aeroginosa upon
  blooming
• The toxins specifically and irreversibly inhibit
  protein phosphatases
• The microcystins are very potent carcinogens and
  have an LD50 50mg/kg.
• Microcystins are usually found in surface waters,
  but they can be found in practically any surface
  water source
• They have been encountered in many countries-
  USA, Canada, Brazil, France, China, Hungary,
  Finland, etc.

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ANTITOXIN PROPERTIES
General structure of the microcystins
Microcystin LR
Microcystin RR
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CONCLUSIONS

• Nanoparticles can reversibly adsorb large amounts
  of strong disinfectants such as chlorine, iodine,
  etc.
• Nanoparticles express bactericidal activity by
  themselves, even without halogen present
• AP-MgO/X2 can kill spores on contact
• Nanoparticles attack the microbial cells in
  several ways
• - electrostatic attraction and sticking
• - high abrasiveness
• - basic character
• - oxidizing power
• Halogenated nanoparticles are effective for
  detoxification of microcystins, and preliminary
  evidence indicates effectiveness for fungi.

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Benefits to Animals/Food

• Air Purity and Purification
• Sensors for Toxins
• Nanoscale Photocatalysts for Air Purification
• Nanoscale Powders and Porous Pellets for
  Adsorbing Toxins
• Water Purity and Purification
• Sensors for Toxins
• Nanoscale Photocatalysts for Water Purification
• Nanoscale Powder and Porous Pellets for Adsorbing
  Toxins

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Benefit to Animals/Food

• Plant Growth
• Soil Microbes

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• On-Going Projects
• Breathable Air Security Institute and Consortium
  (BASIC)
• Targeted Excellence ProjectKSU
• Senator Roberts Committee on Future Science and
  Technology
• Materials Science and Nanoscience Task Force
• Center for Biopolymers by Design
• Nano-biopolymer Composites
• Green Plastics
• Nanotechnology for Solar Energy Utilization

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Products Available

• Mitigation
• FAST-ACT (First Applied Sorbent Treatment
  Against Chemical Threats)
• OdorKlenz
• ChemKlenz
• Sensing
• Bourne, M. A Consumers Guide to MEMS and
  Nanotechnology, Bourne Research LLC, Scottsdale,
  AZ 85755
• Lab-m-a-Chip Micro Cantilevers

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• Some Additional Key References
• El-Sayed, et. al., On the Universal Scaling
  Behavior of the Distance Decay of Plasmon
  Coupling in Metal Nanoparticle Pairs A Plasmon
  Ruler Equation, Nano Letters, 2007, 7,
  2080-2088.
• Englebienne, Use of Colloidal Gold Surface
  Plasmon Resonance Peak Shift to Infer Affinity
  Constants from the Interactions between Protein
  Antigens and Antibodies Specific for Single or
  Multiple Epitopes, Analyst, 1998, 123,
  1599-1603.
• Klabunde, editor, Nanoscale Materials in
  Chemistry, John Wiley Publishers, 2001, New York,
  NY, First Edition (2nd Edition in Preparation).

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Morozov, et. al., Complementation of a Potato
Virus X Mutant Mediated by Bombardment of
Plant Tissues with Cloud Viral Movement
Protein Gases, J. Gen. Virol., 1997, 78,
2077-2083. Itaya, et. al., Cell-to-Cell
Trafficking of Cucumber Mosaic Virus
Movement Protein Green Fluorescent Protein
Fusion Produced by Biolistic Gene Bombardment in
Tobacco, The Plant Journal, 1997, 12,
1223-1230. OBrien, et. al., Diolistics
Incorporating Fluorescent Dyes into
Biological Samples Using a Gene Gun, Trends in
Biotech., 2007, 25, 530-534.
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Wallace, et. al., Colorimetric Detection of
Chemical Warfare Simulants, New J. Chem.,
2005, 29, 1469-1474. Giordan Collins,
Synthetic Methods Applied to the Detection
of Chemical Warfare Nerve Agents, Current
Organic Chemistry, 2007, 11,
255-265. Kumar, et. al., editors,
Nanofabrication Toward Biomedical
Applications, Wiley-VCH, New York
(2005). Fryxell, et. al., editors, Environmental
Applications of Nanomaterials, Imperial
College Press, Danvers, MA (2007).
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Koper and Klabunde, Nanoparticles for
Destructive Sorption of Biological and
Chemical Contaminants, U.S. Patent
6,057,388 (2000). Koper, et. al., Reactive
Nanoparticles as Destructive Adsorbents for
Biological and Chemical Contamination, U.S.
Patent 6,417,423 (2002). Stoimenov, et. al.,
Metal Oxide Nanoparticles as Bactericidal
Agents, Langmuir, 2002, 18, 6679-6686.
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Wong, et. al., Visible Light-Induced
Bactericidal Activity of Nitrogen Doped
Titanium Photocatalyst Against Human
Pathogens, Appl. and Envir. Microbiology,
2006, 72, 6111-6116. Ranjit, et. al.,
Antibacterial Activity of ZnO Nanoparticle
Suspensions on a Broad Spectrum of
Microorganisms, FEMS Microbiol. Lett., 2008,
279, 71-76.
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Acknowledgements

• Professors Students
• Stefan Bossmann Johanna Häggström
• Jun Li Alexander Smetana
• Charles Rice Dmytro Demydov
• Vera Prasad Dambar Hamal
• Larry Erickson Xiangxin Yang
• Funds
• Department of DefenseARO and Marines
• National Science Foundation
• Materials
• NanoScale Corporation
• 1310 Research Park Drive
• Manhattan, KS 66502
• www.nanoscalecorporation.com
• [phone]

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Front Row Yen-Ting Kuo, Zhiqiang (Aaron) Yang,
K.J. Klabunde, Xiangxin Yang Back Row Dambar
Hamal, Erin Beavers, Johanna Häggström, Sreeram
Cingarapu