Nanotoxicology. Some nanomaterial properties raise toxicity concerns. Small size. High surface area. Fibrous morphology

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1 Nanotoxicology Some nanomaterial properties raise toxicity concerns Small size - small aerodynamic diameter deep lung penetration - high permeability in biological membranes - enhanced cellular uptake - specific interactions with DNA, proteins (of similar size) High surface area - high surface activity - facilitated transport the Trojan horse effect Fibrous morphology - agglomeration and airway blockage - difficulty with lung clearance - are carbon nanotubes the next asbestos?

2 The Challenge: Carbon Nanomaterial Diversity and Complexity Carbon nanomaterials vary widely in - size ( nm) - shape (fibrous, equi-axed, lamellar, conical) - surface chemistry (hydrophilic/phobic) - coatings (polymers, surfactants, biomolecules). - composition (esp. Fe, Co, Ni) Single nanomaterial samples are complex, containing: - amorphous and graphitic particulate byproducts - wide distributions of tube size and length - catalyst residues of variable and often unknown > chemistry (metals, carbides, oxides) > size > degree of encapsulation (accessibility)

3 Metals Content in Selected Commercial Carbon Nanotube Samples \ Vendor A AP SWNT Ni-Y (35%) B C D E F G AP SWNT AP SWNT High purity (HP) AP SWNT RFP SWNT Unpurified MWNT Purified MWNT Unpurified MWNT Purified MWNT Unpurified SWNT Purified SWNT Ni-Co (25%) Ni-Y (25%) Co-Mo (<2%) Ni-Y (30%) Ni-Y (15%) Fe (4.2%) Fe (0.1%) Fe (4.25%) Fe (3.29%) Fe (22.2%) Fe (10.9%)

4 Nickel catalyst residues in single-wall nanotube samples As-produced Ni SWNT bundle 10 nm Vendor purified

5 What is known about nickel toxicity? Ni in some forms is a known human carcinogen The nickel-ion hypothesis: nickel toxicity, carcinogenesis mainly depend on the intracellular nickel (II) ion concentrations, independent of the original nickel compound to which an organism Is exposed [Snow, 1998].

6 Bioavailability of Nickel in Carbon Nanotubes Liu et al. Brown University

7 The Role of Iron in Carbon Nanotubes 10 nm Bioavailability? Fe C shell tube

8 Carbon Nanotube Iron Generates Free Radicals and DNA Damage CNTs/CNFs with Fe ferrozine chelated Fe (redox inactive) Guo et al., Brown University Ascorbate Fe 2+ O 2 OH + Fe desferoxamine chelated Fe (redox inactive) % Single Strand Breaks Asbestos Unpurified CNT Purified CNT Ground CNT Oxidized CNT 10 0

9 Targeted Removal of Bioavailable Metal in Carbon Nanotubes 3 Mobilized Nickel (ppm) Purified sample from vendor A After overnight water soak After 3 M HCl treatment followed by 1, 2, or 3 hot water washes Total Ni in SWNTs (wt-%)

10 The Opportunity Fabrication / purification / formulation all affect key toxicity variables: - size, shape, surface chemistry - metals content and location Brown University approach: Understand relationships between toxicity and specific material features (size, shape, metals content, surface chemistry) to guide the development of green carbon nanomaterials Most nanomaterials are: - fabricated, not natural - developmental, not commercial often no large barriers to reformulation Nanomaterial Fabrication CNN website HEALTH Toxicity Assays Scientists question possible nanotech risks Tuesday, December 13, 2005 PROVIDENCE, Rhode Island (AP)

11 Possible exposure routes to nanophase metal catalyst residues Nanomaterial lifecycle R&D Fabrication Purification X Product/device manufacture Market X X X X Laboratory personnel manufacturing workers environment consumers, public

12 The Nanotoxicology Team Sponsored Projects CNN website HEALTH Scientists question possible nanotech risks Tuesday, December 13, 2005 PROVIDENCE, Rhode Island (AP) Physical and chemical determinants of carbon nanotube and nanofiber toxicity, EPA STAR Grant, 2004 (Hurt, Kane) Washington Post, Sunday, December 11, 2005 Superfund Basic Research Grant, Projects 2,6 on Nanotoxicology (Kane, Hurt, Zhitkovich) Micropatterned nanotopography chips for probing the cellular basis of toxicity and biocompatibility, NSF NIRT Grant 2005 (Hurt, Crawford, Kane, Morgan, Brown, and Sarachick) More Research Urged on Nanoparticle Risk By MICHELLE R. SMITH The Associated Press PROVIDENCE, R.I. -- Those stain-resistant khakis you just picked up at the mall, the tennis ball that holds its bounce longer and sunscreen that's clear instead of white have something in common nanotechnology...."these issues are being discussed openly," said Agnes Kane, a pathologist at Brown University, Engineering Pathology and laboratory medicine Molecular Phar., Physiology, Biotechnology Sociology Environmental Health+Safety

13 Themes The Alliance for Molecular and Nanoscale Innovation (AMNI) at Brown University Center for Nanoscience and Soft Matter (CNSSM) Center for Advanced Materials Research (CAMR) Conventional Grain Size NanoMedicine Working Group Nanoscale Grain Size 6

14 Backups

15 Applications: Nanomedicine Engineered nanoparticles for delivery, labeling - sized for intra-arterial injection - surface modified for uptake by target cells - detectable by fluorescence, MRI - major application: early cancer detection and treatment Nanostructured implant surfaces - improved cell adhesion, proliferation - improved biocompatibility Nanofiber networks as tissue engineering scaffolds - biomimetic extracellular matrix Nanoscale cell biology - use of concepts and tools of physical sciences to understand the nanoscale machinery within cells (membranes and receptors, pumps, transcription machinery, protein folding machinery, biological motors)

16 National Public Radio April 28th 2006 Weighing the Potential Risks of Nanotechnology Talk of the Nation, Science Friday

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