1 Increasing Production of Engineered Nanomaterials Christine Hendren

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Increasing Production of Engineered Nanomaterials Christine Hendren, Duke University

Egyptian Eye Makeup and Hair Dye (~ 2000 BC): Fabrication of quantum dots in your hair!! The composition and supramolecular organization of keratins can control Pb. S nanocrystal growth inside a hair Nano Lett. , 2006, 6 (10), pp 2215– 2219

Maya Blue Paint (2000 BC – AD 250): An hybrid organic-inorganic composite nanomaterial Resistance to acid and biocorrosion, color retention after centuries in the extreme conditions of the rain forest Science 273, 223 (1996)

The Lycurgus Cup (~ 4 AD): Most sophisticated glass objects before the modern era www. nanowerk. com/spotlight/ NPs are silver-gold alloy, with a ratio of silver to gold of about 7: 3, containing in addition about 10% copper.

Nanotubes and nanowires in ancient Damascus blades (~900 AD) Multiwalled tubes, bent like a rope, with the characteristic layer distance d 0. 34 nm Young’s modulus and tensile strength of CNT is about 10 and 20 times higher than that of steel Nature 444, 286 (2006)

Nanoparticles are Ubiquitous in Water and Wastewater The Clark Fork River in Western Montana Source: Hochella et al. , 2007 Mine Drainage Hydrothermal Vent Sediment Porewater

Nanoparticles are Ubiquitous in Water and Wastewater Municipal Wastewater Sewage Sludge Drinking Water Distribution System Benn & Westerhoff, 2008 Environ. Sci. Technol. , 2008, 42 (11), 4133– 4139 Kim et al. , 2010 Environ. Sci. Technol. 44, 19, 7509 -7514 Hochella et al. , 2007 J. Environ. Monit. 9, 13061316

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What do environmental researchers have to do with nano? Source Formation Stability Mobility Bioavailability Toxicity Receptor 1 0

Source: Aggarwal et al. , Advanced Drug Delivery Reviews, 61, 428 -437, (2009)

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Levard et al. , ES&T, 2012, 46 (13), pp 6900– 6914

Kaegi et al. Environ. Sci. Technol. 2011, 45, 3902– 3908. 1 7

Capped Ag. NPs “Pristine” Nano. Composix, Inc. Floc particle Capped-Sulfidized Ag. NPs “Transformed” Levard et al. , 2011 18

p. H 7 5 m. M Na. NO 3 19

p. H 7 5 m. M Na. NO 3 20

Nanoparticles as an unintended by-product Bioreduction of hexavalent uranium, U(VI), to tetravalent uranium, U(IV), which precipitates as uraninite. Assumption: the formation of highly insoluble uraninite (UO 2) will inhibit the mobilization of uranium. Source: Suzuki et al. , 2002, Nature Source: oceanworld. tamu. edu/. . . /Images/schematic. gif Zero-valent iron (ZVI) Permeable Reactive Barrier (PRB) Δ in chemical & biological gradient

Electrons 10 -26 Mineral Bacterial Human Cluster Cells being Red Sea 10 -9 10 -6 100 106 Sun 109 Distant Galaxies 1026 Meters Contact Information https: //blogs. umass. edu/borislau E-mail: borislau@engin. umass. edu 22

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Source: Andrew Maynard, Woodrow Wilson Center, Project on Emerging Nanotechnologies

Are these two particles the same? Core composition, size, and shape Hydrodynamic diameter Ligand composition Ligand packing density Would you expect them to have the same fate and transport behaviors in the environment?

Big impact due to small difference on NP surface! Only the structured NPs penetrated the plasma membrane without bilayer disruption • Core particle size (4. 3 to 4. 9 nm) and shape • Ratio of hydrophilic to hydrophobic ligands (2: 1) • Ligand-shell packing density (11 to 15%) Verma et al. , Nature Materials 7, 588 - 595 (2008)

Zhong et al. , 2006 Adv. Mater. , 18, 2426 Hochella et al. , 2007 J. Environ. Monit. 9, 1306 -1316 Wen et al. 2005, J. Phys. Chem. B, 109, 215 - 220. Park et al. , 2004 Nat. Mater. 3, 891 -895

Size-Dependent Reactivity of Hematite Nanoparticles Hematite’s catalytic efficiency (surface area normalized rates) in Mnoxidation reactions increases by 1 to 2 orders of magnitude when going from 37 nm to 7 nm in size Good contaminant scavenger with a significant increased sorption affinity for aqueous Cu 2+ Madden and Hochella, 2005. Geochim. Cosmochim. Acta, 69, 389 -398 Madden et al. , 2006. Geochim. Cosmochim. Acta, 70, 4095 -4104

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