Harvard-NIEHS Center overview: Cores and Activities Philip - PowerPoint PPT Presentation

Harvard-NIEHS Center overview: Cores and Activities Philip Demokritou, Center Director

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Collaborating Institutions Our Center builds upon the infrastructure and interdisciplinary experience of five existing academic research centers/Institutes in the fields of nanomaterial synthesis, characterization, nanobiology and nanotoxicology research : Center for Nanotechnology and Nanotoxicology at Harvard School of • Public Health; (Dr Demokritou) Center for Nanoscale Systems (CNS) at Harvard School of Engineering • and Applied Sciences; (Dr Bell) Laboratory for Advanced Carbon-based Nanomaterials at MIT; (Dr • Strano) Particle Engineering Research Center (PERC ) at University of Florida; (Dr • Moudgil) Forest Bio-products Research Institute at University of Maine. (Dr • Bousfield) 3

Our mission statement  We will work across disciplines, share new ideas, develop industry- relevant reference ENMs, and work with the nanotox consortium to develop multidisciplinary projects and methods to advance our understanding on nano-safety. 4

Where Applications of Engineered Nanomaterials and • Nanotechnology meet Nanosafety research Vision: Integrate material & exposure science and nanotoxicology risk assessment – to pave the way towards sustainable nanotechnology Research Areas: Environmental nanotechnology, safer by design synthesis of – ENMs, exposure science, inhalation and cellular toxicology, life cycle implications of nano-enabled products and development of novel methods for the physico- chemical and toxicological characterization of nanomaterials Mission: Bring together ALL stakeholders: industry, academia, policy makers and – the general public for sustainable development of NT industry Industrial Partners: Over 20 partners ( BASF, Panasonic, Nanoterra, STERIS, – AVECTAS , etc) International in nature: Extensive network of collaborators including US Federal – Agencies, and Universities around the world (ETH Zurich, NTU- Singapore, RIVM, MIT, SUNY, UMass, Northeastern Univ., NIOSH, CPSC, etc)

Funding Sources

Website: http://hsph.harvard.edu/nano

Harvard Center For Nanotechnology and Nanotoxicology (2015-2016) Back Row (left to right): Ya Gao, Georgios Pyrgiotakis, Thomas Donaghey, Ramon Molina, Glen Deloid, Phil Demokritou, Dilpreet Singh, Joe Brain, Akira Tsuda, Edgar Diaz, Jin-Ah Park, Yanli wang and Xunzhi Zhu Sitting (from left to right): Caroline Cirenza, Sylvia Rodrigues, Archana Vasanthakumar, Sandra Pirela, Christa Watson, Jiayuan Zhao, Jenifer Mitchel, Guanghe Wang.

ENM Synthesis Core Metals /Metal Oxides (FSP): P. Demokritou Metals/Metal Oxides (Wet synthesis): B. Moudgil Carbon based ENMs (Graphene, CNTs, etc): M. Strano Nanocellulose: D. Bousfield

Philip Demokritou, Harvard University ENM SYNTHESIS USING FLAME SPRAY PYROLYSIS (AEROSOL REACTORS)

Flame Spray Pyrolysis Synthesis: Principle of operation  “Bottom up” approach for Me/MeO synthesis  Industry relevant method  A liquid precursor which contains the solution of an organo-metal is pumped though a nozzle.  Fine droplets are formed and dispersed using O2.  Droplets are ignited using a small CH4 flamelet  Primary Particles are formed by “homogenous nucleation”  Larger size aggregates and agglomerates are subsequently formed .  Particle formation and properties can easily be controlled by adjusting the flame conditions . 11

Versatile Engineered Nanomaterial Generation System (VENGES) Features:  A Platform for pcm characterization ENM sampling/ Sampling & in-vitro , in-vivo tox studies collection Exposure  Based on industry relevant , flame filter spray pyrolysis (FSP) aerosol T 1 reactors Q S HEPA Q A Q P  Q R Versatile: All Me and MeO can be Animal exposure synthesized 50 cm CO 2 , CO, chamber FMPS P-TRAK NO 2 BUFFER RH, T 2  P-c-m properties can be modified (primary particle and aggregate HEPA HEPA sizes, crystalinity, shape, etc). Exposure Monitoring Equipment CH 4 /O 2 Q D  O 2 support ENMs are produced continuously in dispersion flame liquid precursor the gas phase allowing to transfer Animal Exposure Flame Synthesis System them with controlled agglomeration to inhalation chambers. Synthesis (Demokritou et al., Inh Tox. 2010)

In flight SiO 2 coating of ENMs using the Harvard VENGES: Core-shell ENMs Particle Collection Filter Coating Reactor during Synthesis (1) Demokritou et al. Inh. Toxicology, 2010 (2) Gass et al. Sus. Che. & Eng, 2012

A Safer by Design Concept for flame-generated ENMs Elements of a Safer by Design Approach • Reduce Toxicological footprint • Maintain functional properties of ENMs (optoelectronic, mechanical, etc) • Scalability is the big challenge Tox. Pathways for Me and MeOx Scalability? (1) Sotiriou et al., Curr Opin Chem Eng 2011 , 1, 3 – 10 (2) Xia et al., ACS Nano 2011 , 5, 1223 – 1235 (3) Gass et al. Sus Chem and Eng, 2013 , 7, 39 (4) Teleki et al., Chem. Mater. 2009, 21, 2094 – 2100 (5) Sotiriou et al., Adv. Funct. Mater. 2010, 20, 4250 – 4257

ZnO Case Study: “Safer by design” cosmo-ceutical products • The Yan: ZnO Nanorods can block effectively UV while remain transparent to visible light 1 • The Yin: ZnO release ions and is photocatalytically active -> ROS generation- > Genotoxic 2 1. Sotiriou et al. ES:Nano, 2014 2. Watson et al. ACS Nano, 2014

Brij Moudgil, University of Florida SYNTHESIS OF METAL AND METAL OXIDES USING HIGH PRECISION & THROUGHPUT HYDROTHERMAL REACTORS (WET CHEMISTRY)

Facilities and Equipment at the University of Florida • Most of the proposed particulate systems related research activities at the University of Florida will be conducted at the Particle Engineering Research Center (PERC). PERC has a dedicated 25,000 ft 2 facility (Particle Science & Technology Building) and 17,000 ft 2 of laboratory space for the characterization and synthesis of particulate systems. • Techniques are available for physical, mechanical and chemical analysis of particle systems including size, shape, surface area and porosity, surface chemistry, rheology, tribology, interfacial phenomena, powder mechanics, powder flow and segregation. Processing facilities are provided in a 5000 ft 2 high-bay pilot plant and • including crystallization, classification, size reduction, spray drying, coating, filtration and a wide variety of other techniques. Particle synthesis techniques include a 20 L stirred reactor, spray dryer, fluid bed dryer, wet and dry coating techniques, laser deposition and mechanofusion. 17

• The PERC works closely with the Major Analytical Instrumentation Center (MAIC), the Interdisciplinary Center for Biotechnology Research (ICBR), and the Center for Environmental & Human Toxicology and has access to their facilities and equipment. MAIC specializes in materials characterization with a variety of state of the art methods such as high resolution scanning and transmission electron microscopy, x-ray photoelectron spectroscopy, and other techniques. See http://www.maic.mse.ufl.edu for a full list of capabilities. • The ICBR provides state-of-the-art facilities for biological sample analysis ranging from transmission electron microscopy of biological samples to tandem mass spectrometry to gene chip analysis. See http://www.biotech.ufl.edu for a full list of capabilities. • The Center for Environmental & Human Toxicology is working closely with the PERC to resolve issues in nanoparticle toxicity (see http://www.nanotoxicology.ufl.edu) and has expertise in performing and interpreting in vitro and in vivo toxicity studies. 18

• Image Pro v4.5 Optical Analysis Software, Paar Physica UDS 200 Rheometer, Optical Microscopes, Coulter LS 13320 Particle Size Analyzer, Colloidal Dynamics Acoustosizer, Brookhaven ZetaPlus, Microtrac Nanotrac. For a full listing of capabilities, see https://rsc.aux.eng.ufl.edu/resources/default.asp?s=PAIC. • The center researchers also have access to facilities at Columbia University (NSF I/UCRC Partner with UF) including atomic force microscope (AFM), quartz crystal microgravimatry (QCM), surface plasmon resonance spectroscope (SPR), Fourier Transform Infrared (FTIR) spectrophotometer, fluorescence spectrophotometer, microcalorimeter, surface area analyzer, scanning electron microscope - energy dispersive x-ray fluorescence (SEM-EDX), inductively coupled plasma (ICP) spectrophotometer, UV/visible spectrometer, particle size analyzer, High performance liquid chromatograph (HPLC/GPC), electron spin resonance spectrometer (ESR), Brookhaven photon correlation spectroscopy (PSC), analytical ultra-centrifuge, dynamic laser scattering equipment, zeta meters. 19

Capabilities/Expertise Relevant to HSPS-NIEHS Project Metal and Metal Oxide Materials NPs Method Size Shape spheres, rods, reduction of salts in Au 1-100 nm other shapes aqueous conditions possible polyol method Ag reduction of salts in < 50 nm spheres aqueous conditions chemical reduction in Co 10-100 nm spheres flow reactor thermal decom- Fe <100 nm spheres, rods position sonochemical thermal Al 10-100 nm spheres decomposition Mn chemical reduction 10-100 nm spheres vacuum evaporation hexagonal Zn 10-160 nm & Condensation prisms Stober synthesis spheres, rods, 5 nm-1 μ m SiO 2 surfactant-templated needles synthesis 20