Biodurability of Single-Walled Carbon Nanotubes Depends on Surface Functionalization.

Recent research has led to increased concern about the potential adverse human health impacts of carbon nanotubes, and further work is needed to better characterize those risks and develop risk management strategies. One of the most important determinants of the chronic pathogenic potential of a respirable fiber is its biological durability, which affects the long-term dose retained in the lungs, or biopersistence. The present article characterizes the biodurability of single-walled carbon nanotubes using an in vitro assay simulating the phagolysosome. Biodurability is observed to depend on the chemistry of nanotube surface functionalization. Single-walled nanotubes with carboxylated surfaces are unique in their ability to undergo 90-day degradation in a phagolysosomal simulant leading to length reduction and accumulation of ultrafine solid carbonaceous debris. Unmodified, ozone-treated, and aryl-sulfonated tubes do not degrade under these conditions. We attribute the difference to the unique chemistry of acid carboxylation, which not only introduces COOH surface groups, but also causes collateral damage to the tubular graphenic backbone in the form of neighboring active sites that provide points of attack for further oxidative degradation. These results suggest the strategic use of surface carboxylation in nanotube applications where biodegradation may improve safety or add function.

[1]  Karluss Thomas,et al.  Research strategies for safety evaluation of nanomaterials, part V: role of dissolution in biological fate and effects of nanoscale particles. , 2006, Toxicological sciences : an official journal of the Society of Toxicology.

[2]  Daniel Morris,et al.  Targeted Removal of Bioavailable Metal as a Detoxification Strategy for Carbon Nanotubes. , 2008, Carbon.

[3]  J. L. Macdonald,et al.  Mesothelial cell proliferation and biopersistence of wollastonite and crocidolite asbestos fibers. , 1997, Fundamental and applied toxicology : official journal of the Society of Toxicology.

[4]  M. Jaurand,et al.  Particle and Fibre Toxicology Mesothelioma: Do Asbestos and Carbon Nanotubes Pose the Same Health Risk? , 2022 .

[5]  K. Balasubramanian,et al.  Chemically functionalized carbon nanotubes. , 2005, Small.

[6]  Ya‐Ping Sun,et al.  Carbon dots for multiphoton bioimaging. , 2007, Journal of the American Chemical Society.

[7]  Latha A. Gearheart,et al.  Electrophoretic analysis and purification of fluorescent single-walled carbon nanotube fragments. , 2004, Journal of the American Chemical Society.

[8]  Jing Yang,et al.  One-step synthesis of fluorescent carbon nanoparticles by laser irradiation , 2009 .

[9]  Stefanie Hellweg,et al.  Exposure to manufactured nanostructured particles in an industrial pilot plant. , 2008, The Annals of occupational hygiene.

[10]  John Parthenios,et al.  Chemical oxidation of multiwalled carbon nanotubes , 2008 .

[11]  K. Kellar,et al.  Biopersistence of inhaled organic and inorganic fibers in the lungs of rats. , 1994, Environmental health perspectives.

[12]  A. L. Le Faou,et al.  Macrophage Culture as a Suitable Paradigm for Evaluation of Synthetic Vitreous Fibers , 2008 .

[13]  Giorgia Pastorin,et al.  Crucial Functionalizations of Carbon Nanotubes for Improved Drug Delivery: A Valuable Option? , 2009, Pharmaceutical Research.

[14]  Alexander Star,et al.  Biodegradation of single-walled carbon nanotubes through enzymatic catalysis. , 2008, Nano letters.

[15]  Jeffrey W Card,et al.  Pulmonary applications and toxicity of engineered nanoparticles. , 2008, American journal of physiology. Lung cellular and molecular physiology.

[16]  B. Fubini,et al.  Surface reactivity in the pathogenic response to particulates. , 1997, Environmental health perspectives.

[17]  Agnes B Kane,et al.  Biopersistence and potential adverse health impacts of fibrous nanomaterials: what have we learned from asbestos? , 2009, Wiley interdisciplinary reviews. Nanomedicine and nanobiotechnology.

[18]  G. Oberdörster,et al.  Nanotoxicology: An Emerging Discipline Evolving from Studies of Ultrafine Particles , 2005, Environmental health perspectives.

[19]  Craig A. Poland,et al.  Carbon nanotubes introduced into the abdominal cavity of mice show asbestos-like pathogenicity in a pilot study. , 2008, Nature nanotechnology.

[20]  P. Baron,et al.  Exposure to Carbon Nanotube Material: Aerosol Release During the Handling of Unrefined Single-Walled Carbon Nanotube Material , 2004, Journal of toxicology and environmental health. Part A.

[21]  R. Hurt,et al.  Nanotoxicology: the asbestos analogy revisited. , 2008, Nature nanotechnology.

[22]  Gwi-Nam Bae,et al.  Monitoring Multiwalled Carbon Nanotube Exposure in Carbon Nanotube Research Facility , 2008 .

[23]  Scott E McNeil,et al.  Nanotechnology safety concerns revisited. , 2008, Toxicological sciences : an official journal of the Society of Toxicology.

[24]  R. Hurt,et al.  Liquid crystal engineering of carbon nanofibers and nanotubes , 2004 .

[25]  Stanislaus S. Wong,et al.  Effect of ozonolysis on the pore structure, surface chemistry, and bundling of single-walled carbon nanotubes. , 2008, Journal of colloid and interface science.

[26]  J. Kanno,et al.  Induction of mesothelioma in p53+/- mouse by intraperitoneal application of multi-wall carbon nanotube. , 2008, The Journal of toxicological sciences.

[27]  F. Fang Antimicrobial reactive oxygen and nitrogen species: concepts and controversies , 2004, Nature Reviews Microbiology.

[28]  K. Ravichandran,et al.  Phagosome maturation: going through the acid test , 2008, Nature Reviews Molecular Cell Biology.

[29]  C. Balasubramanian,et al.  Isolation and characterization of fluorescent nanoparticles from pristine and oxidized electric arc-produced single-walled carbon nanotubes. , 2006, The journal of physical chemistry. B.

[30]  M. Itkis,et al.  Determination of the acidic sites of purified single-walled carbon nanotubes by acid–base titration , 2001 .

[31]  C. R. Martin,et al.  The emerging field of nanotube biotechnology , 2003, Nature Reviews Drug Discovery.

[32]  R. Hurt,et al.  Controlling water contact angle on carbon surfaces from 5° to 167° , 2006 .

[33]  Xin Wang,et al.  Biodistribution of Pristine Single-Walled Carbon Nanotubes In Vivo† , 2007 .

[34]  J. James,et al.  Pulmonary toxicity of single-wall carbon nanotubes in mice 7 and 90 days after intratracheal instillation. , 2003, Toxicological sciences : an official journal of the Society of Toxicology.

[35]  Mark D. Hoover,et al.  Characterization of phagolysosomal simulant fluid for study of beryllium aerosol particle dissolution. , 2005, Toxicology in vitro : an international journal published in association with BIBRA.

[36]  Peter Wick,et al.  Nanomaterial cell interactions: how do carbon nanotubes affect cell physiology? , 2009, Nanomedicine.

[37]  R. Hurt,et al.  High capacity mercury adsorption on freshly ozone-treated carbon surfaces. , 2008, Carbon.

[38]  C. Morscheidt,et al.  In vitro assessment of biodurability: acellular systems. , 1994, Environmental health perspectives.

[39]  R. Aitken,et al.  Carbon nanotubes: a review of their properties in relation to pulmonary toxicology and workplace safety. , 2006, Toxicological sciences : an official journal of the Society of Toxicology.

[40]  G. Oberdörster,et al.  Significance of particle parameters in the evaluation of exposure-dose-response relationships of inhaled particles , 1996 .

[41]  Stephen Olin,et al.  Testing of Fibrous Particles: Short-Term Assays and Strategies , 2005, Inhalation toxicology.