Comparative photoactivity and antibacterial properties of C60 fullerenes and titanium dioxide nanoparticles.

The production of reactive oxygen species (ROS) by aqueous suspensions of fullerenes and nano-TiO2 (Degussa P25) was measured both in ultrapure water and in minimal Davis (MD) microbial growth medium. Fullerol (hydroxylated C60) produced singlet oxygen (1O2) in ultrapure water and both 1O2 and superoxide (O2-*) in MD medium, but no hydroxyl radicals (OH*) were detected in either case. PVP/C60 (C60 encapsulated with poly(N-vinylpyrrolidone)) was more efficient than fullerol in generating singlet oxygen and superoxide. However, two other aggregates of C60, namely THF/nC60 (prepared with tetrahydofuran as transitional solvent) and aqu/nC60 (prepared by vigorous stirring of C60 powder in water), were not photoactive. Nano-TiO2 (also present as aggregates) primarily produced hydroxyl radicals in pure water and superoxide in MD medium. Bacterial (Escherichia coli) toxicity tests suggest that, unlike nano-TiO2 which was exclusively phototoxic, the antibacterial activity of fullerene suspensions was linked to ROS production. Nano-TiO2 may be more efficient for water treatment involving UV or solar energy, to enhance contaminant oxidation and perhaps for disinfection. However, fullerol and PVP/ C60 may be useful as water treatment agents targeting specific pollutants or microorganisms that are more sensitive to either superoxide or singlet oxygen.

[1]  Tai Hyun Park,et al.  Design of TiO2 nanoparticle self-assembled aromatic polyamide thin-film-composite (TFC) membrane as an approach to solve biofouling problem , 2003 .

[2]  Atsuko Miyajima,et al.  [60]Fullerene as a Novel Photoinduced Antibiotic , 2003 .

[3]  T. Hirano,et al.  Singlet Oxygen Generation Photocatalyzed by TiO2 Particles and Its Contribution to Biomolecule Damage , 2006 .

[4]  T. Xia,et al.  Toxic Potential of Materials at the Nanolevel , 2006, Science.

[5]  Navid B. Saleh,et al.  Titanium dioxide (P25) produces reactive oxygen species in immortalized brain microglia (BV2): implications for nanoparticle neurotoxicity. , 2006, Environmental science & technology.

[6]  H. Ukeda,et al.  Spectrophotometric assay for superoxide dismutase based on tetrazolium salt 3'--1--(phenylamino)-carbonyl--3, 4-tetrazolium]-bis(4-methoxy-6-nitro)benzenesulfonic acid hydrate reduction by xanthine-xanthine oxidase. , 1997, Analytical biochemistry.

[7]  P. Alvarez,et al.  Comparative toxicity of nano-scale TiO2, SiO2 and ZnO water suspensions. , 2006, Water science and technology : a journal of the International Association on Water Pollution Research.

[8]  Mark R Wiesner,et al.  Comparison of the abilities of ambient and manufactured nanoparticles to induce cellular toxicity according to an oxidative stress paradigm. , 2006, Nano letters.

[9]  J. West,et al.  The Differential Cytotoxicity of Water-Soluble Fullerenes , 2004 .

[10]  Sixto Malato,et al.  The photo-fenton reaction and the TiO2/UV process for waste water treatment − novel developments , 1999 .

[11]  J. West,et al.  Nano-C60 cytotoxicity is due to lipid peroxidation. , 2005, Biomaterials.

[12]  Zoran Markovic,et al.  The mechanism of cell-damaging reactive oxygen generation by colloidal fullerenes. , 2007, Biomaterials.

[13]  Kinetics of fullerene triplet states , 1997 .

[14]  K. Sumathy,et al.  A review and recent developments in photocatalytic water-splitting using TiO2 for hydrogen production , 2007 .

[15]  Pedro J J Alvarez,et al.  Fullerene water suspension (nC60) exerts antibacterial effects via ROS-independent protein oxidation. , 2008, Environmental science & technology.

[16]  Ruomei Gao,et al.  Nanomaterials and singlet oxygen photosensitizers: potential applications in photodynamic therapy , 2004 .

[17]  C. Yao,et al.  Rate constants for reaction of hydroxyl radicals with several drinking water contaminants , 1992 .

[18]  M. Hoffmann,et al.  Photoreductive Mechanism of CCl4 Degradation on TiO2 Particles and Effects of Electron Donors. , 1995, Environmental science & technology.

[19]  Yukihiro Goda,et al.  Active oxygen species generated from photoexcited fullerene (C60) as potential medicines: O2-* versus 1O2. , 2003, Journal of the American Chemical Society.

[20]  M. Kasha,et al.  Singlet molecular oxygen in the Haber-Weiss reaction. , 1994, Proceedings of the National Academy of Sciences of the United States of America.

[21]  P. Alvarez,et al.  Mechanisms of photochemistry and reactive oxygen production by fullerene suspensions in water. , 2008, Environmental science & technology.

[22]  I. Rosenthal,et al.  Dye-sensitized-photo-oxidation—a new approach to the treatment of organic matter in sewage effluents☆ , 1977 .

[23]  T J Dougherty,et al.  Identification of singlet oxygen as the cytotoxic agent in photoinactivation of a murine tumor. , 1976, Cancer research.

[24]  P. Alvarez,et al.  Assessing the antibiofouling potential of a fullerene-coated surface , 2008 .

[25]  J. Hoigné Inter-calibration of OH radical sources and water quality parameters , 1997 .

[26]  B. Epe,et al.  Singlet oxygen as an ultimately reactive species in Salmonella typhimurium DNA damage induced by methylene blue/visible light. , 1989, Carcinogenesis.

[27]  Delina Y Lyon,et al.  Antibacterial activity of fullerene water suspensions: effects of preparation method and particle size. , 2006, Environmental science & technology.

[28]  D. Bahnemann,et al.  Photolysis of chloroform and other organic molecules in aqueous titanium dioxide suspensions , 1991 .

[29]  M. Jekel,et al.  The Use of para-Chlorobenzoic Acid (pCBA) as an Ozone/Hydroxyl Radical Probe Compound , 2005 .

[30]  I. Fridovich Biological effects of the superoxide radical. , 1986, Archives of biochemistry and biophysics.

[31]  E. Oberdörster Manufactured Nanomaterials (Fullerenes, C60) Induce Oxidative Stress in the Brain of Juvenile Largemouth Bass , 2004, Environmental health perspectives.

[32]  M R Wiesner,et al.  Fullerol-sensitized production of reactive oxygen species in aqueous solution. , 2005, Environmental science & technology.

[33]  S. Chellam,et al.  Inactivation of bacteriophages via photosensitization of fullerol nanoparticles. , 2007, Environmental science & technology.

[34]  Mark R Wiesner,et al.  Antibacterial activity of fullerene water suspensions (nC60) is not due to ROS-mediated damage. , 2008, Nano letters.

[35]  D. Guldi,et al.  Activity of water-soluble fullerenes towards OH-radicals and molecular oxygen 1 1 Dedicated to Joe Silverman at the occasion of his 75th birthday. , 1999 .

[36]  Jeyong Yoon,et al.  Different Inactivation Behaviors of MS-2 Phage and Escherichia coli in TiO2 Photocatalytic Disinfection , 2005, Applied and Environmental Microbiology.

[37]  V. Rylkov,et al.  Photodynamic inactivation of influenza virus with fullerene C60 suspension in allantoic fluid. , 2007, Photodiagnosis and photodynamic therapy.

[38]  M. Elovitz,et al.  Hydroxyl Radical/Ozone Ratios During Ozonation Processes. I. The Rct Concept , 1999 .

[39]  E. Cabiscol,et al.  Oxidative stress in bacteria and protein damage by reactive oxygen species. , 2000, International microbiology : the official journal of the Spanish Society for Microbiology.

[40]  G. Bartosz Use of spectroscopic probes for detection of reactive oxygen species. , 2006, Clinica chimica acta; international journal of clinical chemistry.

[41]  Zoran Markovic,et al.  Distinct cytotoxic mechanisms of pristine versus hydroxylated fullerene. , 2006, Toxicological sciences : an official journal of the Society of Toxicology.

[42]  Y. Nosaka,et al.  Formation and Behavior of Singlet Molecular Oxygen in TiO2 Photocatalysis Studied by Detection of Near-Infrared Phosphorescence , 2007 .

[43]  Edward J. Wolfrum,et al.  Bactericidal Activity of Photocatalytic TiO2 Reaction: toward an Understanding of Its Killing Mechanism , 1999, Applied and Environmental Microbiology.

[44]  Delina Y Lyon,et al.  Bacterial cell association and antimicrobial activity of a C60 water suspension , 2005, Environmental toxicology and chemistry.

[45]  M. Okochi,et al.  TiO2-Mediated Photochemical Disinfection of Escherichia coli Using Optical Fibers. , 1995, Environmental science & technology.

[46]  J. Hoigne,et al.  Singlet oxygen in surface waters. 3. Photochemical formation and steady-state concentrations in various types of waters. , 1986, Environmental science & technology.

[47]  C. Brabec,et al.  Plastic Solar Cells , 2001 .

[48]  J. Hughes,et al.  Photochemical production of reactive oxygen species by C60 in the aqueous phase during UV irradiation. , 2007, Environmental science & technology.