Sulfidation of silver nanoparticles: natural antidote to their toxicity.

Nanomaterials are highly dynamic in biological and environmental media. A critical need for advancing environmental health and safety research for nanomaterials is to identify physical and chemical transformations that affect the nanomaterial properties and their toxicity. Silver nanoparticles, one of the most toxic and well-studied nanomaterials, readily react with sulfide to form Ag(0)/Ag2S core-shell particles.

Nanoparticle aggregation: challenges to understanding transport and reactivity in the environment.

Unique forms of manufactured nanomaterials, nanoparticles, and their suspensions are rapidly being created by manipulating properties such as shape, size, structure, and chemical composition and through incorporation of surface coatings. Although these properties make nanomaterial development interesting for new applications, they also challenge the ability of colloid science to understand nanoparticle aggregation in the environment and the subsequent effects on nanomaterial transport and reactivity. This review briefly covers aggregation theory focusing on Derjaguin-Landau-Verwey-Overbeak (DLVO)-based models most commonly used to describe the thermodynamic interactions between two particles in a suspension.

Environmental occurrences, behavior, fate, and ecological effects of nanomaterials: an introduction to the special series.

The release of engineered nanomaterials (ENMs) into the biosphere will increase as industries find new and useful ways to utilize these materials. Scientists and engineers are beginning to assess the material properties that determine the fate, transport, and effects of ENMs; however, the potential impacts of released ENMs on organisms, ecosystems, and human health remain largely unknown. This special collection of four review papers and four technical papers identifies many key and emerging knowledge gaps regarding the interactions between nanomaterials and ecosystems.

Theoretical framework for nanoparticle reactivity as a function of aggregation state.

Theory is developed that relates the reactivity of nanoparticles to the structure of aggregates they may form in suspensions. This theory is applied to consider the case of reactive oxygen species (ROS) generation by photosensitization of C(60) fullerenes. Variations in aggregate structure and size appear to account for an apparent paradox in ROS generation as calculated using values for the photochemical kinetics of fullerene (C(60)) and its hydroxylated derivative, fullerol (C(60)(OH)(22-24)) and assuming that structure varies between compact and fractal objects.

Mechanisms of bacteriophage inactivation via singlet oxygen generation in UV illuminated fullerol suspensions.

Nonenveloped viruses are shown to be inactivated by singlet oxygen ((1)O2) produced in UVA photosensitized aqueous suspensions of a polyhydroxylated fullerene (C60(OH)22-24; fullerol, 40 microM). Experiments were performed with MS2, a ssRNA bacteriophage, as well as two dsDNA phages: PRD1, which has an internal lipid membrane, and T7, which entirely lacks lipids. MS2 was highly susceptible to inactivation, having a rate constant of 0.

Comparative toxicity of C60 aggregates toward mammalian cells: role of tetrahydrofuran (THF) decomposition.

C60 fullerene is a promising material because of its unique physiochemical properties. However, previous studies have reported that colloidal aggregates of C60 (nC60) produce toxicity in fish and human cell cultures. The preparation method of nC60 raises questions as to whether the observed effects stem from fullerenes or from the organic solvents used during the preparation of the suspensions.

Evaluation of the oxidation of organic compounds by aqueous suspensions of photosensitized hydroxylated-C60 fullerene aggregates.

Ultraviolet (UV) irradiated polyhydroxylated fullerene (fullerol) nanomaterials are examined for their potential to degrade organic compounds via reactive oxygen species (ROS) mediated by a photosensitization process. Organic compounds were selected for their sensitivity to individual species of reactive oxygen (hydroxyl radical (*OH-) for degradation of salicylic acid (SA); singlet oxygen (1O2) for degradation of 2-chlorophenol (2CP), and superoxide (O2*-) for oxidation of ethanol) and were monitored over time in aqueous suspensions of fullerol aggregates. Only the 2CP showed significant degradation underscoring the specificity of the fullerol in producing singlet oxygen in these conditions.

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.

Mechanisms of photochemistry and reactive oxygen production by fullerene suspensions in water.

Buckminsterfullerene (C60) is a known photosensitizer that produces reactive oxygen species (ROS) in the presence of light; however, its properties in aqueous environments are still not well understood or modeled. In this study, production of both singlet oxygen and superoxide by UV photosensitization of colloidal aggregates of C60 in water was measured by two distinct methods: electron paramagnetic resonance (EPR) with a spin trapping compound, and spectrophotometric detection of the reduced form of the tetrazolium compound XTT. Both singlet oxygen and superoxide were generated by fullerol suspensions while neither was detected in the aqu/nC60 suspensions.

Transport and retention of colloidal aggregates of C60 in porous media: effects of organic macromolecules, ionic composition, and preparation method.

The physical-chemical behavior of the fullerene C60 in environmental and physiological media is of interest for understanding the potential transport, exposure, and impacts of these materials on organisms and ecosystems. We considerthe role of electrolyte composition and concentration, the effect of organic macromolecules, and the mode of preparation of colloidal aggregates of C60 (nC60) on the deposition of these colloids in a porous medium such as a groundwater aquifer or a water treatment filter. Results for nC60 deposition are qualitatively consistent with trends anticipated by theory.

Inactivation of bacteriophages via photosensitization of fullerol nanoparticles.

The production of two reactive oxygen species through UV photosensitization of polyhydroxylated fullerene (fullerol) is shown to enhance viral inactivation rates. The production of both singlet oxygen and superoxide by fullerol in the presence of UV light is confirmed via two unique methods: electron paramagnetic resonance and reduction of nitro blue tetrazolium. These findings build on previous results both in the area of fullerene photosensitization and in the area of fullerene impact on microfauna.